static.oxxy.com · 2 7th BLACK SEA BASIN CONFERENCE ON ANALYTICAL CHEMISTRY 10 15 SEPTEMBER 2015...

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7th BLACK SEA BASIN CONFERENCE ON ANALYTICAL CHEMISTRY

(7th BBCAC)

ABSTRACTS AND PROGRAMME

10 � 15 September 2015

Golden Sands, Varna, BULGARIA

bbcac2015.oxxy.com/conference

7th Black Sea Basin Conference on Analytical Chemistry, 10-15 September 2015, Golden Sands, Bulgaria


(7th BBCAC)

ABSTRACTS AND PROGRAMME

10 � 15 September 2015

Golden Sands, Varna, BULGARIA


http://bbcac2015.oxxy.com/conference

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10 � 15 SEPTEMBER 2015Golden Sands, Varna, BULGARIA


This conference continues the previous successful organized BBCAC conferences in Odessa (Ukraine), 2001; in Şile-Istanbul (Turkey), 2003; in Constanta (Romania), 2005; in Golden Sands (Bulgaria), 2007; in Fatsa (Turkey), 2009; in Trabzone (Turkey), 2013.

CONTINUATION COMMITTEE

Prof. Dr. Göksel AKÇIN, TurkeyProf. Dr. Şeref GÜÇER, TurkeyProf. Dr. Raluca MOCANU, RomaniaProf. Dr. Irina KARADJOVA, BulgariaProf. Dr. Alexander ZACHARIA, UkraineProf. Dr. Nur ONAR, TurkeyProf. Dr. Münevver SÖKMEN, TurkeyAssoc. Prof. Dr. Belgin IZGI, Turkey

The 7th BBCAC is organized by

University of Sofia � St. Kliment Ohridski� � Faculty of Chemistry and Pharmacy

Medical University � Prof. Dr. Paraskev Stoyanov� - VarnaInstitute of General and Inorganic Chemistry � Bulgarian Academy of

SciencesUniversity of Plovdiv � Paisii Hilendarski� � Faculty of Chemistry

The Organizing Committee is grateful toÿ Prof. Dimiter TSALEV (University of Sofia), Bulgariaÿ Prof. Sonja ARPADJAN-GANEVA (University of Sofia), Bulgariaÿ Assoc. Prof. Albena DETCHEVA (Bulgarian Academy of Sciences),

Bulgariaÿ Prof. Dr. Irina KARADJOVA (University of Sofia), Bulgaria

for the abstracts review process.


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INTERNATIONAL SCIENTIFIC COMMITTEE

Prof. Dimiter TSALEV (University of Sofia), BulgariaProf. Sonja ARPADJAN-GANEVA (University of Sofia), BulgariaProf. Krasimir IVANOV (Medical University � Varna), BulgariaProf. Mona STANCHEVA (Medical University � Varna), BulgariaAssoc. Prof. Violeta STEFANOVA (University of Plovdiv), BulgariaProf. Elissaveta IVANOVA (Bulgarian Academy of Sciences), BulgariaProf. Şeref GÜÇER (Uludağ University), TurkeyProf. Trajce STAFILOV (Sts. Cyril and Methodius University), Republic of MacedoniaProf. Alexander ZACHARIA (Odessa National University), UkraineMikhail BOLSHOV (Academy of Science), RussiaDuka GEORGY (Academy of Sciences), MoldovaVictoria SAMANIDOU (University of Tessaloniki), GreeceDavid TAVKHVELADZE (Georgian Technical. University), Georgia

NATIONAL ORGANIZING COMMITTEE

Prof. Irina KARADJOVA (co-chair), University of SofiaAssoc. Prof. Lubomir MACEDONSKI (co-chair), Medical University � VarnaAssoc. Prof. Veselin KMETOV, University of PlovdivAssoc. Prof. Albena DETCHEVA, Bulgarian Academy of SciencesAssoc. Prof. Ivanka DAKOVA, University of SofiaAssoc. Prof. Galina GENCHEVA, University of SofiaChief Assist. Prof. Elisaveta MLADENOVA, University of SofiaAssist. Katja PEJTCHEVA, Medical University � Varna

7th BBCAC co-chair

Prof. Dr. Irina Karadjova (co-chair)Faculty of Chemistry and Pharmacy, University of Sofia, 1 James Bourchier Blvd., Sofia 1164, BULGARIA, e-mail: [email protected], Tel. +359 2 8161356, fax +359 2 9625438

Assoc. Prof. Dr. Lubomir Macedonski (co-chair)Faculty of Pharmacy, Medical University � Prof. Dr. Paraskev Stoyanov� �Varna, 55 Marin Drinov Str., 9002 Varna, BULGARIA, e-mail: [email protected], Tel. +359 52 677 074


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Thursday10th Sept.

14:00� 19:00 Registration 19:30 � 20:00 Opening ceremony� Animation� Hall

20:00 −22:00

Dinner

Friday

11th Sept.

8:30� 15:00 Registration

9:00 � 9:30 IL19:40 � 10:10 IL2

10:20 � 10:50 Coffee

10:50 � 11:05 O111:10 � 11:25 O211:30 � 11:45 O311:50 � 12:05 Exhibition 112:10 � 12:25 Exhibition 2

12:35� 14:00 Lunch

17:00 � 19:00

Poster session 1

(P1 � P46)

20:00 �22:00Dinner

Sat

12st Sept.

9:00 � 9:30 IL39:40 � 10:10 IL4

10:20 � 10:50 Coffee

10:50 � 11:05 O411:10 � 11:25 O511:30 � 11:45 O611:50 � 12:05 O712:10 � 12:25 O8

12:30 � 14:00 Lunch

17:00 � 19:00

Poster session 2

(P47 � P88)

20:00 �22:00Dinner


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Sun

13th Sept.

9:00 � 9:30 IL59:40 � 10:10 IL6

10:20 � 10:50 Coffee

10:50 � 11:05 O911:10 � 11:25 O1011:30 � 11:45 O1111:50 � 12:05 O12

12:30 � 14:00 Lunch

14:00 � 19:00

Excursion to Balchik and Kaliakra

20:00 �22:00Dinner

Monday

14th Sept.

9:30 � 10:00 IL7 10:10 � 10:25 O13

10:30 � 11:00 Coffee

11:00 � 11:15 O1411:20 � 11:35 O15

12:30� 14:00 Lunch

14:00 �

(optional)trip to Varna

20:00 �24:00OfficialConferenceDinner

Thuesday

15th Sept.

9:45 � 10:30 IL8

Closing

12:30 � 14:00 Lunch

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7th BBCAC Programme (Preliminary)

Thursday, 10th Sept. 2015

14:00 � 19:00 Registration

19:30 � 20:00 Opening ceremony � � Animation� Hall

20:00 � 22:00 Diner

Friday, 11th Sept. 2015

8:30 � 15:00 Registration

9:00 � 10:20 Oral session 1, Chairmen: Şeref Güçer

9:00 � 9:30 IL1 Münevver Sökmen (Turkey)� Nanoparticles for water remediation�9:40 � 10:10 IL2 Mustafa Soylak (Turkey)� Nanosized materials for solid phase extraction and solid phase microextraction of trace metals�

10:20 � 10:50 Coffee

10:50 � 12:30 Oral session 2, Chairmen: Alexander N. Zacharia

10:50 � 11:05 O1 Habib Razmi (Iran)� Graphene oxide/eggshell membrane nanosorbent: Preparation and application to the removal of heavy metals from water samples�11:10 � 11:25 O2 Hossein Abdolmohammad-Zadeh, Elaheh Rahimpour (Iran)� An ultrasound-assisted approach for grafting of cobalt ferrite nano-particles with oxine in the presence of sodium dodecyl sulfate for separation and direct determination of Al(III) ion�11:30 � 11:45 O3 Tülin Aydemir, Günay İrem Altındağ (Turkey)� The use of macromolecular material chitosan for enzymes immobilization�11:50 � 12:05 Exhibition 1 � Chroma12:10 � 12:25 Exhibition 2 � ACM2

12:35 � 14:00 Lunch17:00 � 19:00 Poster session 1 (P1 � P46)20:00 � 22:00 Dinner


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Saturday, 12th Sept. 2015

9:00 � 10:20 Oral session 3, Chairmen: Münevver Sökmen

9:00 � 9:30 IL3 Hana Dočekalová (Czech Republik)� Prediction of bioavailabilty of metals in aquatic systems: comparison between Diffusive gradient in thin films technique and living organisms�

9:40 � 10:10 IL4 Alexander N. Zacharia, Mikhail Arabadji, Alexander Chebotarev (Ukraine)� Graphite filter furnace atomizer as effective tool for direct atomic absorption analysis of some biological materials �

10:20 � 10:50 Coffee

10:50 � 12:30 Oral session 4, Chairmen: Kiril Simitchiev

10:50 � 11:05 O4 Nil Ozbek, Mustafa Ozcan (Turkey)� Simultaneous determination of Co, Al and Fe by HR-CS-GFAAS�11:10 � 11:25 O5 Aslı Baysal, Nil Ozbek, Suleyman Ince, Ersin Kılıç, Suleyman Akman (Turkey)� Determination of sulfur in human hair using HR-CS-GFAAS and correlation with total protein, albumin and thiol related compounds�11:30 � 11:45 O6 Umran Seven Erdemir (Turkey)� Assessment of multielement bioavailabilities in tea (Camellia sinensis L.) samples consumed in Turkey�11:50 � 12:05 O7 Mehmet Akyüz, Şevket Ata, Berrin Gürler (Turkey)� Distributions of nitrosamines in gastric juices of gastrointestinal patient�12:10 � 12:25 O8 Mehmet Yaman (Turkey)� ICP-AES determination of nickel and chromium in eggplant and soil samples�

12:30 � 14:00 Lunch

17:00 � 19:00 Poster session 2 (P47 � P88)

20:00 � 22:00 Dinner


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Sunday, 13th Sept. 2015

9:00 � 10:20 Oral session 5, Chairmen: Hana Dočekalová

9:00 � 9:30 IL5 Spas Kolev (Australia)� Environmental monitoring and analysis on a paper-based platform�

9:40 � 10:10 IL6 Şeref Güçer (Turkey)� Analytical chemistry, innovation and economic development�

10:20 � 10:50 Coffee

10:50 � 12:30 Oral session 6, Chairmen: Petya Kovacheva

10:50 � 11:05 O9 Mihai Branzei, Ion Pencea, Catalin Eugen Sfat, Alecs Andrei Matei, Ramona-Nicoleta Turcu, Mihai Cojocaru (Romania)� Combined ED(P)-XRFS and WAXD analysis of the metallurgical wastes�11:10 � 11:25 O10 Kiril Simitchiev, Violeta Stefanova, Veselin Kmetov, Vanya Zapryanova, Mariya Petleshkova, Kiril Gavazov, Teodora Stefanova, Antonio Canals(Bulgaria)� Cloud Point Extraction � fundamentals and applicability with different techniques for instrumental analysis�11:30 � 11:45 O11 Secil Candir, Ibrahim Narin (Turkey)� A Novel cloudpoint extraction procedure for speciation of chromium�11:50 � 12:05 O12 Makhan Lal, Anil Duhan (India)� Simultaneous analysis of Carbendazim, Flusilazole and Streptocycline used for post-harvest storage of onions by matrix solid phase extraction and liquid-liquid extraction followed by HPLC-UV detection�

12:30 � 14:00 Lunch

14:00 � 19:00 Excursion to Balchik and Kaliakra

20:00 � 22:00 Dinner


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Monday, 14th Sept. 2015

9:30� 10:40 Oral session 7, Chairmen: O. Yavuz Ataman

9:30 � 10:00 IL7 Vera I Slaveykova (Switzerland)� Trace metal bioavailability � a key player in surface water quality assessment�

10:10 � 10:25 O13 Onur Şenol, Yücel Kadioğlu, Reşat Apak (Turkey)� Determination of in-vitro antioxidant capacity of cardiovascular drugs�

10:30 � 11:00 Coffee

11:00 � 11:40 Oral session 8, Chairmen: Elisaveta Mladenova

11:00 � 11:15 O14 Chinar M. Rashid, Nabil A. Fakhre, Umi K. Ahmed (Iraq)� Derivative Spectroscopic Determination of Enrofloxacin in Some Natural Samples�11:20 � 11:35 O15 Mahmood Ali Hasan, Thabit S. Al-Ghabsha (Iraq)� Spectrophotometric determination of catecholamines (levodopa, methyldopa, dopamine and adrenaline) depending on the charge transfer complex formation reaction with TCNQ in both aqueous and ethanolic solutions�

12:30 � 14:00 Lunch14:00 � trip to Varna, optional20:00 � 22:00 Official Conference Dinner

Thusday, 15th Sept. 2015

9:45 � 10:30 IL8 O. Yavuz Ataman (Turkey)� Tungsten coil traps meet ICPMS and a short review of BBCAC history�

Closing

12:30 � 14:00 Lunch


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IL1Nanoparticles for water remediation

Münevver Sökmen

Karadeniz Technical University, Faculty of Science, Department of Chemistry, 61080 Trabzon, Turkey

[email protected]

Nanomaterials offer the potential for the efficient removal of various pollutants and biological contaminants in the area of environmental remediation. Nanomaterials may be in various shapes/morphologies. Nanoparticles, nanotubes, nanowires, nanorods, nanofibres or nanocomposites (combination of nanoparticles with polymers) etc. are used as adsorbent or catalysts in many applications. Nanomaterials are produced for the:

∑ detection and removal of gases (SO2, CO, NOx,etc.);∑ contaminated chemicals (arsenic, iron, manganese, nitrate, heavy metals,etc.);∑ organic pollutants (aliphatic and aromatic hydrocarbons);∑ biological substances, such as viruses, bacteria, parasites and antibiotics.

Due to their very low size nanomaterials show a better performance in environmental remediation than other conventional techniques. More smaller size means larger surface area and higher surface-to-volume ratio. These two parameters are important for both adsorption and catalytic behaviour. The current studies and research trends for future prospects will be discussed in details. Specific applications of TiO2 photocatalyst for water remediation will be summarized.


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IL1Nanoparticles for water remediation

Münevver Sökmen

Notes:........................� � � � � � � � � � � � � � � � � � � � � � � � � � � � �...� � � � ......� � � � � � � � � � � � � � � � � � � � � � � � � � 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IL2Nanosized materials for solid phase extraction and solid phase

microextraction of trace metals

Mustafa Soylak

Erciyes University, Faculty of Sciences, Chemistry Department, 38039, Kayseri, Turkey

[email protected]

Nowadays, the preparation of novel nanosized material which has resistant for acid and bases; high surface area, high adsoption capacity, usable many times without any losses its adsorption properties are very popular part of analytical chemistry. Carbon nanotubes (CNTs), modified carbon nanotubes (m-CNTs), nanocomposittes, titanium dioxide nanoparticles (nano-TiO2), and magnetic nanoparticles (MNPs), nanoflowers etc. have been used for the solid phase extraction, solid phase microextraction and speciation of trace metal ions.

Preparation, characterization and usage of novel nanosized materials for solid phase extraction and solid phase microextraction of trace metal ions from environmental samples have been discussed in this presentation.

AcknowledgementThe author is grateful for the financial support of the Unit of the Scientific Research Project of Erciyes University (Project no: FDK-2014-4991).


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IL2Nanosized materials for solid phase extraction and solid phase

microextraction of trace metals

Mustafa Soylak

Notes:........................� � � � � � � � � � � � � � � � � � � � � � � � � � � � �...� � � � ......� � � � � � � � � � � � � � � � � � � � � � � � � � 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IL3Prediction of bioavailabilty of metals in aquatic systems:

comparison between Diffusive gradient in thin films technique and living organisms

Hana Dočekalová

Department of Chemistry and Biochemistry, Faculty of Agronomy, Mendel University in Brno, Zemědělská 1/1665, CZ-61300 Brno, Czech Republic

[email protected]

Metal bioavailability and bioaccessibility in the environment are critical to the risk of assessment process. There is, therefore, great interest in finding efficient environmental monitoring methods for their determination. Analytical testing of chemical pollutants based on various separation and leaching procedures provides a simple classification of water, soil and sediment metal fractions, but these are based on arbitrary responses to chemical reagents and do not provide information on the potential impact of pollution on the resident organisms. Therefore, there is a need for a simple procedure which reliably estimates metals accessibilityand predicts the uptake of toxic metals by plants and animals. There is, thus, an ever increasing interest in using biomonitoring methods such as analysis of organisms that are bioaccumulators. However, it is not generally assumed that different organisms transport metals by the same mechanisms and the transport is affected by external environmental conditions. A lack of understanding of the basic physiological, biochemical, and molecular mechanisms prevents the correct evaluation of their influence on metal transport to living organisms. Therefore, new approaches are still being sought to obtain a better characterization of bioaccessible forms of metals and their transport to the living specimens. An in situ technique known as Diffusive gradient in thin films technique (DGT) capable of quantitative measurement of labile metal species in aqueous systems has been developed. This technique working on the principle of Fick´s 1st law of diffusion is based on a simple tight-fitting piston designed assembly that accumulates metal ions on a selective binding cation-exchange resin, immobilized in thin layer of hydrogel, after passage through a well-defined diffusion layer.

The lecture presents some of our results focused on the relationship between concentrations of metals measured by DGT and their elevated levels in aquatic moss (Frontinalis antipyretica), terrestrial plants (Raphanus sativus, Taraxacum officinale) and fish (Cyprinus carpio L.). Our results demonstrate that DGT predicts metal uptake by living organisms and can be used as physical surrogates for plant and fish metal uptake. Thus, DGT offers the possibility of a simple test procedure for metal bioavailability assessment.


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IL3Prediction of bioavailabilty of metals in aquatic systems:

comparison between Diffusive gradient in thin films technique and living organisms

Hana Dočekalová

Notes:........................� � � � � � � � � � � � � � � � � � � � � � � � � � � � �...� � � � ......� � � � � � � � � � � � � � � � � � � � � � � � � � 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IL4Graphite filter furnace atomizer as effective tool for direct atomic

absorption analysis of some biological materials

Alexander Zacharia, Mikhail Arabadji, Alexander Chebotarev

I.I. Mechnikov Odessa National University, Department of Analytical Chemistry, Dvoryanskaya Str., 2,65082 Odessa, Ukraine

[email protected]

It is well known that electrothermal atomic absorption spectrophotometry (ETAAS) are widely used for the determination of the total trace elements concentration in various biological samples. However, at these several drawbacks, especially its macro components interference effect on the atomic absorption value of the elements to be determined, as well as non-specific absorbance of light, must be taken into account. In recent years not only Stabilized Temperature Platform Furnace (STPF) technique for elimination of a number of interferences, but graphite filter furnace (FF) atomizer has been shown to be a very powerful tool for quantitation of Pb, Cd and Cu in organic-based materials. Unfortunately, in analytical practice of toxicological, medical and other corresponding laboratories for ETAAS analysis of serum, whole blood, urine and other biologicals this device are not practically used.

The goal of this work has been to develop a procedure for the direct ETAAS determination of Pb, Cd, Mn, Cu, Zn and Se in some of biological materials using graphite filter furnace (FF) atomizer.

In operation parameters of program heating FF atomizer there was established the detection limit, interference effect from mineral and organic components of biological materials and corresponding background signal, including evaporation in the presence of some chemical modifiers (CM).

The graphite FF atomizer with CM is an effective application for the direct ETAAS determination of Pb, Cd, Mn, Cu, Zn and Se in blood, urine and saliva samples. This method can be used instead of other methods that require laborious and time-consuming procedure of sample preparation.

The FF atomizer provide ~ 2 − 2.5 fold increasing in sensitivity for the ETAAS determination of listed elements in comparison with a graphite platform as well as significant removal of some interference effects including background absorption.The proposed method can be used for the determination of ≥ 0.0015, 0.0002, 0.0003, 0.0008, 0.0002 and 0.0020 ppm of Pb, Cd, Mn, Cu, Zn and Se, respectively, in blood, urine and saliva.

It was established that concentrations of listed elements in analyzed biological fluids varied between 0.00025 and 0.075 µg·g-1. The results prove that the determined concentration of Pb, Cd, Mn, Cu, Zn and Se in these biologicals are in accordance with the reference valuesin literature. The time of one element determination does not exceed 7 min with Sr 6 %.


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IL4Graphite filter furnace atomizer as effective tool for direct atomic

absorption analysis of some biological materials

Alexander Zacharia, Mikhail Arabadji, Alexander Chebotarev

Notes:........................� � � � � � � � � � � � � � � � � � � � � � � � � � � � �...� � � � ......� � � � � � � � � � � � � � � � � � � � � � � � � � 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IL5Environmental monitoring and analysis on a paper-based

platform

Spas D. Kolev

School of Chemistry, The University of Melbourne, Victoria 3010, Australia

[email protected]

Microfluidic paper-based analytical devices ( PADs) have gained considerable popularity in recent years as a new type of disposable analytical sensing devices which meet the increasing needs of rapid, accurate and low-cost monitoring and analysis for environmental protection and healthcare. They utilize the capabilities of cellulose fibres in paper, which form a hydrophilic porous matrix, to transport liquids by capillary force only.

The present paper describes the development and application of PADs for environmental monitoring of nutrients such as phosphate, nitrite, nitrate and ammonia, and toxic heavy metal ions such as copper(II). The hydrophilic liquid penetration channels and detection zones in these devices were ink-jet printed using the sizing agent alkyl ketene dimer (AKD). Analytical colour reactions were utilized for analyte detection with the colour intensity being measured by a conventional flatbed scanner. On-line sample pre-treatment steps such as reduction of nitrate to nitrite, membrane-based gas-diffusion separation of ammonia and selective extraction of copper(II) into a polymer inclusion membrane, incorporating the colour reagent 1-(2� -pyridylazo)-2-naphthol (PAN), have been successfully implemented for the first time on a paper-based platform thus further expanding the analytical capabilities of this approach. The proposed PADs were successfully applied to natural samples and very good agreement with the corresponding reference methods was observed.

AcknowledgementThe author is grateful for financial support of Projects DP1094179 and LP110200595 of the Australian Research Council.


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IL5Environmental monitoring and analysis on a paper-based

platform

Spas D. Kolev

Notes:........................� � � � � � � � � � � � � � � � � � � � � � � � � � � � �...� � � � ......� � � � � � � � � � � � � � � � � � � � � � � � � � 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IL6Analytical chemistry, innovation and economic development

Şeref Güçer

Emeritus professor in Uludag University, Faculty of Science & Arts, Department of Chemistry,16059 Görükle, Bursa, Turkey

[email protected]

The modern definition of Analytical chemistry is redefined by Valcercel and outlined as an information science and include such keywords as � metrology� , � quality� , � process� and � problem� [1.] Now days, information is accepted as driving force of society, economy and science and technology. Technological innovation that we used in our work is the process through which new or improved technologies are developed and brought into widespread use. It is now well understood that countries effort to increase or sustain their economic welfare, is bound to produce world-class technology. In order to actualize this vision, new products and services which fulfill the wishes of society, are needed.

The International Union of Pure and Applied Chemistry (IUPAC) considered ways in which it could foster opportunities for international cooperation. The result was the establishment of Chemical Research Applied to World Needs (CHEMRAWN) as a mechanism through which member nations of IUPAC could aid in identifying and solving important chemistry problems that have a direct impact on world needs [2].

UNESCO� s Natural Sciences Sector implements major international science programmes aimed at promoting and supporting sustainable development in all its Member States [3].

Many of the concepts of analytical chemistry: methods (general aspects, separations, spectrochemical, electrochemical, nuclear chemical) and applications (particularly to environmental and human health problems) are now find applications in quality standards such as EFQM, ISO EN 17025, 17020 etc. In a problem solving, the keypoint is to find proper analytical parameters which is than related instrumental method of analysis. The essential first step in any quantitative analysis is the selection of method. The choice is sometimes difficult and requires experience in the level of accuracy. The selected usually method represents a compromise between the accuracy, time and money available for the analysis. Finally, the complexity of the samples and the number of its components always influence the choice of instrumental methods.

In our presentation, the role of Analytical chemistry which is frequently applied in chemical Industry and triple helix model for technological innovation and its impact to economy were discussed.Reference[1] M.Valcercel, Trend Anal.Chem., 16 (1997)124.[2] Chemical Research Applied to World Needs (CHEMRAWN) (2010) http://www.iupac.org/web/ins/021 (accessed 6 January 2011).


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[3] UNESCO Natural Sciences Sector (2010) Science for Sustainable Development, UNESCO, Paris, http://www.unesco.org/science/psd/publications/rep_usa_eur_05.shtml (accessed 6 January 2011).

Notes:........................� � � � � � � � � � � � � � � � � � � � � � � � � � � � �...� � � � ......� � � � � � � � � � � � � � � � � � � � � � � � � � 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IL7Trace metal bioavailability � a key player in surface water quality

assessment

Vera I. Slaveykova

Institute Forel, School of Earth and Environmental Science,Faculty of Science, University of Geneva, Switzerland

[email protected]

The bioavailability, defined as � the extent of absorption of a substance by a living organism compared to a standard system� is considered as a key concept allowing to quantitatively link the changes in the trace metal concentrations and speciation with the intensity of the biological effects that they induced to aquatic organisms. In the current presentation, the concept of bioavailability will be introduced and different issues related to its application to assess the impact of metals in aquatic systems will be critically examined.

Special attention will be paid on the biotic ligand model (BLM) which gained recently widespread acceptance in the scientific and regulatory community. The capabilities of the BLM as a tool to integrate chemical speciation, bioavailability and effect of metals in the risk assessment will be illustrated with case study of the priority pollutants Cd and Pb and their effects to aquatic microorganisms. The results will be discussed with respect to the possible applications of the BLM as an alternative of the chemical and toxicological experimentation for the establishment of the site-specific water quality criteria of trace metals.

The existing challenges and concerns about the BLM application in more complex environmental settings including the role of dissolved organic carbon, temporal and spatial dynamics of trace metals, multiple metal interactions, as well as the tolerance to metal toxicity observed for aquatic microorganisms living in areas with elevated metal concentrations will be considered.

AcknowledgementThis work is supported by the Swiss National Science Foundation.


23

IL7Trace metal bioavailability � a key player in surface water quality

assessment

Vera I. Slaveykova

Notes:........................� � � � � � � � � � � � � � � � � � � � � � � � � � � � �...� � � � ......� � � � � � � � � � � � � � � � � � � � � � � � � � ........................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................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24

IL8Tungsten coil traps meet ICPMS and

a short review of BBCAC history

O. Yavuz Ataman*, Selin Bora, Gülay Ertaş, Anılcan Yılmaz

Department of Chemistry, Middle East Technical University, 06800 Ankara, Turkey

*[email protected]

In atomic spectrometry, atom traps using flame heated slotted quartz tube atomizer, quartz or tungsten coil based devices to trap analyte hydrides followed by detection using atomic absorption or fluorescence spectrometry have been developed and used. This study includes the presentation of data where tungsten coil traps are used in conjunction with inductively coupled plasma mass spectrometry (ICPMS).

For hydride generation (HG), a flow system was used. Sample was in 1.0 M HCl and reductant was 0.50% (w/v) NabH4 stabilized in 0.2% (w/v) NaOH. The volatile analyte species were transported from a U-type gas-liquid separator (GLS) to plasma using Ar carrier gas with 1.2 L/min flow rate. HG system was connected directly to inlet of torch without any spray chamber and nebulizer system. W-trap was located between the plasma inlet and the GLS outlet. In order to protect W-trap against oxidation, 106 mL/min H2 was passed through the atom trap. Presence of hydrogen both due to the mentioned gas flow and gas formation during HG causes ICP to go off. In order to prevent this effect, a make-up Ar flow of 125 mL/min was introduced after the W-trap and before the entrance to ICP. The analyte in solution is converted to its hydride which is then directed to W-coil heated at an optimized temperature; this step is called collection. Following this step, the W-coil atom trap is heated to a higher temperature causing analyte vapours to be transported into ICP where detection takes place in revolatilization step. The signal is a transient with a half width less than 0.5 s.

Sensitivities using nebulization, HG and W-coil trap-HG were compared for Bi and Te determination by ICPMS. When slopes of calibration plots are considered, as compared to nebulization, W-trap-HG signals were 125 and 106 times more sensitive for Bi and Te, respectively. For 1.0 min collection period, LOD values were found to be 2.4 ng/L for Bi and 6.0 ng/L for Te. Simultaneous detection of these two analytes was also possible.

Regarding the history of BBCAC (Black Sea Basin Conference on Analytical Chemistry) we are to recall the first event in Odessa, Ukraine in September 2001. Professor Alexander Zacharia initiated the event that will become later a series of scientific meetings in several countries on Black Sea. Locations, dates, pictures and some anecdotes will be presented.


25

IL8Tungsten coil traps meet ICPMS and

a short review of BBCAC history

O. Yavuz Ataman*, Selin Bora, Gülay Ertaş, Anılcan Yılmaz

Notes: ........................� � � � � � � � � � � � � � � � � � � � � � � � � � � � � ........� � � � ......� � � � � � � � � � � � � � � � � � � � � � � � � � ...........................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................


26

O1Graphene oxide/eggshell membrane nanosorbent: Preparation and application to removal of heavy metals from water samples

Habib Razmi

Electroanalytical Chemistry Research Lab., Faculty of Basic Science, Azarbaijan Shahid Madani University, P.O. Box: 53714-161, Tabriz, Iran s-1

[email protected] [email protected]

In this study, graphene oxide doped eggshell membrane (GO/ESM) powder was used as a new adsorbent to remove heavy metal ions from drinking water samples. The efficiency of GO/ESM for removing Hg(II) and Pb(II) from drinking water samples was examined by anodic stripping voltammetry. Adsorption characteristics of these metal ions were studied and it was found to be well fitted by Langmuir binding isotherm.

Graphene oxide nano-sheets immobilized on the eggshell membrane provide high surface to volume ratio increasing the adsorption efficiency of the ESM biopolymer. According to the adsorption isotherms examined, adsorptive capacities of GO/ESM were calculated as 54.83 and 25.13 mg g-1 for Hg(II) and Pb(II), respectively.

AcknowledgementThe author is grateful for financial support of Project by Azarbaijan Shahid Madani University.


27

O1Graphene oxide/eggshell membrane nanosorbent: Preparation and application to removal of heavy metals from water samples

Habib Razmi

Notes:........................� � � � � � � � � � � � � � � � � � � � � � � � � � � � �...� � � � ......� � � � � � � � � � � � � � � � � � � � � � � � � � ........................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................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28

O2An ultrasound-assisted approach for grafting of cobalt ferrite nano-particles with oxine in the presence of sodium dodecyl sulfate for separation and direct determination of Al(III) ion

Hossein Abdolmohammad-Zadeh, Elaheh Rahimpour

Department of Chemistry, Faculty of Sciences, Azarbaijan Shahid Madani University,35 Km Tabriz-Marageh Road, P.O. Box 53714-161, Tabriz, Iran


A simple dispersive solid-phase micro-extraction method based on CoFe2O4 nano-particles (NPs) functionalized with oxine (8-hydroxyquinoline (8-HQ)) with the aid of sodium dodecyl sulfate (SDS) was developed for separation of Al(III) ions from aqueous solutions. Al(III) ions are separated at pH 7 via complex formation with 8-HQ using the functionalized CoFe2O4 nano-particles sol solution as a dispersed solid-phase extractor. The separated analyte is directly quantified by a spectrofluorometric method at 370 nm excitation and 506 nm emission wavelengths. A comparison of the fluorescence of Al(III)� 8-HQ complex in bulk solution with that of Al(III) ion interacted with 8-HQ/SDS/CoFe2O4 NPs revealed a nearly 5-fold improvement in intensity. The experimental factors influencing the separation and in situ monitoring of the analyte were optimized. Under these conditions, the calibration graph was linear in the range of 0.1−300 ng mL−1 with a correlation coefficient of 0.9986. The limit of detection and limit of quantification were 0.03 ng mL� 1 and 0.10 ng mL� 1 , respectively. The inter-day and intra-day relative standard deviations for six replicate determinations of 150 ng mL� 1 Al(III) ion were 2.8 % and 1.7 %, respectively. The method was successfully applied to direct determine Al(III) ion in various human serum and water samples.

AcknowledgementThe financial support from the Research Council of Azarbaijan Shahid Madani University (ASMU, Iran (Grant no. 10799)) is gratefully acknowledged.


29

O2An ultrasound-assisted approach for grafting of cobalt ferrite nano-particles with oxine in the presence of sodium dodecyl sulfate for separation and direct determination of Al(III) ion

Hossein Abdolmohammad-Zadeh, Elaheh Rahimpour

Notes:........................� � � � � � � � � � � � � � � � � � � � � � � � � � � � �...� � � � ......� � � � � � � � � � � � � � � � � � � � � � � � � � ..........................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................


30

O3The use of macromolecular material chitosan for enzymes

immobilization

Tülin Aydemir*, Günay İrem Altındağ

Celal Bayar University, Science and Arts Faculty, Chemistry Department, Muradiye, Manisa, Turkey

*[email protected]

Chitosan, a deacetylated derivative of chitin, is a natural polymeric biomaterial, low toxic, biodegradable and biocompatible. Based on its many favourable characteristics, chitosan has attracted considerable attention in the areas such as biotechnology, biomedicine, food and cosmetics. Recently, there has been a growing interest in chemical or physical modification of chitosan to improve its solubility and widen its environmental and biomedical applications. The renewable biopolimer chitosan is known as an ideal support material for enzyme immobilization. Enzymes are often immobilized onto or into solid supports to increase their thermostability, operational stability and recover.

In the present study, chitosan was modified with multi-walled carbon nanotubes (MWCNTs), and laccase was immobilized covalently on MWCNTs-Chitosan beads by using glutaraldehyde as a cross-linking agent. The morphological properties of the MWCNTs-Chitosan composite were studied with scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), and thermal gravimetric analysis (TGA). The morphological results indicate the successful modification and the formation of MWCNTs-Chitosan composites. The yield of the immobilization and enzyme activity was found to be 63% and 3.51 U/gr carrier at pH 5.0 and 30°C. Improved pH, thermal and storage stabilities of the immobilized laccase were obtained, compared to the free counterpart. Immobilized laccase could be reused for 10 consecutive cycles retaining 65% of its initial activity. The results show that prepared MWCNTs� Chitosan composites are biocompatible and possess high enzyme immobilization efficiency, favoring potential application as protein carrier systems. Application of the immobilized system for the removal of textile dye Crystal Violet was investigated in a batch system and decolorization values of about 60% were obtained after 5 h.


31

O3The use of macromolecular material chitosan for enzymes

immobilization

Tülin Aydemir, Günay İrem Altındağ

Notes:........................� � � � � � � � � � � � � � � � � � � � � � � � � � � � �...� � � � ......� � � � � � � � � � � � � � � � � � � � � � � � � � ........................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................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32

O4Simultaneous determination of Co, Al and Fe by HR-CS-GFAAS

Nil Ozbek*, Mustafa Ozcan

Istanbul Technical University, Faculty of Science and Letters, Chemistry Department,34469 Maslak, Istanbul, Turkey

*[email protected]

In the past, classical atomic absorption spectrometers were line sourced and only capable of single element determination at each run. The single element nature and sample analysis time were the biggest disadvantages of AAS. In order to avoid them, there was continuous interest in the development of a multi-element AAS instrument that would increase the analytical rate but would have the excellent sensitivities and detection limits of single element AAS.

High resolution continuum source atomic absorption spectrometers bring many advantages like multi element determination in a one run, monitoring several lines of the same element or use of internal standard in trace element analysis. However, the HR CS AAS, which allows simultaneous multi element determination, has some limitations. First, the atomic lines of target elements must be close to each other, i.e. in the same spectral window, then the concentrations of the target elements must be in the linearity range for selected wavelengths and finally the thermal behavior of the elements should be similar (like atomization and pyrolysis temperatures etc.).

In this study, simultaneous determination of Al, Co and Fe by high resolution continuum source graphite furnace atomic absorption spectrometer (HR-CS GFAAS) wasperformed satisfactorily. For this purpose, the spectral area between 237.148 and 237.403 was monitored and Al, Co and Fe absorbances were detected at absorption lines at 237.312 nm, 237.185+237.283+237.386 nm and 237.362 nm, respectively. The characteristic concentrations and LOD values for the working wavelengths of Al, Co and Fe were 0.00573, 0.048, 0.054 mg L-1 and 0.014, 0.012, 0.011 mg L-1, respectively. The linear working ranges were spread over LOQ-2.5, LOQ-10 and LOQ-10 mg L-1 for Al, Co and Fe, respectively. At the end, Al, Co and Fe in several certificated reference materials and waste water samples were determined satisfactorily by HR-CS GFAAS. With the proposed method a fast and straightforward simultaneous determination by HR CS AAS for the above mentioned elements is possible.


33

O4Simultaneous determination of Co, Al and Fe by HR-CS-GFAAS

Nil Ozbek, Mustafa Ozcan

Notes:........................� � � � � � � � � � � � � � � � � � � � � � � � � � � � �...� � � � ......� � � � � � � � � � � � � � � � � � � � � � � � � � ........................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................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34

O5Determination of sulfur in human hair using HR-CS GFAAS and

correlation with total protein, albumin and thiol related compounds

Asli Baysal1*, Nil Ozbek2, Suleyman Ince1, Ersin Kılıç1, Suleyman Akman2

1T.C. Istanbul Aydin University, Health Services Vocational School of Higher Education,34295 Sefakoy Kucukcekmece, Istanbul, Turkey

2Istanbul Technical University, Faculty of Science and Letters, Department of Chemistry,34469 Maslak, İstanbul, Turkey

*[email protected]

Human hair can be effectively used for biological monitoring as well as for the investigation of the effects of environmental, nutritional or occupational sources on the body. Human proteins, amino acids, sulfur related compounds are mostly the key components to find source, relation of the different effects or disorders in the human body. Sulfur has great affinity to some metals and compounds, besides that these affinity affect the humans positively or negatively [1-4].

In this work, sulfur was determined in human hair samples via molecular absorption of CS using a high-resolution continuum source electrothermal atomic absorption spectrometry. For these purpose, hair samples were washed once with acetone; triple with distilled-deionized water and again once with acetone and dried at 75°C and then samples were dissolved in microwave digestion using HCland extracted with HCl hydrolysation using 12 hrs at 110oC incubation[5,6]. The sample preparation method and the validity of the method for the analytes were tested using standard reference material. The results were in the uncertainty limits of the certified values at 95% confidence level.

Most of the autistic children have high heavy metal concentrations, these heavy metals are thiol related metals. Thiol groups in human body are existed in amino acid or protein based molecules. To investigate of relation between high heavy metal concentration and main biological unit (amino acid, protein) in autistic disorder patients, the sulfur concentrations and total protein, albumin and thiol related compounds in hair samples obtained from were healthy children and having autism disorder children were compared.

References[1] A. Baysal, S. Akman, Spectrochimica Acta Part B 65, 340� 344 (2010)[2] A. Baysal, S. Akman, Microchemical Journal 98, 291� 296 (2011)[3] Y. An, Z. Schwartz, G. Jackson, Rapid Commun. Mass Spectrom., 27, 1481−1489 (2013)[4] A. Fido, S. Al-Saad, Autism, 9(3), 290� 298 (2005)[5] M. O. Han, J.A. Chun, W.H. Lee, J. W. Lee, C. H. Chung, J. Cosmet. Sci., 58, 527−534 (2007)[6] M. Fountoulakis, H. W. Lahm, Journal of Chromatography, 826, 109−134 (1998)


35

O5Determination of sulfur in human hair using HR-CS GFAAS and

correlation with total protein, albumin and thiol related compounds

Asli Baysal, Nil Ozbek, Suleyman Ince, Ersin Kılıç, Suleyman Akman

Notes:........................� � � � � � � � � � � � � � � � � � � � � � � � � � � � �...........� � � � ......� � � � � � � � � � � � � � � � � � � � � � � � � � .................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................


36

O6Assessment of multielement bioavailabilities in tea(Camellia sinensis L.) samples consumed in Turkey

Umran Seven Erdemir

Department of Chemistry, Faculty of Arts and Sciences, Uludag University, 16059 Bursa, Turkey

[email protected]

Tea (Camellia sinensis L.) can be seen as a popular beverage after water [1]. For the reason that it is included in everyday diet and largely consumed worldwide, the determination of major and trace elements content together with the estimation of their daily intake are very important [2]. On the other hand, total elemental levels may not reflect the bioavailable amounts for humans [3,4]. Therefore, the determination of elements that are available for absorption will be more important for associated with the consumption [5].

Several methods have previously been used to determine mineral bioavailability. These methods commonly consist of simulating gastrointestinal digestion [6]. In this study, multielemental levels of Turkish black, green, and earl grey tea samples were determined. Additionally, the bioavailabilities of the elements were studied by in-vitro methods and evaluated in terms of sufficient intake interactions. Elements in the samples and digests were determined by inductively coupled plasma-mass spectrometry (ICP-MS). Analytical validation parameters were investigated in terms of linearity, limits of detection, interday/intraday precision, and tea leaves standard reference material.

References[1] Ozdemir, Y., and S. Gucer. 1998. Food Chemistry 61: 313� 317.[2] Pohl, P., and B. Prusisz. 2007. Food Chemistry 102: 1415� 1424.[3] Moreda-Pineiro, J., A. Moreda-Pineiro, V. Romaris-Hortas, R. Dominguez-Gonzalez, E. Alonso-Rodriguez, P. Lopez-Mahia, S.

Muniategui-Lorenzo, D. Prada-Rodriguez, and P. Bermejo-Barrera. 2012. Food Chemistry 134: 339� 345.[4] Lei, B. L., L. Chen, Y. Hao, T. H. Cao, X. Y. Zhang, Y. X. Yu, and J. M. Fu. 2013. Ecotoxicology and Environmental Safety 96: 160�

167.[5] Intawongse, M. and J. R. Dean. 2006. TRAC-Trends in Analytical Chemistry 25: 876� 886.[6] Frontela, C., G. Ros, and C. Martínez. 2011. Journal of Cereal Science 54: 173� 179.


37

O6Assessment of multielement bioavailabilities in tea(Camellia sinensis L.) samples consumed in Turkey

Umran Seven Erdemir

Notes:........................� � � � � � � � � � � � � � � � � � � � � � � � � � � � �...� � � � ......� � � � � � � � � � � � � � � � � � � � � � � � � � ........................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................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38

O7Distributions of nitrosamines in gastric juices of gastrointestinal

patients

Mehmet Akyüz1*, Şevket Ata2, Berrin Gürler1

1Bülent Ecevit University, Faculty of Pharmacy, Department of Analytical Chemistry,67600 Zonguldak, Turkey

2Bülent Ecevit University, Faculty of Arts and Sciences, Department of Chemistry,67100 Zonguldak, Turkey

*[email protected]

A gaschromatography-massspectrometry method has been proposed for the determination of various nitrosamines in gastric juice samples of patients with the gastrointestinaltract problems. The obtained recoveries for nitrosamines ranged from 94.0 (NDMA) to 99.30 (NDPheA) %, and the precision of this method, as indicated by the relative standard deviations was within the range of 0.70 (NDPheA) and 2.57 (NDMA) %. The detection limits obtained from calculations by using GC-MS results based on S/N=3 were found within the range from 0.29 to 1.10 pg/mL.

Total nitrosamine concentrations were found to be at the highest concentration levels up to 2431.12 pg/mL in cancerpatients, whereas they were found to be at the lowest concentration levels down to 12.18 pg/mL in gastritis patients. The classification results of the gastric juice samples in different patient groups were very satisfactory, allowing 100 % of patients to be correctly grouped. The mathematical model based on nitrosamine concentrations might be considered as a biomarker for the classification of gastric juices of patients and might act as an indicator of increased risk for stomach cancer.

AcknowledgementThe authors are grateful for financial support of Project Number 2007-13-02-02 of Bülent Ecevit University.


39

O7Distributions of nitrosamines in gastric juices of gastrointestinal

patients

Mehmet Akyüz, Şevket Ata, Berrin Gürler

Notes:........................� � � � � � � � � � � � � � � � � � � � � � � � � � � � �...� � � � ......� � � � � � � � � � � � � � � � � � � � � � � � � � ........................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................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40

O8ICP-AES determination of nickel and chromium in eggplant and

soil samples

Mehmet Yaman

Firat University, Faculty of Science, Department of Chemistry, Elazig, Turkey


Prolonged consumption of unsafe concentrations of heavy metals in foodstuffs may lead to the disruption of numerous biological and metabolic processes in the human body. Contamination of vegetables with heavy metals may mainly be due to irrigation with contaminated water. Vegetable Solanum melongena (eggplant) is interested in studies because some species of Solanum (for example Solanum nigrum L.) have been considered as metal hyperaccumulator.

In this study, three groups of eggplant were grown depending on Ni and Cr concentrations in irrigation water. After harvesting, leaf and fruit (edible part) samples of each one were digested using microwave oven. Ni and Pb determinations were carried out by ICP-AES and ICP-MS. Soil samples that eggplants were grown in were also analyzed by using ICP-AES after digestion. From the obtained results, Ni and Cr concentrations were found in ranges of 0.42 − 0.71 and 0.28 − 0.41 mg kg-1 for fruits, 1.6 − 3.5 and 0.6 − 0.9 mg kg-1 for leaves, and 44 − 49 and 25 − 30 mg kg-1 for soils.


41

O8ICP-AES determination of nickel and chromium in eggplant and

soil samples

Mehmet Yaman

Notes:........................� � � � � � � � � � � � � � � � � � � � � � � � � � � � �...� � � � ......� � � � � � � � � � � � � � � � � � � � � � � � � � ........................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................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42

O9Combined ED(P)-XRFS and WAXD analysis of the metallurgical

wastes

Mihai Branzei, Ion Pencea, Catalin Eugen Sfat, Alecs Andrei Matei, Ramona-Nicoleta Turcu, Mihai Cojocaru

Materials Science and Engineering Faculty, University POLITEHNICA of Bucharest, Splaiul Independentei 313, sector 6, Bucharest, Romania.


As a consequence of the extended development of the Romanian metallurgical industry during communist era many huge waste dumps were left to greener pastures. These waste dumps must be removed because they are still contaminating the surrounding area by flying dust and the subsoil due to the leaching of heavy metals and other pollutants. Previous measurements have shown that a metallurgical waste may contain: 25 � 60% FexOy, 10 � 20% Al2O3, 5 � 15% TiO2, 10 � 25% SiO2 and 3 � 7% Na2O depending on the source, but Pb, Cd, Cr, As, Hg etc. The recycling technology should be tailored depending on the content of the waste. Thus, an exact chemical analysis is mandatory for deciding the recycling technology of such a waste. The issue of the solid waste chemical analysis is a complex one because the concentration of an element could be estimated as a whole e.g. 40% wt, but it is spread in different compounds as is iron spreaded in Fe2O3, Fe3O4, FeS etc. The ED-XRFS technique that used polarized excitation radiation, denoted as ED(P)-XRFS, has increased the analytical performances of the method as: sensitivity, precision, accuracy, but mainly LOD and LOQ. The Wide Angle X-ray Diffraction (WAXD) is the most efficient method for qualitatively and quantitatively phase analysis of powdered material. Based on the balance between the performance criteria and cost, ED(P)XRF and WAXD methods were used to estimate phase composition and elemental concentrations of the specimens taken from different areas of a waste dump. A mathematical model was developed to convert the elemental concentrations obtained by ED(P)-XRFS into phase composition based on the phase pattern given by WAXD measurement. A MATLAB routine was developed to fit the ED(P)-XRFS with the WAXD results.

The novelties addressed in the paper consist in:1) The usage of ED(P)-XRFS technique for increasing of the analytical performances.2) Coupling the most efficient methods for elemental and phase analysis i.e. ED(P)-

XRFS and WAXD.3) A proper software implemented in MATLAB for increasing the exactness of the

metallurgical waste composition estimation based on ED(P)-XRFS and WAXD.4) The diminishing of the decision risk in choosing the proper technology for

removing/recycling of a specific waste dump.


43

O9Combined ED(P)-XRFS and WAXD analysis of the metallurgical

wastes

Mihai Branzei, Ion Pencea, Catalin Eugen Sfat, Alecs Andrei Matei, Ramona-Nicoleta Turcu, Mihai Cojocaru

Notes:........................� � � � � � � � � � � � � � � � � � � � � � � � � � � � �...� � � � ......� � � � � � � � � � � � � � � � � � � � � � � � � � 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


44

O10Cloud Point Extraction � fundamentals and applicability with

different techniques for instrumental analysis

Kiril Simitchiev1*, Violeta Stefanova1, Veselin Kmetov1, Vanya Zapryanova2, Mariya Petleshkova2, Kiril Gavazov3, Teodora Stefanova3,

Antonio Canals4

1Department of Analytical Chemistry and Computer Chemistry, University of Plovdiv � Paisii Hilendarski� , 24 Tzar Assen Str., 4000 Plovdiv, Bulgaria

2student at Faculty of Chemistry, University of Plovdiv � Paisii Hilendarski� , 24 Tzar Assen Str.,4000 Plovdiv, Bulgaria

3Department of General and Inorganic Chemistry with Methodology of Chemistry Education,University of Plovdiv � Paisii Hilendarski� , 24 Tzar Assen Str., 4000 Plovdiv, Bulgaria

4Department of Analytical Chemistry and Food Science, University of Alicante, P.O. Box 99, 03080 Alicante, Spain

*[email protected]

The Cloud Point Extraction (CPE) can be regarded as a well-established separation/concentration procedure which has passed its early ages since it was proposed for the first time almost 40 years ago (in 1978). During the last decade it was common for the scientific articles to define the cloud point extraction as a new green alternative to the classical liquid-liquid extraction but now CPE could be also classified as � classical� . Evidence for this can be found in t he continuously increasing applications of cloud point extraction for sample preparation prior to the analysis of organic and inorganic substances.

The lecture will reveal the fundamentals of CPE with emphasis on the similarities and the differences in comparison to liquid-liquid extraction.

Nonionic and ionic surfactants are used in CPE as extractants so an overview of the self-assembling as well as the � cloud point phe nomenon� of this amphiphile molecules in water media will be presented.

Examples from the authors� experience including the CPE of different extractable forms of the analytes (metal chelates, polynuclear hydroxo-bridged complexes, ion-association complexes and organic substances) in combination with several instrumental techniques for detection (ICP-MS, ICP-OES, MP-AES and UV-VIS) will be presented and discussed.

AcknowledgementPart of the presented results were obtained with the financial support of Project Number NI15-HF-001 (NPD, University of Plovdiv � Paisii Hilendarski� ). The authors also acknowledge T.E.A.M. Ltd. for the complimentary supplied spectrometer Agilent 4200 MP-AES at Faculty of Chemistry, University of Plovdiv.


45

O10Cloud Point Extraction � fundamentals and applicability with

different techniques for instrumental analysis

Kiril Simitchiev, Violeta Stefanova, Veselin Kmetov, Vanya Zapryanova, Mariya Petleshkova, Kiril Gavazov, Teodora Stefanova, Antonio Canals

Notes:........................� � � � � � � � � � � � � � � � � � � � � � � � � � � � �...� � � � ......� � � � � � � � � � � � � � � � � � � � � � � � � � 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46

O11A novel cloudpoint extraction procedure for speciation of

Chromium

Secil Candir1*, Ibrahim Narin2

1Erciyes University, Institute of Health Science, 38039 Kayseri, Turkey2Erciyes University, Faculty of Pharmacy, 38039 Kayseri, Turkey

*[email protected]

Chromium exists primarily as trivalent and hexavalent chromium species. Speciation of chromium is very important in environmental samples and human health. Trivalent chromium is present cationic forms as Cr3+ and is an essential for human body. But, hexavalent chromium is toxic and exists as an anion, either as dichromate or chromate forms.

A speciation procedure for Cr3+ in environmental samples is presented in this work, prior to their flame atomic absorption spectrometric determinations. The cloud point extraction procedure is based on making micelle with non-ionic surfactant Tween 80 for Cr3+. After reduction of Cr6+, the system was applied to the total chromium. Cr6+ was calculated as the difference between the total chromium content and the Cr3+ content.

Accuracy of developed speciation procedure was checked by SRM analysis. Satisfactory results for the analysis of total chromium in the certified stream sedimentNCS DC 73309 andGBW 7310 for the validation of presented method were obtained. The method� s preconcentration factor was calculated as 25. The detection limit (LOD) and qualification limit (LOQ) of Cr3+ was found 2.2 and 15.6 µg/L, respectively. The presented procedure was applied to the waste water and pharmaceutical samples with successfully.

AcknowledgementThe authors would like to thank the Erciyes University Research Council for financial helps (Project No: TSD-09-991).


47

O11A novel cloudpoint extraction procedure for speciation of

Chromium

Secil Candir, Ibrahim Narin

Notes:........................� � � � � � � � � � � � � � � � � � � � � � � � � � � � �...� � � � ......� � � � � � � � � � � � � � � � � � � � � � � � � � 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48

O12Simultaneous analysis of carbendazim, flusilazole and

streptocycline used for post-harvest storage of onions by matrix solid phase extraction and liquid-liquid extraction followed by

HPLC-UV detection

Makhan Lal, Anil Duhan*

Department of Horticulture, Agrochemicals Residues Testing Laboratory, Department of Agronomy,CCS Haryana Agricultural University, Hisar, Haryana, India-125004

*[email protected]

A single-step methanol based extraction method was developed and validated for simultaneous estimation of the residues of carbendazim, flusilazole and streptocycline compounds used for preventing fungal and bacterial attack during post-harvest storage of onions. Solvents like distilled water, acetone, acetonitrile, methanol, acetonitrile-water, methanol-water and acetone-water at different compositions were optimized for better recovery of the compounds under acidic medium through matrix solid phase dispersion (MSPD) and liquid-liquid extraction (LLE) methods. MSPD involved the direct loading of finely macerated onion leaves samples with anhydrous Na2SO4 in a glass column having a bed of alumina: activated charcoal mixture (3:0.2 gm, w/w) over a cotton plug and elution with 150 ml methanol: 0.5% aqueous formic acid (9:1, v/v), which resulted in maximum extraction. The extract thus obtained was concentrated over rotavapour and directly used for analysis without any further clean-up step. Another method based on liquid-liquid extraction (LLE) was also implemented which involved extraction through mechanical shaking of finely macerated onion leaves samples in anhydrous Na2SO4 with extracting solvent having same composition as in MSPD. For clean-up, the residues were dissolved in 5 ml of acetonitrile after concentrating over rotavapour and transferred into 10 cm neutral alumina: activated charcoal mixture (10:0.5 gm, w/w) packed column between two layers of anhydrous Na2SO4. The matrix was eluted using 25 ml acetonitrile and evaporated the solvent to dryness and adjusted the final volume of the sample by adding 1 ml methanol and injected into HPLC with PDA detector at 254 nm. The use of a C18 HPLC column and a binary mobile phase methanol: 0.5% aqueous formic acid (9:1, v/v) in gradient elution mode was proposed to provide enough retention and resolution for these polar compounds. Both methods were optimized, considering different parameters, and under optimum conditions. The limits of quantification for all target compounds were ≤ 0.05 mg/kg with recoveries (%) at fortification levels of 0.05, 0.1, and 0.5 mg/kg being within 86 � 95% for MSPD (RSD ≤ 6%) and 72 � 83% for LLE (RSD ≤ 8%). On the basis of extraction efficiency, economy and time expenditure taken into account, MSPD extraction was found superior one. The study will be useful in promoting a single step effective residue monitoring and ensuring safe use of these antibiotics and


49

antifungal in managing diseases caused during post-harvest storage of onions and other food products.

Notes:........................� � � � � � � � � � � � � � � � � � � � � � � � � � � � �...� � � � ......� � � � � � � � � � � � � � � � � � � � � � � � � � 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50

O13Determination of in-vitro antioxidant capacity of cardiovascular

drugs

Onur Şenol1, Yücel Kadioğlu2, Reşat Apak3

1Atatürk University2Erzincan University3İstanbul University

[email protected]

Antioxidants are molecules or enzymes that prevent the hazardous effect of reactive species and free radicals to the cells or tissues of whole body[1]. Many antioxidant molecules are recorded in literature and their antioxidative power was measured by either in vivo or in vitro techniques [2].

In our study, it was aimed to determine the antioxidant capacity of cardiovascular drugs which are valsartan, olmesartan, irbesartan, telmisartan, eprosartan, losartan, candesartan, enalapril and captopril. In order to determine their antioxidant capacity, different in vitro antioxidant capacity methods were applied to these drugs which are CUPRAC, FRAP and ABTS. In addition to these methods [1], lipid peroxidation level of each drug was also evaluated with thiobarbituric acid (TBA) method while anticholinesterase activity was determined by donepezil equivalence method.

According to the results, the increasing order of CUPRAC assay was calculated to be Olmesartan < Valsartan < Irbesartan < Enalapril < Losartan < Telmisartan < Kaptopril < Candesartan < Eprosartan, while the same order for FRAP assay was: Candesartan < Olmesartan < Eprosartan < Valsartan < Irbesartan < Telmisartan < Losartan < Enalapril < Kaptopril and for ABTS assay was: Enalapril < Kaptopril < Eprosartan < Irbesartan < Losartan < Candesartan < Telmisartan < Olmesartan < Valsartan. Lipid peroxidation values were Enalapril< Kaptopril < Olmesartan < Irbesartan < Eprosartan < Candesartan < Telmisartan < Losartan < Valsartan, while anticholinesterase activity values were determined as Irbesartan< Candesartan< Enalapril < Losartan < Eprosartan <Telmisartan< Valsartan < Olmesartan < Kaptopril.

The results were evaluated and chemometrically interpreted. Partial least square discriminant analysis and hierarchial cluster analysis of these drugs were achieved and the groups of angiotensin receptor antagonists and angiotensin converting enzyme inhibitors were successfully separated from each other in terms of their antioxidant and lipid peroxidation properties.

The results found by different assays gave varying orders because of the differences among mechanisms, reagents and the related redox potentials of these methods. All drugs exhibited a range of low-to-moderate antioxidant capacities, and the drug groups could be classified by the partial least square discriminant analysis method.


51

References[1] Huang DJ, Ou BX, Prior RL. The chemistry behind antioxidant capacity assays. Journal of Agricultural and Food Chemistry. 2005;53:1841−56.[2] Apak R, Guclu K, Ozyurek M, Karademir SE. Novel total antioxidant capacity index for dietary polyphenols and vitamins C and E, using their cupric ion reducing capability in the presence of neocuproine: CUPRAC method. Journal of Agricultural and Food Chemistry. 2004;52:7970-81.

Notes:........................� � � � � � � � � � � � � � � � � � � � � � � � � � � � �...� � � � ......� � � � � � � � � � � � � � � � � � � � � � � � � � 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52

O14Derivative spectroscopic determination of Enrofloxacin in some

natural samples

Chinar M. Rashid1, Nabil A. Fakhre1*, Umi K. Ahmed2

1Department of Chemistry, College of Education, Salahaddin University, Erbil, Iraq2Program Head of MSc. Forensic Science, Department of Chemistry, Faculty of Science,

Universiti Teknologi Malaysia

*[email protected]

Enrofloxacin is the first specified Fluoroquinolones developed for veterinary application, which belongs to the second generation of quinolone antibiotics fluorinated in position 6 and bearing a piperazinyl moiety in position 7. Similar to other Fluoroquinolones, Enrofloxacin is used in the treatment of systemic infections including urinary tract, respiratory, gastrointestinal, and skin infections. Because of a very broad spectrum of activities against both Gram-negative and Gram-positive bacteria and lower side effects, Enrofloxacin has also been widely used for the treatment of some infectious diseases in pets and livestock. However, Enrofloxacin residues may persist in animal body and may result in the development of drug-resistant bacterial strains or allergies [1]. A new, simple, rapid, wide applicable range and reliable derivative spectrophotometric method has been developed for determination of enrofloxacin in some natural samples.

References[1] Hai-tang Z. , Jin-qing J., Zi-liang W., Xin-yao C., Xing-you L., San-hu W., Kun Z., Jin-shan C. Development of an indirect competitive ELISA for simultaneous detection of enrofloxacin and ciprofloxacin. Journal of Zhejiang University-SCIENCE B (Biomedicine & Biotechnology, 2011, 12(11):884-891.


53

O14Derivative spectroscopic determination of Enrofloxacin in some

natural samples

Chinar M. Rashid, Nabil A. Fakhre, Umi K. Ahmed

Notes:........................� � � � � � � � � � � � � � � � � � � � � � � � � � � � �...� � � � ......� � � � � � � � � � � � � � � � � � � � � � � � � � 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54

O15Spectrophotometric determination of catecholamines (levodopa,

methyldopa, dopamine and adrenaline) in pure and pharmaceutical formulations depending on the charge transfer complex formation reaction with TCNQ in both aqueous and

ethanolic solutions

Mahmood A. Hasan1*, Thabit S. Al-Ghabsha2

1Department of Chemistry, Faculty of Science, University of Duhok, Iraq2Department of Chemistry, Faculty of Education, University of Mosul, Iraq

*[email protected]

Two spectrophotometric methods are developed for the determination of some catecholamines based on their reaction with 7,7,8,8-Tetracyanoquinodimethane, TCNQ reagent forming colored charge transfer complexes.

Method one describes the determination of catecholamines (levodopa, methyldopa, dopamine and adrenaline) in the aqueous solution as n-donors forming blue charge transfer complexes with TCNQ as π-acceptor; the complexes formed at 80oC have maximum absorptions at 612 nm. Beers law is obeyed over the concentration range of 0.2 − 5.5, 0.2 −8.5, 0.2 − 5.0 and 0.5 − 5.0 µg ml-1 with molar absorpitivity of 44520, 41890, 39190 and 18100 L mol-1 cm-1 for levodopa, methyldopa, dopamine and adrenaline respectively. The accuracy (average recovery) range is between 99.02% and 101.78% and the precision (RSD) ≤ 2.5% for all catecholamines. The stability constants range is between 0.55 x 1011 L3 mol-3

for adrenaline and 4.40 x 1011 L3 mol-3 for levodopa, the complexes are stable for more than 100 hours in room temperature and more than 45 days in freezer (about -15oC). The method is applied successfully for determination of these drugs in pharmaceutical formulations and compared favorably with British Pharmacopeia standard methods. T-test values are less than the tabulated values at 95% confidence level. The compositions of all charge transfer complexes are found to be 1:3 catecholamines:TCNQ by both Job� s and mole ratio methods.

Method two describes the development of a spectrophotometric method for the determination of catecholamines (levodopa, methyldopa and dopamine) in the ethanol-water solution depending on the charge transfer complex formation reaction with TCNQ at 55 −60oC, and the measurement of the quantitative enhancement of the TCNQ absorbance at 840 nm. Beers law is obeyed over the concentration range of 0.05 − 1.0, 0.04 − 2.6 and 0.02 − 1.5 µg ml-1 with molar absorpitivity of 24370, 18720 and 17420 L mol-1 cm-1 for levodopa, methyldopa, and dopamine respectively. The accuracy range is 101.61% and 102.23% and the precision (RSD) ≤ 2.03%. The stability constants range is between 0.5222 x 104 L3 mol-3 for dopamine and 1.0925 x 104 L3 mol-3 for levodopa and, the complexes are stable for more than 2 hours in room temperature. The compositions of all charge transfer complexes are found to


55

be 1:1catecholamines:TCNQ by both Job� s and mole ratio methods.The two methods are applied successfully for the determination of the catecholamines

in their pharmaceutical preparations.

Notes:........................� � � � � � � � � � � � � � � � � � � � � � � � � � � � �...� � � � ......� � � � � � � � � � � � � � � � � � � � � � � � � � 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56

P1Multiresidue analysis of organochlorine pesticides pollution in the

Ergene River using QuECheRS extraction and GC-MS

Cemile Ozcan1*, Mehmet Yaman2

1Science and Art Faculty, Department of Chemistry, Kirklareli Universty2Firat University, Sciences Faculty, Department of Chemistry, Elazig, Turkey

*[email protected] *[email protected]

Ergene River Basin, in Thrace region (Turkey), has an area of 17.323 km². Agricultural area and industrial activities have caused increases in toxicity and pollution in the ecological environment. Pesticides are potential chemical pollutants extensively used for agriculture purposes due to low cost and high effectiveness. They may accumulate in living creature as decomposition which can remain or less degradate in the environment (such as ∑DDT and ∑HCH). Among the most important sources of pesticides originating from agricultural applications and industrial pollutants of soil, the inorganic and organic fertilizers, fungicides, liming, sewage sludge and irrigation waters can be counted. In general, factory and agricultural pollutants when released into water systems bind to particulate matter, in which after eventually becoming decanted, are incorporated into the sediments.

The water and sediment samples were collected seasonally in April 2012 and January 2013. An efficient and sensitive method for simultaneous determination of 18 pesticides in Ergene river and sediments have been developed and validated. Water samples were extracted using EPA Method 3510 (separatory funnel) while solid samples were extracted by using the quick, easy, cheap, effective, rugged and safe (QuEChERS) extraction method. The target pesticides were analyzed with a good reproducibility and low detection limits by using gas chromatography-mass spectrometry with electron impact ionization-possitive mode (GC-MS-EI (+)). The limits of quantification were between 0.06-63.0 ng kg� 1. The RSDs of the migration time ranged from 2.4% to 7.7% for the eighteen analytes, indicating the good repeatability of the method. Concentrations of organochlorine pesticides(hexachlorocyclohexane (∑HCH), aldrin, heptachlor, dieldrin, endosulfan, methoxychlor and dichlorodiphenyltrichloroethane (∑DDT)) were determined in samples collected from selected different points in Ergene River. The developed method was successfully applied in the determination of the pesticides in Ergene river and sediment. All organochlorine pesticides were found below of the MRL values in water samples.

AcknowledgementThe authors are grateful for financial support of Kirklareli Universty.


57

P2ICP-MS determination of lanthanides in plant digest after LLE

with 3-Ethylamino-but-2-enoic acid phenylamide

Evelina Varbanova*, Plamen Angelov, Violeta Stefanova

University of Plovdiv, 24 Tzar Asen Str.

*[email protected]

A new ligand from enaminone type (3-Ethylamino-but-2-enoic acid phenylamide) is investigated for liquid-liquid extraction of lanthanides (La, Ce, Eu, Nd, Gd and Er). Optimized procedure is applied for separation and determination of lanthanides in digested plant material. The optimized extraction procedure is compatible with Inductively Coupled Plasma Mass Spectrometry as final method for trace lanthanide determination. Different calibration strategies i.e. water calibration, matrix matched calibration and internal standardization, are tested and the last one is proposed for instrumental determination of target elements. Among tested candidates for internal standard, Re is proven to be the most effective. Spectral interferences from plasma and sample matrix components are studied and interference-free isotopes are used for analysis. Isobaric and polyatomic overlaps from Ba are eliminated by separating lanthanides from the matrix during the extraction procedure. The studied compound shows high potential as effective ligand for LLE of lanthanides prior to their determination in plants. Selectivity towards alkali and alkaline-earth elements is demonstrated. The accuracy of the proposed method for extraction of REEs is approved by analysis of Reference material for plants.

AcknowledgementThe authors are grateful for financial support of Project Number NI15-HF-001 (NPD, University of Plovdiv � Paisii Hilendarski� ).


58

P3Development and validation of an Ion-Pair Liquid

Chromatography method for determination of asenapine in tablets

Sakine Atila Karaca*, Duygu Yeniceli Uğur

Anadolu University, Faculty of Pharmacy Department of Analytical Chemistry, Eskişehir, Turkey

*[email protected]

Asenapine is a new atypical antipsychotic drug which is approved for the treatment of schizophrenia and acute manic or mixed episodes of bipolar disorders.

A new, simple and spesific method was developed and validated for the determination of asenapine in tablets using high performance liquid chromatography.

An Agilent 1290 Infinity Binary LC system (equipped with a binary pump, a degasser, an autosampler and a thermostatted column compartment) was used for analyses. The separation of asenapine and carbamazepine (used as internal standard) was performed on an Agilent Eclipse XDB-C8 column (4.6 x 150 mm, 3.5 µm particles) with phosphate buffer (20mM, pH 3) containing 10 mM heptane-1-sulfonic acid sodium salt and acetonitrile (60:40, v/v) as mobile phase at a flow rate of 1 ml/min. UV detection was at 220 nm.

Retention times of asenapine and carbamazepine were 3.5 and 4.7 min, respectively. Method was validated in terms of linearity, precision, accuracy, specificity, stability, robustness and ruggedness. Good linear response was obtained over the range of 0.50 − 100 µg/ml for asenapine. LOD and LOQ values of asenapine were 0.1078 µg/ml and 0.3594µg/ml, respectively.

Fully validated method was successfully applied to asenapine tablets.

AcknowledgementThe authors appreciate Research Council of Anadolu University for the support of the Project (Project No: 1302S023).


59

P4Application of starch-protected silver nanoparticles in selective

colorimetric detection of Iron(III) ions in aqueous medium

Penka Vasileva1*, Irina Karadjova2

1Laboratory of Nanoparticle Science and Technology, Department of General and Inorganic Chemistry, Faculty of Chemistry and Pharmacy, University of Sofia � St. Kliment Ohridski� , Bulgaria

2Department of Analytical Chemistry,Faculty of Chemistry and Pharmacy, University of Sofia � St. Kliment Ohridski� , Bulgaria

*[email protected]

Silver nanoparticles (Ag NPs) are well known for their strong interactions with light through the resonant excitations of the collective oscillations of the conduction electrons on the particles, the so-called local surface plasmon resonances (LSPR). Our studies on the ability of the starch-protected silver nanoparticle dispersion for the preparation, characterization and calibration of LSPR-based optical sensor for determination of Fe(III) trace amount were summarized. The morphology, structure and thermal behavior of starch-stabilized silver nanoparticles were characterized by UV� vis spectroscopy, TEM and XRD techniques, DLS and ζ-potential, TG/DTA and DSC measurements. The nanoparticles are quasi-spherical, with narrow size distribution and average diameter of l5.4 ± 3.9 nm. It was found that the starch-stabilized silver nanoparticles obtained in our synthesis have a LSPR band at 408 mn, high colloidal stability and oxidation ability for the reduction of Fe(III) to Fe(II). Furthermore, a degradation of highly clustered silver nanoparticles by their oxidation to Ag+ was observed. Hence, a remarkable change in the LSPR absorbance strength, which depends on the Fe(III) concentration, was established. As a result, the yellow colour of starch-stabilized silver nanoparticle solution is gradually changed to transparent colour. On the basis of this mechanism, the characterization of LSPR-based optical Fe(III) sensor is carried out. This LSPR-based optical sensor has a very good sensitivity and a linear response over the range of 1 − 10-ppm Fe(III). Furthermore, the detection limit of this sensor is found to be 0.2 ppm. Added/found method was used to confirm the validity of proposed AgNPs sensor for determination of iron(III). This LSPR-based optical sensor for Fe(III) has the potential to be applied for iron speciation in ground and tap waters.

AcknowledgementThe authors are grateful for financial support of Project 10/2015 of Scientific Research Fund of Sofia University � St. Kliment Ohridski� .


60

P5Raffinose � new reducing/stabilizing agent for preparation of

silver nanoparticles as analytical probe

Lyubomir Djerahov1,2*, Penka Vasileva2

1Department of Analytical Chemistry,2Laboratory of Nanoparticle Science and Technology, Department of General and Inorganic Chemistry

Faculty of Chemistry and Pharmacy, University of Sofia � St. Kliment Ohridski� , Bulgaria

*[email protected]

Silver nanoparticles have been already explored as colorimetric probes for metal ions, but their capabilities for chromium speciation are not reported. In this study, silvernanoparticles (Ag-Raff NPs) with narrow size distribution were synthesized by a green approach employing raffinose as both reducing and stabilizing agent. The adsorption behaviors of Cr(III) and Cr(VI) on Ag-Raff NPs were studied systematically, and a simple,sensitive and selective method was developed for the separation and determination of chromium species in water samples using Ag-Raff NPs as both solid-phase extraction adsorbent and LSPR-based optical sensor. It was found that Ag-Raff NPs is selective sorbent towards Cr(III) at pH 9 � 10, reached by ammonia solution, while Cr(VI) remains in the solution. The retained Cr(III) is subsequently eluted with 1 mol L-1 HNO3 and determined by flame atomic absorption spectrometry. Cr(VI) in the effluate is reduced with ascorbic acid to Cr(III) at the presence of Ag-Raff NPs and determined through the optical response of the nanoparticles. The calibration curve for Cr(VI) was found to be linear in the range of 2.5 − 7.5 μmol/L; quantification limit of 0.9 μmol/L; relative standard deviation from 6% to 10% for the concentration level of 0.9 − 7.5 μmol/L. Interference studies performed in the presence of various elements showed very good selectivity of Ag-Raff NPs toward Cr(VI).

AcknowledgementThe author L. Djerahov (PhD student) is grateful for financial support from Bulgarian Ministry of Education and Science.


61

P6Determination of Cd(II), Cu(II) and Co(II) ions in water and food

samples by FAAS with online preconcentration using novel modified silica gel

Sezen Sivrikaya1,2*, Mustafa Imamoglu1

1Sakarya University, Sciences and Arts Faculty, Chemistry Department, 54187 Sakarya, Turkey2Bulent Ecevit University, Engineering Faculty, Environmental Engineering Department,

67100 Zonguldak, Turkey

*[email protected]

Trace metal analysis in natural water, wastewater, biological, industrial and other complex samples is one of the most challenging areas of analytical chemistry. As a result of human exposure to metals such as Cd(II), Cu(II) and Co(II), brain, kidneys, respiratory system, nerves system, and reproductive system can be damaged. Consequently, development of sensitive and reliable analytical methods is necessary to monitor the levels of metal contamination in the food and other environmental samples.

Determination of the trace metals by many sensitive and powerful instrumental techniques such as FAAS and ICP-OES is often difficult due to matrix interferences and improprer detection limits. In these cases, preconcentration and/or separation processes are necessary to improve the detection limits and eliminate matrix effects. Several methods have been used for this purpose, such as solid phase extraction (SPE), co-precipitation, solvent extraction, electrothermal decomposition, and membrane extraction. The SPE technique is very popular due to allowing an automation of the preconcentration procedure and so, SPE combined with flow injection analysis have been widely used at preconcentration studies.

In this study, an online preconcentration procedure using silica gel functionalized with 2-[N,N'-bis(2,3-dihydroxybenzaldimin)]aminoethylamine was developed for the determination Cd(II), Cu(II) and Co(II) ions. The structure of the prepared sorbent was confirmed by using elemental analysis, thermogravimetry/differential thermal analysis and Fourier transform infrared spectroscopy (FTIR). The effects of parameters such as pH, sample and eluent flow rates, matrix ions, and type, concentration and volume of eluent on the online preconcentration of these ions were examined. The preconcentration method was validated by determination of cadmium(II), copper(II), and cobalt(II) levels in Virginia Tobacco Leaves (CTA-VTL-2) and Water-Trace Elements (NWTM-15.2) certified reference materials. The proposed method was successfully applied for determination of Cd(II), Cu(II) and Co(II) concentrations in water and food samples.

AcknowledgementThis work was supported by the Sakarya University Research Fund with Project Number 2012-50-02-036.


62

P7Solid phase extraction of Pd(II) using silica gel modified with

Schiff bases

Petranka Petrova1*, Irina Karadjova2, Maya Chochkova1, Ivanka Dakova2

1South-West University � Neofit Rilski� , Faculty of Mathematics and Natural Sciences, Department of Chemistry, 66 Ivan Mihailov Str, 2700 Blagoevgrad, Bulgaria

2Sofia University � St. Kliment Ohridski� , Faculty of Chemistry and Pharmacy, 1 J. Boucher Blvd.,1164 Sofia, Bulgaria

*[email protected]

The sorption of Pd(II) as metal complexes with 4-aminoantipyrine derivatives on Schiff bases modified silica gel (Sig-Schiff bases) in the presence hydrochloric acid solutions was studied. Quantitative sorption of Pd(II) was acieved on the Sig-Schiff bases containing azomethine group on the surface, in the presence of 0.1 � 1 mol/L HCl. Sorption behavior of noble metal toward new sorbents was further studied in a studied in a column mode. The influence of various chemical parameters: sample acidity, type and concentration of eluent, sorption and desorption kinetics, sample and eluent flow rates have been optimized for quantitative sorption of Pd(II). Metal loaded on the sorbent can be recovered using 0.7 M thiourea in 2 M HCl solution as eluent, with desorption efficiency exceeding 97% under selected experimental conditions. FAAS was used to quantify Pd(II) in eluates and effluates. The presence of competitor ions as Al(III), Cu(II), Fe(III), Mn(II), Ni(II), Zn(II) has insignificant influence on binding properties of sorbent. The recycling of the Sig-Schiff baseswas effective for at least three sorption/desorption cycles.

AcknowledgementThe authors are grateful for financial support of Project SRP A19/15 of South-West University � Neofit Rilski� , Blagoevgrad, Bulgaria.


63

P8Analytical methods for quantitative determination of

Olopatadine hydrochloride in pharmaceutical preparation

Berk Toker, Engin Er, Nevin Erk*

Ankara University, Faculty of Pharmacy, Department of Analytical Chemistry, 06100 Ankara, Turkey

*[email protected]

This study is concerned with the quantitative analysis of Olopatadine hydrochloride (OPT) by using different methods. The first one is a voltammetric method which is used for electrochemical determination of OPT. Electrochemical oxidation of OPT was determined at +1.201 V vs. Ag/AgCl in 0.5 M H2SO4 with diffusion controlled and irreversible. The second method applied was HPLC. HPLC was carried out on reverse phase Waters®� Symmetry Shield RP-18 HPLC column (150 mm × 4.6 mm, 5µm) column using a mixture of acetonitrile: methanol: water, in the ratio 10:60:30 (v/v/v) as mobile phase at a flow rate of 0.75 mL/min. UV detection was performed with diode-array detector. A simple, rapid, selective and stable HPLC method was developed for the determination of OPT. Linear working range was found to be 10.0 − 80.0 µg mL-1 with the detection limits of 0.173 µg mL-1

for OPT. Caffeine was used as internal standard for the purpose of quantification of the drug in HPLC. In the third method, first-order derivative spectrophotometry, for the determination of OPT the derivative absorption amplitude at 288.8 and 308.4 nm was used. The linear working range of OPT was found to be 20.0 − 140.0 µg mL-1 with the correlation coefficients of 0.9997 and 0.9996, respectively. Detection limit was estimated to be 0.346 and 0.600 µgmL-1 for 288.8 nm and 308.4 nm, respectively. All the proposed methods were fully validated and a comparison was made for assay determination of OPT in formulations. The results confirm that the methods are suitable for its intended purpose.

AcknowledgementThe authors thank to Abdi İbrahim A.Ş. and Selma AYDOĞAN for providing standard Olopatadine hydrocholoride.


64

P9Mercury contamination and its potential risk due to fish consumption from two lakes near Black Sea, Bulgaria

Katya Peycheva*, Lubomir Makedonski, Mona Stancheva

Department of Chemsitry, Faculty of Pharmacy, Medical University of Varna,55 Marin Drinov Str., 9000 Varna

*[email protected]

Many aspects of Hg contamination have been evaluated during recent decades. Fishes and other aquatic organisms bioaccumulate Hg in their tissues as the contaminant moves through food chain. The characteristics of the fish itself (i.e., its diet, age, and size), the Hg input to a particular area, and the biogeochemical dynamics influenced by a suite of watershed characteristics all affect the mercury concentration in an individual fish.

This study aimed to investigate mercury (Hg) contamination in various freshwater fish species from Varna Lake and Beloslav Lake, to compare these results with the mercury levels in one marine fish from Bulgarian Black sea coast and to assess the potential risks of fish consumption. Furthermore, estimated daily intake (EDI), weekly intake (EWI) and potential health risks were determined using target hazard quotient (THQ) equation. Results revealed the concentration of Hg in freshwater fish species were ranged from 0.0125 to 0.0523 mg/kg and for the marine fish species was up to 0.07 mg/kg w.w. The magnitude of EWI values of Hg in fish species showed that consumption per week for body weight (60 kg for females and 68 kg for males) for the local people was found to be in the range of 0.02 to 0.11 mg/kg bw. In addition, the magnitude values of target THQ for fishes were in the range of 0.025 to 0.140 for females and 0.026 to 0.148 for males. All those levels have not exceeded the limit standard or < 1 for potential health risks which means safe for consumption.


65

P10Determination of trace folic acid in food samples

Halil İbrahim Ulusoy1*, Hilal Acıdereli1, Songül Ulusoy2, Selim Erdoğan3

1Cumhuriyet University, Faculty of Pharmacy, Department of Analytical Chemistry, 58140 Sivas, Turkey2Cumhuriyet University, Faculty of Science, Department of Chemistry, 58140 Sivas, Turkey

3İnonu University, Faculty of Pharmacy, Department of Analytical Chemistry, 44100 Malatya, Turkey

*[email protected]

Folic acid is one of the B group vitamins that its deficiency causes important health troubles. Then, it is advised to use multivitamin drugs including folic acid or to take it by daily diet by means of natural foods. The monitoring of folic acid levels in real samples is so important because of its effects on health. Unfortunately, the amount of folic acid in most real samples is lower than detection limit of common instrumental methods. So, it generally a pre-concentration and separation method needs for trace analysis.

A pre-concentration and determination method was developed for Folic Acid (Vitamin B9) at trace amounts based on cloud point extraction (CPE) and HPLC analysis. In the presented method, a stable complex was formed between folic acid and Fe(III) ions in the presence of pH 4.0 buffer. Then, the formed complexes were extracted to nonionic surfactant phase consisting of PONPE 7.5. Surfactant rich phase (SRP) was separated by decantation after centrifugation and then surfactant-rich phase was diluted with 500 µL of 0.1 M HCl in 50% methanol. Absorbance signals were monitored by using a diode array detector (DAD) for folic acid at 282 nm. Under the optimized conditions, linear ranges were obtained in the range of 50 − 1000 ng mL-1 for folic acid. The detection and quantification limits of method were calculated as 15.2 ng mL-1 and 48.3 ng mL-1, respectively. The relative standard deviations were 2.90 and 2.20% for 5 replicate measurements at 100 ng mL-1 concentration level. The method was validated by the analysis of three certified reference materials (NIST 3280, BCR-485 and ERM-BD6000) and recovery test. Finally, the method was applied to the determination of vitamin B1 and B2 in real samples including baby foods, milk and cereals.

AcknowledgementThis study has been supported by Cumhuriyet University Scientific Research Projects Commission as the research project with the F-412 code.


66

P11CoSO4 as supplement in bee feeding � Co content in bee products

and bee organism

Elisaveta Mladenova1*, Ralitsa Balkanska2, Irina Karadjova1,Tsvetomil Voyslavov1

1Sofia University � St. Kl. Ohridsky� , Faculty of Chemistry and Pharmacy, Department of Analytical chemistry, 1, James Bourchier Blvd., 1164 Sofia, Bulgaria

2Institute of Animal Science, Department � Special branches � bees� , 2232 Kostinbrod, Bulgaria

*[email protected]

Honey is one of the most widely consumed bee products in a human diet. Both propolis and royal jelly have a long history of medicinal use and can be consumed fresh or taken in supplement form. Biological activities of honey, propolis and royal jelly, and their function as antibacterial, antioxidant, antitumor, anti-inflamatory and antiviral agents are attributed to the content of various chemical compounds such as flavonoids, essential amines and combination of essential elements. The actual chemical composition depends on many factors such as the bee feeding, pollen source, climate and environmental conditions. Salts of essential chemical elements have been studied as supplements in bee� s food which showed positive effect on bees� productivity and Vitamin C exchange in the bee organism. The purpose of the work presented is to investigate the influence of CoSO4, as supplement in bee feeding, on the Co content in the bee organism (bee heads, bee bodies and bee excrements) and bee products (honey, propolis, wax, royal jelly). CoSO4 was added to the sugar syrup for bee feeding at three concentration levels − 4, 10 and 15 mg/L CoSO4. Control experiment without CoSO4 was carried out as well. Experiments were performed with two bee families, farmed in the Institute of Animal Science, Kostinbrod, Bulgaria. Co content in bee organism and bee products was determined after acid (HNO3) digestion and ICP-MS measurement.

AcknowledgementThe author Elisaveta Mladenova (young scientist) is grateful for financial support from Bulgarian Ministry of Education and Science.


67

P12Spectrophotometric determination of Mercury after

Supramolecular solvent-based Microextraction (Ss-ME) in environmental samples

Funda Aydın1*, Erkan Yılmaz2, Mustafa Soylak2

1Yüzüncü Yıl University, Faculty of Pharmacy, Department of Basic Sciences, 65080 Van, Turkey2Erciyes University, Faculty of Sciences, Department of Chemistry, 38039 Kayseri, Turkey

*[email protected]

Mercury has highly toxic effects for all living organisms because of its accumulative character in the environment. Mercury is used in different areas, mainly electricity-generating power stations, gold and mercury mining, pharmaceutical products, cement, pesticides, medical equipment industries and dentistry (amalgam). Because the mercury threat is increasing day-by-day, the determination of mercury is becoming more important. Instead of using the traditional extraction methods, microextraction techniques have been used in different fields of analytical chemistry as a very successful sample preparation tool. The miniature extraction techniques based on the formation of supramolecular solvent are easy to use, fast, inexpensive and compatible with analytical instruments. Supramolecular solvents are nano-structured liquids which are generated from the amphiphiles through a sequential self-assembly process occurring on two scales, molecular and nano. In the study, we selected Ss-ME analytical method as easy and practical technique and we investigated the suitability of Ss-ME-UV-VIS spectrophotometry which is inexpensive and commonly available in many laboratories for trace mercury(II) speciation in environmental matrices. 1-(2-pyridylazo)-2-naphthol (PAN) was used as chelating agent. Hg(II)-PAN complex extracted at pH 9.5 to the supramolecular phase (1-decanol/THF) which ensure the formation of micelles in the nano and molecular size and determined. The optimum experimental conditions obtained for the proposed method are pH 9.5 (phosphate buffer), 500 µL of PAN (2.0 x 10-3 M), 200 µL of 1-decanol, 300 µL of THF, 1 min of ultrasonic bath and 5 min of centrifugation time. The validation of the methodology was carried out by analyzing the standard reference materials.Also, the developed method was successfully applied to determine mercury(II) content in different environmental water samples.

AcknowledgementThe authors are grateful for financial support of Yüzüncü Yıl University (grant no. 2014-ECZ-B207).


68

P13Organochlorine pollutants in freshwater fish from coastal lakes in

Bulgaria

Stanislava Georgieva*, Mona Stancheva, Angelika Georgieva

Medical University − Varna

*[email protected]

This study was carried out to assess the levels and distribution of organochlorine pollutants in coastal lakes near Varna city and Burgas city, Bulgaria, using wild fish as bioindicators to evaluate the coastal water quality. Levels of polychlorinated biphenyls (PCB), chlorinated pesticides (DDT and its metabolites, hexachlorobenzene) and hexachlorobutadiene were determined in fish collected from Lake Varna, Lake Beloslav, Lake Burgas and Lake Mandra in autumn 2014. Organochlorine compounds were investigated in several fish species: goby (Neogobius melanostomus), golden grey mullet (Mugil auratus), silverside (Atherina boyeri), gibel carp (Carassius gibelio), roach (Rutilus rutilus) and perch (Perca fluviatilis). The results for freshwater fish were compared with data from the study of three marine fish species collected from the Black Sea: goby (Neogobius melanostomus), sprat (Sprattus sprattus sulinus) and grey mullet (mugil cephalus).

The fifteen congeners of PCBs, HCB, HCBD, DDT and its two main metabolites DDE and DDD were determined by capillary gas chromatography system with mass spectrometry detection. The organochlorine levels in the wild fish were found in the order DDTs > PCBs. The other contaminants HCB and HCBD were below the analytical detection limit. The levels of DDTs were determined from 1.81 to 17.97 ng/g (in perch and golden grey mullet, respectively) wet weight and PCBs concentrations were found from 0.42 to 8.05 ng/g ww (in goby and golden grey mullet, respectively).

The results indicate that contamination by organochlorine compounds are higher in fish sampled in the Lake Varna than those from Lake Burgas and Lake Mandra. PCBs and DDTs residues in freshwater fish were lower than concentrations in marine fish species. The sum of the six Indicator PCBs in all fish species did not exceed the recommended European maximum limit of 75 ng/g wet weight. The concentrations of DDTs and PCBs were found lower compared to those in similar fish species from other European lakes.


69

P14Determination of total sulfur in different types of vinegars by high

resolution flame molecular absorption spectrometry

Nil Ozbek, Suleyman Akman*

Istanbul Technical University, Faculty of Science and Letters, Chemistry Department,34469 Maslak, Istanbul, Turkey

*[email protected]

Vinegar is a liquid produced usually by oxidation of the alcohol in grapes or different fruits by fermentation and used as a condiment or food preservative. It can be produced from variety of substances with different flavors and qualities.

Generally grapes are exposed to sulfur dioxide during production and transportation stage to prevent mold and decaying. When these grapes are used in vinegar production, sulfur compounds can present. In addition, in fermentation stage, yeast naturally produces a little amount of SO2, generally less than 10 mg L-1. Also sulfur compounds, mainly sodium metabisulfite (Na2S2O5), are added as preservative to vinegars for its antibacterial and antioxidant properties. In the presence of acidic matrix, sodium metabisulfite releases sulfur oxides. Sulfur in vinegars can release sulfur dioxide in the forms of H2SO3, HSO3

-and SO32-

as well as combined with compounds such as phenols, acetaldehyde and sugar. It can prevent mold and decaying but other than its advantageous properties, sulfur content may cause allergic reactions including respiratory reactions i.e. asthmatics, anaphylaxis etc. Because of its negative health effects, the addition of sulfur forms as preservatives, are authorized according to defined standards and doses for its health effects.

In this study, total sulfur concentrations in vinegar samples were determined in air-acetylene flame via molecular absorption of carbon monosulfide (CS) using a high-resolution continuum source absorption spectrometer. The molecular absorption for CS was measured at 258.056 nm. Due to non-spectral interferences as well as different sensitivities of some sulfur compounds in vinegars, the sulfur species in the samples were oxidized to sulfate using HNO3

and H2O2 and analyte addition technique was applied necessarily in all quantifications. The LOD and characteristic concentration for the method were 11.6 and 44.0 mg L-1, respectively. The sulfur concentrations of various vinegar samples were ranged from ≤ LOD to 163.6 mg L-

1.


70

P15Method development for the determination of Ca, Cu, Mg, Mn, K, Fe, P and Zn in different types of breads by Microwave Induced

Plasma-Atomic Emission Spectrometry

Nil Ozbek, Suleyman Akman*

Istanbul Technical University, Faculty of Science and Letters, Chemistry Department,34469 Maslak, Istanbul Turkey

*[email protected]

Bakery products, especially bread, is the most popular food in the world since prehistoric ages. It is consumed commonly in Middle East countries, including Turkey as an indispensable food. Although it is simply prepared from dough and water, many ingredients such as preserving agents, leavening agents, milk, egg, sugar, spice, dried-fruit, nuts, seeds, corn flour, oaten, whole wheat flour etc. are added to improve its ease of manufacturing, shelf life, taste and nutrition value. Therefore, mineral contents of breads are expected to be influenced from their ingredients as well as baking conditions.

Microwave induced plasma-atomic emission spectrometry (MIP-AES) is a novel promising technique which uses a 2.45 GHz microwave magnetic field and nitrogen gas to sustain a high temperature plasma (approximately 5000 K). The most attractive advantage of MIP-AES over atomic emission spectrometry (ICP-AES) and inductively coupled plasma�mass spectrometry (ICP-MS) techniques is the low running costs due to gas-consumption because nitrogen is maintained mostly extracted from air by a nitrogen generator. Another advantage of MIP-AES compared to AAS is that refractive and/or carbide forming elements can be more easily determined because temperature of plasma is much higher than those of flames and graphite furnace. Therefore, MIP-AES is a competitive technique with many challenges and advantages.

In this study, a novel method was developed for the determination of calcium, magnesium, potassium, iron, copper, zinc, manganese and phosphorous in various kinds of breads samples sold in Turkey by microwave plasma-atomic emission spectrometry (MIP-AES). Breads were dried at 100oC for one day, ground thoroughly and then digested using nitric acid/hydrogen peroxide (3:1). The analytes in certified reference wheat flour and maize flour samples were determined in the uncertainty limits of the certified values as well as the analytes added to the mixture of ground bread and acid mixture prior to digestion were recovered quantitatively (> 90% ). Therefore, all determinations were made by linear calibration technique using aqueous standards. The LOD values for Ca, Mg, K, Fe, Cu, Mn, Zn and P were 13.1, 1.10, 11.8, 4.47, 1.10, 0.41, 3.0, 7550 ng mL-1, respectively.


71

P16Determination of phenolic acids in pomegranate juice made from

Denizli by LC/MS/MS

Mürüvvet Karakaplan, Mustafa Özcan*

Istanbul Technical University, Science and Letters Faculty, Chemistry Department,34469 Maslak, İstanbul, Turkey

*[email protected]

Pomegranate is a fruit that has many benefits for health. Consumption of pomegranate juice as dietary antioxidants has been shown beneficial to diabetic and hypertensive patients. The Pomegranate juice was reported to be effective in the prevention ofatherosclerosis, low-density lipoprotein oxidation, prostate cancer, plateletaggregation and various cardiovascular diseases. Pomegranate fruit juice and Ellagic acid are potential chemopreventive agents for prostate cancer.

Pomegranate juice has taken great attention in the last years due to its nutritional value and the antioxidant properties. On the determination of phenolic acids in foodstuffs, UV spectrophotometry, gas chromatography, thin-layer chromatography, high-performance liquid chromatography, liquid chromatography mass spectrometry and capillary electrophoresis systems are used.

In this study, four phenolic acids, gallic, chlorogenic, caffeic, p-coumaric and ferulic acid were determined in freshly squeezed pomegranate juice, commercial pomegranate juice and pomegranate juice concentrate beverages. For this purpose, an analytical method using liquid chromatography − triple quadrupole mass spectrometry was developed for the characterization and quantification of phenolic acid in pomegranate juices. Then freshly squeezed pomegranate juices, commercial pomegranate juices and pomegranate juices concentrate were analysed for the quantitative determination of phenolic acids in juices with these methods.


72

P17Determination of mercury in spent and new fluorescent lamps by

HG-AAS

Seçil Kırlangıç1, Serdar Aktaş2, Mustafa Özcan1*

1Istanbul Technical University, Science and Letters Faculty, Chemistry Department,34469 Maslak, İstanbul, Turkey

2Marmara Üniversity, Faculty of Engineering, Department of Metallurgical and Materials Engineering,34722, İstanbul, Turkey

*[email protected]

Fluorescent lamps raise important environmental concerns because of their high content of mercury, a known toxic metal. When the lamps are discarded, mercury may contaminate soil, plants, animals, and water. Fluorescent lamps� s extensive use over the years has caused growing concerns over their proper disposal. Therefore; the limit allowed by the European Community is 5 mg per compact fluorescent lamp.

A fluorescent lamp is basically constituted of a glass tube internally coated with phosphorescent powders composed of calciumhalophosphate with 1 � 2% antimony and manganese � [Ca5(F,Cl)(PO4)3:Sb, Mn]� . The quantity of the minor components may change slightly, depending on the color of the lamp. An alumina pre-coating may be found between the glass tube and the luminescent powder. The tube is filled with an inert gas (argon, neon, krypton, and/or xenon) at low pressure (0.003 atm) and mercury vapor at low partial pressure. Cathodes made of either tungsten or stainless steel are assembled on the ends of the lamps. The tube is under partial vacuum. Fluorescent lamps rely on mercury as the source of ultraviolet radiation for the production of visible light.

In this study different brands of spent and new fluorescent lamps were characterized for the distribution of mercury. Mercury was determined in the phosphor powders, whichaffects efficiency of lamp. As a technique; hydride generation atomic absorption spectrometry was used, because of the following advantages of the technique for the determination of mercury: (i) element is seperated from the matrix simply and thus interferences are decreased; (ii) limit of detection is lowered to ppb (μg/L) levels.


73

P18Determination of Al, B, Co, Cr, Cu, Fe, Mg, Mn, Pb and Zn in

different types of Turkish vinegars by Microwave Induced Plasma-Atomic Emission Spectrometry

Nil Ozbek*, Suleyman Akman

Istanbul Technical University, Faculty of Science and Letters, Chemistry Department,34469 Maslak Istanbul, Turkey

*[email protected]

Vinegar is used as a condiment and preservative for salad dressings, and other sauces. It is made from various sugary and starchy materials by alcoholic and subsequent acetic fermentation. Therefore, its mineral content is directly influenced from the fruits, fermentation and storing conditions.

Microwave induced plasma-atomic emission spectrometry (MIP-AES) is a new generation nitrogen-based plasma technique which uses a 2.45 GHz microwave magnetic field and nitrogen gas to sustain the plasma. This relatively new technique has many advantages over atomic absorption spectrometers, (i) there is no need of flammable and toxic gases and their gas-cylinders, (ii) since temperature of plasma is higher than this ensured by the AAS-analysis, refractive or carbide forming element determination becomes possible. Since new commercial instruments are available only for three years number of papers about applications of MP-AES on different samples is less as compared to AAS and ICP techniques.

In this study, microwave plasma-atomic emission spectrometry (MIP-AES) was used to determine Al, B, Co, Cr, Cu, Fe, Mg, Mn, Pb and Zn in various vinegar samples produced in Turkey. Prior to analysis, vinegar samples were diluted to appropriate volumes and then directly aspirated to the plasma. The analytes added to the vinegar samples were recovered quantitatively (between 94 and 104%). All determinations were performed using aqueous standards for calibration. The LOD values for Al, B, Co, Cr, Cu, Fe, Mg, Mn, Pb and Zn were 0.62 µg mL-1, 7.67 µg mL-1, 4.55 µg mL-1, 0.52 µg mL-1 , 1.22 µg mL-1, 5.72 µg mL-1, 1.32 µg mL-1, 0.35 µg mL-1, 2.42 µg mL-1 and 26.0 µg mL-1, respectively. Finally, Al, B, Co, Cr, Cu, Fe, Mg, Mn, Pb and Zn concentrations in various types of vinegar samples were determined.


74

P19Speciation extraction of Cr(VI) from Bulgarian soil samples

Tsvetomil Voyslavov*, Stefan Tsakovski, Sonya Ganeva

University of Sofia � St. Kliment Ohridski� , Faculty of Chemistry and Pharmacy,1 James Bourchier Blvd., 1164 Sofia, Bulgaria

*[email protected]

A selective, fast and reliable procedure for determination of Cr(VI) in aqueous and alkali soil extracts was developed. The hexavalent chromium species were isolated in organic phase (xylene) as ion pair with trioctylmethylammonium chloride (Aliquat 336) and quantified by ETAAS. The optimization procedure included examination of the influence of i) shaking time; ii) pH value; iii) extraction time. The optimization was performed using leachates from various soil types. The comparison between the standard EPA 3060A method and the proposed of the present study procedure showed a satisfactory agreement.

The procedure was applied to agricultural and industrially contaminated soils. The content of Cr(VI) varied in the range 40 � 190 [ng/g] in aqueous and 60 � 425 [ng/g] in alkali soil extracts. In addition the distribution of Cr between fulvic and humic acids soil fractions was determined after their chemical separation.

AcknowledgementThe authors are grateful for financial support of Project Number E02/7 of Bulgarian National Science Fund.


75

P20First investigation of bromate in Bulgarian water for human

consumption

Vera Pavlova1*, Alexandar Kirilov2, Zlatka Bratanova1, Irina Karadjova3

1National Centre of Public Health and Analyses, � I. Geschov� Str. 15, 1431 Sofia, Bulgaria2Metrohm Bulgaria Ltd., � Chiprovtsi� Str. 12, 1303 Sofia, Bulgaria

3Sofia University � St Kliment Ohridski� , Faculty of Chemistry, 1 James Bourchier Blvd., Sofia 1126, Bulgaria

*[email protected]

Bromate may be formed in water during ozonation as one of the disinfection byproducts when the bromide ion is present. Under certain conditions, bromate may also be formed in concentrated hypochlorite solutions used to disinfect drinking water. Bromate is a carcinogen. The maximum permissible level of the bromate is 10 µg/l according to the Council Directive 98/83/EC (Drinking Water Directive) which is transposed in Bulgarian legislation as Ordinance № 9/2001 for quality of the drinking water. In this study, 16 samples of water for human consumption (5 mineral, 6 table and 1 spring waters and 4 water samples from drinking water supplies of the biggest cities in Bulgaria � Sofia and Plovdiv) were investigated for occurrence of bromate and bromide. Bromide was detected in 9 samples in concentrations between 0.6 and 105 µg/l. Bromate was found in 2 samples of table water and in a sample of mineral water in the range 4 to 7 µg/l. This is only a first investigation of potential risk for bromate formation during disinfection of water by ozonation in Bulgaria. Nevertheless that there are no samples with concentration higher than the maximal level, the amounts of bromate close to 10 µg/l are an indication that more detailed studies are necessary.


76

P21Speсtrophotometry determination of Manganese (Mn), Chrome

(Cr), Selenium (Se) and Vanadium (V) in plant materials

Ekaterina Raboshvil*, Aleksander Chebotaryov, Aleksander Zacharia,Irina Efimova

Odessa National University, Department of Analytical Chemistry, Dvoryanskaya Str., 2, 65082 Odessa, Ukraine

*[email protected]

The results of spectrophotometric determination of biometals: manganese, chrome, selenium and vanadium in some of plant materials are presented. Despite of its essential physiological role, with increasing of their concentrations these metals can negatively influence on organism live. Therefore, analytical chemistry control over their contents in appropriate materials is actual.

Including well-known methods: electrothermal atomic absorption spectrometry (ET-AAS), inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma-mass spectrometry (ICP-MS) in analytical practice of many industrial and research laboratories the molecular spectrophotometry till now is widely used. However, one of its significant drawbacks is low selectivity.

The present work is devoted to investigation of the possibilities for using of 4-sulfo-2(4′-sulfonaphthalene-1′-azo)-naphthol-1 (Karmoazin), as sensitive and selective redox-reagent for spectrophotometric determination of Mn, Cr, Se and V in different types of legumes, oats and wheat.

As analytical forms for the above mentioned elements determination their appropriate complex compounds with Karmoazin have been proposed. At the same time their main physico-chemical and analytical characteristics were calculated: Mn:R = 1:1; pH − 2; t° ≈ 20°C; λmax = 370 nm; Cr:R = 1:3; pH − 2; t° ≈ 80°C; λmax = 600 nm; Se:R = 1:4; pH − 0.5; t° ≈ 80°C; λmax = 370 nm; V:R = 1:3; pH − 0; t° ≈ 80°C; λmax = 365 nm.

It was established that with changing of pH from strong acid (2М H2SO4) to pH 2.0 as well as the mixture temperature the determination of Mn, Cr, Se and V without previously separation and concentration procedure is possible.

The investigated materials (5� 20 g sample) after dissolving in mineral acids mixture ware analyzed at optimized conditions.

The low limit of detectable concentration of Mn, Cr, Se and V in legumes, oats and wheat are 2.2; 1.1; 3.95 and 0.65 ppm, correspondingly. Trueness of the analysis results were checked by its comparing with different analytical method. In any case the relative standard deviation (Sr) at n=3 and P=0.95 does not exceed 6%.

It was established that the presence of К, Ca, Si, Mg, Na, S, P, Cl, Al, B, Fe, Co, Cu, Mo, Ni, Ti, Zn, F, I, does not interfere the spectrophotometric determination of Mn, Cr, Se and V with Karmoazin. The proposed method is simple and not expensive.


77

P22Synthesis and characterization of new sorbents for solid phase

extraction of triazine herbicides in surface waters

Maria Mitreva1*, Ivanka Dakova1, Irina Karadjova1, Vera Pavlova2,Zlatka Bratanova2

1Faculty of Chemistry and Pharmacy, University of Sofia � St. Kliment Ohridski� , Bulgaria2National Centre of Public Health and Analyses, Sofia, Bulgaria

*[email protected]

Triazine compounds are widely used herbicides in agriculture to protect crops from adverse broadleaf weeds by inhibiting photosynthesis. They have a relatively low absorption in the soil and thus easily pass into the surface water and groundwater. The concentration levels of triazine herbicides found in drinking and natural water samples are typically in the order of μg/L. These levels are too low for direct HPLC analysis. Therefore, a fast and compatible preconcentration step is necessary prior to the analysis. In analytical practice solid phase extraction (SPE) is widely used approach which ensures high preconcentration factors and interference free measurements. However, the extraction efficiency of this technique is strongly dependent on the sorbent material used.

In this study new sorbents (PMAA/Sil) were synthesized, characterized and tested for HPLC determination of triazine herbicides in surface waters. PMAA/Sil were prepared by coupling free radical copolymerization of methacrylic acid and methacryloxypropyltrimethoxysilane and sol� gel processing, using tetramethoxysilane as cross-linker. Scanning electron microscopy and Fourier transform infrared spectroscopy were used for the characterization of the copolymers. The separation and preconcentration characteristics of the sorbents for triazine herbicides were investigated by dispersive solid phase extraction. PMAA/Sil presented high recoveries at pH values in the range of 5 to 8. The desorption of the triazine herbicides carried out successfully when used methanol and a mixture of methanol and acetic acid as eluent. Experiments performed for determination of triazine herbicides in various types surface waters showed that the interfering matrix did not influence the extraction efficiency of PMAA/Sil.

AcknowledgementThe authors are grateful for financial support of Sofia University Scientific Foundation (Grant № 158/2015).


78

P23Development and validation of a reversed� phase HPLC method

for determination of ketoconazole in pharmaceutical formulations

Olga Popovska1*, Zoran Kavrakovski2, Vesna Rafajlovska1

1Ss. Cyril and Methodius University in Skopje, Faculty of Technology and Metallurgy, Rudjer Boskovic 16,1000 Skopje, Republic of Macedonia

2Ss. Cyril and Methodius University in Skopje, Faculty of Pharmacy, Vodnjanska 17,1000 Skopje, Republic of Macedonia

*[email protected]

A simple, accurate and rapid RP� HPLC method has been developed and validated for determination of ketoconazole in pharmaceutical formulations such as tablets, cream and shampoo. The RP� HPLC separation was achieved on the column LiChrospher®100 C-18 (150 mm, 4.6 mm, 5 μm) using mobile phase methanol:water (90:10 v/v) with pH adjusted to 8.90 with phosphate buffer. The flow rate was 1.0 mL/min at 25ºC. The linearity of the method was determined at 296 nm with array detection. The coefficient of determination (R2) was higher than 0.999. The limit of detection (LOD) was 9.383 µg/mL and the limit of quantification (LOQ) was 28.434 µg/mL. The obtained results were statistically evaluated by using ANOVA test. The intra- and interday assay was within 2% relative standard deviation. The accuracy of the method was proved with standard addition method at four levels (0%, 80%, 100% and 120%). The robustness of the method was determined by changing the flow of the mobile phase (0.9 and 1 mL/min), while the column temperature was set at 23 and 25ºC. The determined ketoconazole content in the analyzed pharmaceutical samples was in agreement with the declared values.


79

P24A HPLC method for determination of ketoconazole in small

unilamellar vesicles

Olga Popovska1, Zoran Kavrakovski2, Vesna Rafajlovska1

1Ss. Cyril and Methodius University in Skopje, Faculty of Technology and Metallurgy, Rudjer Boskovic 16,1000 Skopje, Republic of Macedonia

2Ss. Cyril and Methodius University in Skopje, Faculty of Pharmacy, Vodnjanska 17,1000 Skopje, Republic of Macedonia

*[email protected]

The small unilamellar vesicles (SUV) as liposomal formulations of ketoconazole were prepared by using ultrasound method (at 25ºC, for 10 minutes in ultrasonic bath). L-α-phosphatidylcholine (egg yolk), cholesterol and ketoconazole in weight ratio 3.3:1:3.3 were used in the preparation of liposomes. The separation of the liposomal and the free amount of ketoconazole was achieved on a LiChrolut® reversed� phase C-18 cartridge. The ketoconazole content in fractions was determined by RP� HPLC analysis on a LiChrospher®100 column (150 mm x 4.6 mm, 5 µm particle size, Merck, Germany) using mobile phase methanol:water (90:10 v/v) with pH adjusted to 8.90 with phosphate buffer. The column temperature was set at 25ºC. The linearity of the validated HPLC method was determined at 296 nm in the range of 0.05 � 0.25 mg/mL. The intra- and interday assay was within 2% relative standard deviation. The drug encapsulation efficiency was 90%.


80

P25Application of methods for determination of trace elements in

blood serum in children with primary hypertension (PAH)

Atanaska Bozhinova1*, Maria Angelova1, Nadia Kolarova-Ianeva2,Vania Nedkova2

1Department of Chemistry and Biochemistry & Physics and Biophysics, University of Medicine,Pleven, Bulgaria

2Department of Pediatrics, UMHAT D-r Georgi Stranski, University of Medicine, Pleven, Bulgaria

*[email protected]

The aim of our study was to determine serum concentrations of Zn, Cu and Cr (SZn, SCu and SCr) - markers of micronutrient status in adolescents with PAH.

Contingent and method: Investigation was carried out on 75 children with PAH and 25 healthy children - a control group aged 10 − 17 years.

Blood pressure of childrens was measured by standard auscultatory method.Spectrophotometric methods based on Giesse diagnostics" and "Audit Diagnostics"-

Roma-Italy were applied for the determination of SZn, SCu respectively. Modified spectrophotometric method, developed in the laboratory was used for the determination of SCr.

The package IBM SPSS 19.0.0 was used for the statistical processing of the results obtained.

Results: Statistically significantly lower (statistical reliability p < 0.001) results for SZn and SCr content were found for children with PAH � reduction of about 80%.

About 77 − 78% (n = 46 − 47) of the children with PAH and low SZn and SCr (n ≈60) were overweight. The differences between them and children with PAH and normal weight was statistically significant pZn < 0.05 and pCr < 0.05. Odds ratio (OR) indicates that obese adolescents were about 3 times more often deficient in Zn and Cr.; OR Zn = 2.87 and OR Cr = 3.54 with n = 75. SCu in hypertensive students was below normal, statistically unsignificant difference from controls, p > 0.05 was observed. We did not find a correlation between body weight and SCu for students with PAH, 72.3 percent of whom are overweight, P > 0.05.

Conclusions: Suitable analytical methods were applied for determination of SZn, SCuand SCr. Defined optimal conditions for sample mineralization and volume reduction ensures lower limit of detection and better reproducibility, precision, selectivity and sensitivity of in-house method for SCr determination.

A low serum concentration of micronutrients in adolescents with PAH compared to controls may be explained with unhealthy diets. The correlation between scarcity of Zn and Cr and overweight talks about an increased risk of various diseases.AcknowledgmentWe would like to express our gratitude to the Medical University of Pleven.


81

P26UV spectrophotometric method development for the

determination of Iron and Aluminum in natural waters and evaluation of the data obtained from the calibration of PCR and

PLS methods

A. Hakan Aktaş*, Bengisu Mutlutürk

Süleyman Demirel University, Science & Art Faculty, Department of Chemistry, Isparta, Turkey

*[email protected]

In this study, the method for Fe³⁺ and Al³⁺ determination using two distinctive ligand chrome azurol S (CAS) and pyrocatechol violet (PCV) followed by UV-VIS spectrophotometry is described. Optimum parameters (ligand amount, pH, waiting period, relation between metal concentration and absorbance, foreign ion effect) were studied. Experiments performed showed that method based on chrome azurol S (CAS) ensures more stable and reproducible results and this approach was applied for Fe³⁺ and Al³⁺determination in natural waters. Principal component regression method (PCR) andpartial least squares method (PLS) were applied for statistical treatment of results obtained.

AcknowledgementThis research work has been supported by research grants from Süleyman Demirel University Scientific Research Project 3681-YL1-13.


82

P27Analytical Atomic Spectrometry for the determination of

chemical elements in surface waters

Lyubomir Djerahov1*, Katerina Bačeva2, Olga Veleva3, Petya Dimitrova4, Metody Karadjov3*

1Faculty of Chemistry and Pharmacy, University of Sofia � St. Kliment Ohridski� , Bulgaria2Research Center for Environment and Materials, Macedonian Academy of Sciences and Arts, Krste Misirkov 2,

1000 Skopje, Republic of Macedonia2Bulgarian Academy of Sciences, Geological Institute, Acad. G. Bonchev Str. BL. 24, 1113 Sofia, Bulgaria

3Executive Environment Agency, Regional Laboratory Plovdiv, Perushtitsa Str. 1, Plovdiv, Bulgaria

*[email protected]

The primary goal of the Water Framework Directive is to achieve a good ecological and chemical status of surface waters in all the member states. To that purpose, water qualitystandards have been issued, either by the Commission (for the priority substances), or by themember states themselves (for other relevant substances). In case of non-compliance with thestandard, member states are allowed to take natural background concentrations and/or bioavailability into account. However, the WFD does not provide strict regulation pertaining to the derivation of background concentrations. Each member state can decide to do so for itself. Various approaches could be used, however for each approach choosed important analytical task is accurate determination of extremely low concentrations of chemical elements in pristine areas. Analytical methods used could be divided into two big groups �direct multielement methods like ICP-MS or TRXRF or methods based on preliminary separation and enrichment followed by multielement measurement. Biotic ligand model is widely accepted as a tool for bioavailability assessment of chemical elements. Evidently previous accurate determination of total concentration of chemical elements is unavoidable analytical task. In the present study the possibilities of ICP-MS and TRXRF for fast and accurate simultaneous determination of priority and specific (for Bulgaria) pollutants � Al, As, Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn in river and lake waters from national monitoring network have been discussed. As a second alternative approach solid phase extraction by using chitosan membrane with incorporated Ag nanoparticles was tested. Optimal chemical parameters for quantitative sorption of trace elements on membranes were defined. Complete membrane dissolution was proposed as an elution procedure. Both instrumental methods ICP-MS and TRXFR were studied and compared for measurement of chemical elements enriched on the surface of the membrane. Results obtained for several river and lake samples have been presented.

AcknowledgementThe authors are grateful for financial support of Bulgarian Academy of Sciences (Bulgaria Macedonia bilateral projects).


83

P28Simultaneous determination of food colorants in commercial

products by UV spectrophotometry

Fethiye Göde, A. Hakan Aktaş

Süleyman Demirel University, Science & Art Faculty, Department of Chemistry, Isparta, Turkey

[email protected]

The principal component regression (PCR) and partial least squares (PLS) methods were applied to process spectrophotometric data of mixed tartrazine (TA) and sunset yellow (SA). The method was used for simultaneous determination of mixed colorants in commercial products on sale with satisfactory results. Therefore, the PCR and PLS may provide a new approach to determine the mixed colorants is synthetic food drink by spectrophotometry without any preliminary chemical separation. The aim of this work is to propose the application of PCR and PLS methods to resolve mixtures of colorants in commercial products by using solid phase spectrophotometry. The proposed methods are rapid, easy to apply, not expensive and suitable for analyzing of colorants in a commercial products. The method takes advantage of the sensitivity and selectivity.

References[1] Aktaş, A.H., Pekcan, G., (2006). Asian Journal Of Chemistry, 18(3),2025-2031.[2] Dinç, E., Aktaş, A.H., Baleanu, D., Ustundag, O., (2006). Journal of Food and Drug Analysis, 14 (3), 284.


84

P29Determination of Polychlorinated biphenyls (PCBs) in

contaminated soils

Touabet Abdelkrim*, Halfadji Ahmed

Université des Sciences et de la Technologies Houari Boumediene, Laboratoire d� Analyse Organique Fonctionnelle, Faculty of Chemistry, BP 32, El Alia, Bab Ezzouar, 16111 Alger, Algeria

*[email protected]

During last decades, the chemical pollution of the environment did not cease increasing with increasing industrialization and the urbanization. Among the major organic pollutants of our environment one finds hydrocarbons aromatic polycyclic (HAPs) and Polychlorinated biphenyls (PCBs). Environmental risks associated with these compounds are related to the carcinogenic character of several PCB, in addition to their persistence, their hydrophobic character and their toxic properties.

In the first part of this work, we analyzed the PCBs contained in the soils of storage areas of transformers. The quantitative determination showed that the suspected site was effectively polluted. The extraction of PCBs was performed by soxhlet technique. After extraction with an appropriate solvent the extracts were separated by capillary column gas chromatography and the PCBs were identified according to their retention indices then confirmed by gas chromatography hyphenated to mass spectrometry.

In the second part, we carried out the remediation of soils by phytodimerization. The selected plants are the cucumber and cypress. The degradation of PCBs was followed by GLC. The results show a significant decrease of PCBs contained in the polluted soils.


85

P30Model and method validation for the determination of chlorophyll

catabolites

Nina Djapic

Technical Faculty � Mihajlo Pupin� , Djure Djakovica bb, 23000 Zrenjanin, Serbia

[email protected]

The model validation was done with 7 standards which were sufficient to ensure the Y-domain. All models evaluated were based on partial least square regression for one y-variable. Criterion used for quantifying the model performances were deviation, the leverage and the x-residuals. For the method validation, data obtained were compared with results obtained by HPLC reference method. It was found for urobilinogenic chlorophyll catabolites that cross validation calculated estimated well the model. Samples were obtained fromHamamelidaceae autumnal leaves extracts. The Hamamelidaceae autumnal leaves chlorophyll catabolite composition is known. The data evaluation and the absorption spectra for sample series were recorded with two HPLC instruments. The wavelength was in the range 240 � 320 nm. The results obtained showed a minor difference between data recorded.


86

P31Determination of heavy metals in some Turkish beers

Gülşah Teke1, Metehan Yazıcıoğlu2, R. Ertan Anlı3, Sevi Öz1*

1Ahi Evran University, Faculty of Science and Arts, Department of Chemistry, 40100 Kırşehir, Turkey2Ankara University, Faculty of Science, Department of Chemistry, 06100 Ankara, Turkey

3Ankara University, Faculty of Engineering, Department of Food Engineering, 06100 Ankara, Turkey

*[email protected]

In this study, concentration of Cr, Fe, Ni, Cu, Zn, Cd, Sn and Pb heavy metals present in 23 different beers produced by the largest beer maker company of Turkey is determined using electrothermal atomic absorption (ETAAS) method. Results were compared by considering can-bottle, low alcohol containing-high alcohol containing and dark-light beers. Comparison has been made on results with the help of the T test. It concludes that only Cr concentration of can beers is higher than bottle packaging. All the results are below the permissible values. Average values for 23 beers are 50.90 for Cr, 82.4 for Fe, 57.49 for Ni,82.52 for Cu, 425.36 for Zn, 3.70 for Cd and 12.50 μg/L for Pb. The standard addition has been performed with arbitrary beer samples for accuracy assessment of the method and recovery values are found between 92% and 104%.


87

P32Use of radioactive isotopes for determination of geochemical

behavior of Co, Mn, Y and Zn after sharp temperaturechange � a model study

Petya Kovacheva1*, Miryana Slaveikova1, Marin Ayranov2,Dorothea Schumann2

1Faculty of Chemistry and Pharmacy, University of Sofia, 1164 Sofia, Bulgaria2Paul Scherrer Institute, CH-5232 Villigen PSI, Switzerland

*[email protected]

Substantial changes of environmental temperature can influence the soil properties, for example pH, cation exchange capacity (CEC), redox potential, organic matter decomposition, leading to change in microbial activity, element leaching or ion-exchange processes. This might provoke changes in the geochemical fractionation of the elemental contaminants and influence their transfer within the trophic chain. This paper presents the impact of the sharp raise of environmental temperature on the geochemical behavior of Co, Mn, Y and Zn, studied by using their radioactive isotopes: 60Co (T1/2 = 5.27 y), 54Mn (T1/2 = 312.5 d), 88Y (T1/2 = 107 d) and 65Zn (T1/2 = 244 d). Four soil types, taken from different regions in Bulgaria were contaminated with aqueous solution of the radionuclides and stored in climate chamber at two regimes of temperature, air humidity and soil moisture for one month. The geochemical forms of 60Co and 54Mn were studied by three-stage sequential extraction procedure, recommended by the European Community Bureau of Reference (BCR procedure). The water-soluble, exchangeable forms of 88Y and 65Zn, and the forms, bound to humic and fulvic acids were determined by single extractions. HPGe detector Canberra 7221 coupled to a 16000-channel analyzer DSA-1000 was used and the gamma spectra were processed by Genie-2000 Basic Spectroscopy Software. Activity of the radionuclides was measured using the following gamma energies: 60Co at 1173.2 keV and 1332.5 keV gamma peaks, 54Mn at 834.8 keV, 88Y at 1836 keV and 898 keV and 65Zn at 1115.5 keV peak. The general characteristics of the studied soils, including pH in H2O and in 0.1 M KCl, CEC (cmol+ /kg), relative content of sand, silt, clay, humus and the mineral composition of the crystal phase of the soil samples, determined by X-ray diffraction analysis were considered. The results showed that temperature raise leads to immobilization of 54Mn in all soil types and increase of mobile forms of 60Co in chernozem soils. The impact of sharp warming on the geochemical forms of 88Y and 65Zn is higher for soils with sandy-loam texture, compared to those with loamy-sand texture.

AcknowledgementThe authors gratefully acknowledge the financial support of the National Science Fund, Ministry ofeducation, youth and science of Bulgaria, Contract No. DDVU 02-60/2010.


88

P33Removal of Pb(II) from aqueous solutions using nanostructured

hybrid material containing titanium

Albena Detcheva*, Paunka Vassileva, Ralitsa Georgieva

Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences,Acad. G. Bonchev Str., bl. 11, 1113 Sofia, Bulgaria

*[email protected]

High concentrations of toxic ions in surface water are generally associated with the disposal of industrial wastes. Metal-containing industrial effluents constitute a major source of metallic pollution of the hydrosphere. The metals are of special concern because they are non-degradable and therefore persistent. Lead ions exhibit specific toxicity effects; for that reason, they have been classified as priority pollutant.

Numerous techniques and treatment technologies have been developed for removal of toxic elements from contaminated water. Methods based on physical and chemical adsorption recently find wide application and most studies are concentrated on searching for more effective adsorbents. On the other hand, modified silica containing materials can be used for technological applications such as extracting metal ions from aqueous and non-aqueous solutions because they show great adsorption capacity and specificity for metal ions.

In the present study the adsorption properties of a novel di-urethanesil hybrid material modified by titanium was studied. Adsorption experiments towards Pb(II) ions were carried out by means of the batch method, using aqueous solutions with different concentrations and acidity. The initial and equilibrium concentrations of the Pb(II) ions were determined by flame AAS. The results showed that the adsorption was significantly affected by the pH value. Pseudo-first order, pseudo-second order and intraparticle diffusion models were used to analyse kinetic data. Equilibrium modelling data were fitted to linear Langmuir, Freundlich and Dubinin-Radushkevich models. Best fitting was observed by the Freundlich model, which showed correlation coefficient of 0.9951. Thermodynamic parameters, such as ΔG°, ΔH° and ΔS° were calculated. The negative values of Gibbs free energy and enthalpy changes indicate that the adsorption of lead ions is spontaneous and exothermic.

The effects of presence of co-cations on Pb(II) adsorption capacity was also investigated. The adsorption capacities in single- and multicomponent media were determined. It was found that the adsorption of Pb(II) from multicomponent aqueous solutions was affected significantly by the presence of competing ions. Nevertheless the novel nanostructured hybrid material could be used for lead removal from contaminated aqueous solutions.


89

P34Ultrasound assisted ionic liquid dispersive liquid-liquid

microextraction of Curcumin and its spectrophotometricdetermination in food samples

Mustafa Tuzen1*, Yunus Emre Unsal1, Mustafa Soylak2

1Gaziosmanpasa University, Faculty of Science and Arts, Chemistry Department, 60250 Tokat, Turkey2Erciyes University, Faculty of Sciences, Department of Chemistry, 38039 Kayseri, Turkey

*[email protected]

Curcumin (E100) is the basic colour present in the turmeric plant (Curcuma domestica). A new ultrasound-assisted ionic liquid-based microextraction procedure method is developed for the determination of curcumin in food samples by UV visible spectrophotometry. The ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]) is used to extract curcumin from sample solution with the aid of sonication in an ultrasonic bath. The optimum extraction efficiency of curcumin was found after the examined of conditions such as ionic liquid and dispersive solvents, pH, centrifugation speed and time, ultrasonic bath time and temperature. The effects of diverse ions on the recovery of curcumin were also examined. The limit of detection (LOD) and the relative standard deviation (RSD) were 0.51 μg L− 1 and 4.3%, respectively. The method was performed to the determination of curcumin in food samples. This method has some advantages such as simple, minimum use of toxic organic solvent, low cost, environmental friendly, rapid and sensitive.

AcknowledgementThe authors are fully grateful for the financial support of the Unit of the Scientific Research Projects of Gaziosmanpasa University (Project number: 2012/45). Dr. Mustafa Tuzen thanks to Turkish Academy of Sciences for financial support.


90

P35Determination of antidepressants in biological samples using

magnetic solid phase extraction followed by liquid chromatography-ultraviolet detection

Şevket Ata1*, Merve Berber1, Hasan Çabuk1, Mehmet Akyüz2

1Bülent Ecevit University, Faculty of Arts and Sciences, Department of Chemistry, Zonguldak, Turkey2Bülent Ecevit University, Faculty of Pharmacy, Department of Analytical Chemistry, Zonguldak, Turkey

*[email protected]

In this study, a novel and sensitive magnetic solid phase extraction (MSPE) method based on Fe3O4-MgSiO3 magnetic nanocomposite was developed for extraction and preconcentration of new generation antidepressants such as venlafaxine, escitalopram, paroxetine, sertraline and fluoxetine in biological samples followed by liquid chromatography-ultraviolet detection (LC-UV). The influence of factors such as: adsorbent amount, extraction pH and desorption solvent volume on the extraction efficiency of antidepressants was studied. The optimal values were obtained by using central composite design as a response surface methodology. The optimum conditions for quantitative recoveries applying magnetic extraction were found to be adsorbent amount: 12.5 mg, extraction pH: 7.4 and desorption solvent volume: 1.3 mL. Under the optimum experimental conditions, a good linearity was observed for all the analytes, with the square of correlation coefficients (r2) ranging from 0.9986 to 0.9994. The limit of detection and limit of quantification for drugs were found to be in the range of 1.7 − 2.8 and 5.2 − 8.5 ng mL-1, respectively. This method was successfully applied for the analysis of real biological samples at different spiked concentrations, and the obtained recoveries ranged from 72 to 115 % with the relative standard deviations (RSDs) below 4.75 %.

AcknowledgementThe authors wish to thank Bülent Ecevit University for the opportunity and support to carry out this research.


91

P36The solid phase extraction of heavy metals using polysaccharides

coated titanium nanoparticles by GFAAS

Ceren Kuznek1, Asli Baysal2*, Mustafa Ozcan1

1Istanbul Technical University, Faculty of Science and Letters, Department of Chemistry,34469 Maslak, İstanbul

2Istanbul Aydin University, Health Services Vocational School of Higher Education,34295 Sefakoy, Kucukcekmece - Istanbul, Turkey

*[email protected]

To eliminate some interferences, some preconcentration/separation methods can be used for the sorption of metals in different samples. Numerous inorganic and organic, natural and synthetic materials directly or modified with a chelating group, bacteria, etc., have been used as sorbents all of which have their own advantages and disadvantages. Nowadays,

nanomaterials such as nano carbon tubes, nano ZrO2, TiO2, SiO2, and their modified

materials are commonly and successfully used as sorbent [1-3].In this study, a challenging preconcentration/separation method based on the sorption

of cadmium, cobalt, copper, nickel, lead on polysaccharides coated titanium nanoparticles and its analysis by electrothermal atomic absorption spectrometry was described. Optimum conditions for quantitative sorption were investigated. The analyte elements in certified sea-water samples were determined in the range of 95% confidence level. The proposed technique is fast, simple and environmental friendly.

References[1] A.Baysal, M.Kahraman, S.Akman, Current Anal. Chem., 5, 352-357 (2009)[2] N.Aydemir, N. Tokman, A.T. Akarsubasi, A.Baysal, S. Akman, Microchim Acta 175,185� 191 (2011)[3] A.Baysal, A.D. Saatci, M.Kahraman, S.Akman, Microchim. Acta 173,495-502 (2011)


92

P37Determination of the distribution coefficients of lanthanides on

UTEVA resin using radioisotope markers

Genko Marinov1,2*, Maria Milanova1, Dmitry Vladimirovich Filosofov2

1University of Sofia, Faculty of Chemistry and Pharmacy, 1 J. Bourchier Blvd., 1164 Sofia, Bulgaria2 Joint Institute for Nuclear Research, DLNP, 141980 Dubna, Russian Federation

*[email protected]

Due to the lanthanides (Ln(III)) similar properties their separation presents great interest and is still an object of investigations. Different methods are developed and applied for their separation. In order to obtain Ln(III) for model investigations a proton irradiated metallic Ta target can be used. The process includes dissolving of the irradiated Ta target and the separation of the Ln(III) isotopes as a group. The next step is separation of the Ln(III) from one another. For that purpose a known method using of ammonium α-hydroxyisobutyrate on column filled with ion-exchange resin is applied. The so obtained pure elements are then used for the determination of the distribution coefficients on UTEVA (Uranium and TEtraValent Actinides) resin. The relatively new resin UTEVA shows a great promise in separation techniques, although the resin� s primary use is for separation of actinides(IV), and for Am(III) as well. Considering the fact that the trivalent state of Ln is the common one for these elements, it is worth trying to determine the distribution coefficients for Ln(III) with UTEVA resin. The combination of Ln(III) ions is chosen by the intensity of their γ-lines and absence of interference. Gama-spectrometry is the measurement technique used for detection of Ln(III).

AcknowledgementThe authors are grateful for financial support of the Nuclear Regulatory Agency of Bulgaria.


93

P38Optimization of extraction parameters for fat soluble vitamins

and metal analysis in polygonum cognatum Meissn

Halil İbrahim Ulusoy1*, Hilal Acıdereli1, Songül Ulusoy2

1Cumhuriyet University, Faculty of Pharmacy, Department of Analytical Chemistry, 58140 Sivas, Turkey2Cumhuriyet University, Faculty of Science, Department of Chemistry, 58140 Sivas, Turkey

*[email protected]

The analysis of micronutrients in foods is of great interest both as regards nutrition and commercial aspects. These kinds of analysis are so important in order to know contents of foods and environmental samples in view of their toxicity and essential properties. Polygonum cognatum Meissn is a wild edible plant called � madimak� in Turkish. This edible plant is perennial of slender woody stock. It grows on roadsides, slopes and cliffs at altitudes of 720 � 3000 m. The young shoots with leaves are collected in spring. In Turkish folk medicine, it has been used for various purposes, such as its diuretic effect and for the treatment of diabetes mellitus. Best of our knowledge, the detailed chemical analysis of Madimak was performed the first times.

The concentrations of fat soluble vitamins (A and E) and metals (Ca, Cd, Cr, Co, Cu, Fe, Mg, Mn, Pb, Zn) in Polygonum cognatum Meissn (Madımak) plant samples collected from Sivas, Turkey have been determined by HPLC after soxhlet extraction and flame atomic absorption spectrometry after microwave digestion, respectively. Both soxhlet extraction and microwave digestion method were optimized before determinations. The reliability of results was confirmed by recovery experiments in spiked samples. Two different samples obtained from different district were analyzed at optimized conditions. Recovery values were in the range of 96% and 105% while relative standard deviations (RSD) were in the range of 1.7% and 8.5%. The contents of vitamin E in the studies plant were determined as 63.008 ± 4.548 mg kg-1 and 59.178 ± 5.142 mg kg-1. The amount of essential metals such as Mn, Zn, Fe were higher than most of common vegetable and enough to supply daily mineral requirement.

AcknowledgementThe present study was performed with partly contributions obtained from projects (ECZ-002, ECZ-004) supported by Cumhuriyet University Scientific Research Projects Commission.


94

P39Removal of reactive black 5 from aqueous solutions by nano-TiO2

immobilized on activated carbon

Hanane Belayachi*, Sarra Bourahla, Mostefa Belhakem

Université Abdelhamid Ibn Badis, Laboratoire de structure, élaboration et application des matériaux moléculaires, BP 227, Mostaganem, Algérie

*[email protected]

Adsorption onto activated carbon (AC) and oxidation using photocatalyst are widely used techniques for dyes removal from waste water. The aim of this work is to increase the removal capacity of activated carbon by combining AC and titanium dioxide (TiO2) in a Photocatalytically Regenerative Activated Carbon.

Anatase titania were deposited on powder activated carbon made from grape seeds (AGS) by impregnation/mixing method and then the composite photocatalyst was employed for the removal of reactive black 5 from aqueous solution. The TiO2/AGS was characterized by BET, MEB, XRD and optical absorption spectroscopy. The BET surface area and the pore structure of composite photocatalyst (TiO2/AGS) and activated grape seeds (AGS) were evaluated from nitrogen adsorption data at 77 K in relation to process conditions. Our results indicate that the photocatalytic activity of TiO2/AGS was much higher than single phase titania. The adsorption equilibrium of reactive black 5 from aqueous solutions on the examined materials was investigated. Langmuir, Freundlich, and Redlich � Petersen models are in good agreement with the experimental equilibrium data. The degradation kinetics fitted well to the Langmuir-Hinselwood pseudo first order rate low. The photo catalytic activity of TiO2/AGS was much higher than virgin TiO2. COD removal was measured at regular intervals to quantify the mineralization of the dye. Above 96% degree of mineralization was observed. These results suggest that UV-irradiated TiO2 immobilized on activated carbon may be considered as an adequate process for the treatment of diluted colored textile waste water.


95

P40Spectrophotometric methods for the simultaneous estimation of

ezetimibe and rosuvastatin in a binary mixture

Engin ER, Nevin ERK*

1Ankara University, Faculty of Pharmacy, Department of Analytical Chemistry, 06100 Ankara, Turkey

*[email protected]

This work is concerned with the simultaneous estimation of ezetimibe and rosuvastatin in a binary mixture form by two spectrophotometric methods. The first method involved first derivative spectrophotometry. In this method, the first order derivative absorption at 223.045 nm (zero-crossing point of rosuvastatin ) was used for ezetimibe and 223.045 nm (zero-crossing point of ezetimibe) for rosuvastatin. The linear calibration graphs were found to be 4.0 − 36.0 μg ml-1 with a linear correlation coefficient of 0.9970 for ezetimibe and 4.0 − 36.0 μg ml-1 with a linear correlation coefficient of 0.9948 for rosuvastatin in a binary mixture. Other method, ratio spectra first derivative spectrophotometric technique, is based on ratio first derivative spectrophotometry, the amplitudes in the first derivative of the ratio spectra at 236.638 and at 238.582 nm were selected to determine for ezetimibe and rosuvastatin in the binary mixture. The described methods were successfully applied to the analysis of ezetimibe and rosuvastatin in laboratory-prepared mixtures and pharmaceutical dosage forms with good recoveries and their validation was carried out following the ICH guidelines. The results obtained from first derivative spectrophotometric method were comparable with those obtained by using ratio spectra first derivative spectrophotometry. These validated spectrophotometric methods are potentially useful for a routine laboratory analysis because of its simplicity, rapidity, sensitivity, precision and accuracy.


96

P41Fat soluble vitamin� s content of aquaculture freshwater fish from

Bulgaria

Diana A. Dobreva*, Zlatina Peteva, Stoyan Vutov

Medical University of Varna, Department of Chemistry, Faculty of Pharmacy, 55 Marin Drinov St.,9000 Varna, Bulgaria

*[email protected]

Background and objectives: Many studies suggest that fish are valuable health food, high in proteins, bioactive compounds and beneficial fats. They are regarded as the important natural food sources of fat soluble vitamins, which are necessary for a healthy diet. Fish aquaculture has been the world's quickly developing sector of food production branch. Today aquacultured fish currently accounts for over one-quarter of all consumed by humans fish (FAO, 2014). The process of farming helps to control both sides - nutrition duality and safety of this food (NOAA Fisheries, 2011). The some of freshwater fish species, which have been an object of breeding in Bulgaria, are warm water African sharptooth catfish (Clarias gariepinus) and cold-water Rainbow trout (Oncorhynchus mykiss). These fish are some of the most commercially important species from Bulgaria. There is limited information in the scientific literature about fat soluble vitamin� s and fatty acids composition in edible tissue of listed above species. The aims of the present study are to determine and compare vitamin A, D3 and E contents in traditionally consumed in Bulgaria farmed freshwater fish.

Methods: The sample preparation procedure includes saponification and extraction of fat soluble vitamins with n-hexane. The extract was dried under nitrogen flow and redissolved in methanol. HPLC analysis was performed on ODS2 Hypersil (250 x 4, 6, 5um) column with a mobile phase of methanol:water = 97:3, 1 ml/min.

Results: Fat soluble vitamins in edible tissue of farmed fish varied significantly among the analysed species. Three vitamin� s content in all analyzed samples are in order Vitamin E > Vitamin A > vitamin D3 The cholecalciferol content on Rainbow trout fillet was specified only five times higher on behalf of Catfish species. According to the Bulgarian dietary standards for ADA of fat soluble vitamins, analyzed fish show low percentages of the RDI of retinol and alpha-tocopherol, while that of cholecalciferol is over half of the recommended daily needs.

Conclusions: The three fat soluble vitamins were found in higher amounts in farmed Rainbow trout. All analyzed fish species are characterized with high cholecalciferol content compared with RDI.


97

P42Synergetic effect of Co(II) on the cloud point extraction of Cr(III)

Kiril Simitchiev1*, Vanya Zapryanova2, Mariya Petleshkova2,Violeta Stefanova1, Veselin Kmetov1

1Department of Analytical Chemistry and Computer Chemistry, University of Plovdiv � Paisii Hilendarski� , 24 Tzar Assen Str., 4000 Plov div, Bulgaria

2student at Faculty of Chemistry, University of Plovdiv � Paisii Hilendarski� , 24 Tzar Assen Str.,4000 Plovdiv, Bulgaria

*[email protected]

Our previous investigations have shown that Cr(III) can be separated from Cr(VI) via microwave-assisted cloud point extraction using Triton X-114 as surfactant. Cr(III) can be selectively extracted from aqueous media by only maintaining the pH of the initial solution in the range 6 − 9 (no additional ligand have to be added to the extraction system). Probably, under the specified conditions, the analyte is extracted after formation of its polynuclear hydroxo-bridged complexes. At relatively high concentrations of chromium (i.e. 1 mg/l) the obtained analytical recoveries were above 90% but the recovery falls down rapidly when the content of Cr(III) is decreased � ca. 40%, 30% and below 5% for 0.1, 0.05 and 0.01 mg/l, respectively.

The current study attempts to improve the chromium extraction at low concentration levels by evaluating the efficiency of the following three approaches: i) initial heating (hot plate heating or microwave irradiation) of the sample solution before the extractant addition; ii) increasing incubation time under microwave irradiation in the presence of Triton X-114 and iii) addition of Co(II) into the extraction system. The carried out experiments proved that the first two approaches do not lead to any reasonable increase in the recovery of Cr(III). However the addition of Co(II) substantially improved the extraction efficiency of the analyte. Conceivable explanation of the last effect can be found in the formation of heteronuclear hydroxo-bridged complexes, containing both Cr and Co.

Central composite design was used to assess the influence and the possible cross-interactions of the following variables: i) water phase pH (5.5 � 10.5); ii) initial concentration of Cr(III) (0.016 � 0.184 mg/l) and iii) Co(II) : Cr(III) mass ratio in the extraction system (1.6 � 18.4). The interactions am ong the variables were statistically insignificant. When the pH was above 6.5 and meanwhile the initial analyte content exceeded 0.05 mg/l the obtained recoveries for Cr(III) were higher than 80%. The tested range of Co(II) excess had no apparent influence on the analyte recoveries.

AcknowledgementThe authors are grateful for financial support of Project Number NI15-HF-001 (NPD, University of Plovdiv � Paisii Hilendarski� ). The authors also ack nowledge T.E.A.M. Ltd. for the complimentary supplied spectrometer Agilent 4200 MP-AES at Faculty of Chemistry, University of Plovdiv.


98

P43Fatty acid composition of freshwater aquaculture fish species

from Bulgaria

Albena Merdzhanova*, Rositsa Stancheva, Jana Angarska

1Medical University of Varna, Department of Chemistry, Faculty of Pharmacy, 55 Marin Drinov St.,9002 Varna, Bulgaria

*[email protected]

Introduction: Aquaculture has been the world's quickly developing sector of food production branch. Farming fish currently accounts for over one-quarter of all fish directly consumed by humans. Many studies suggest that different fish species are valuable health food which is one of the most important dietary sources of essential polyunsaturated fatty acids (PUFA). Farming of fish helps to control both − the nutrition duality and their safety as a food. The most commercially important freshwater fish species cultivated in Bulgarian are warm water Channel catfish (Ictalurus punctatus), African catfish (Clarias gariepinus) and cold-water Rainbow trout (Oncorhynchus mykiss). The aim of the present work is to evaluate the food quality of these species based on fatty acid composition.

Methods: Total lipids were determined according to Bligh and Dyer procedure. Fatty acid (FA) derivatization was done by base-catalyzed transmethylation using 2M KOH in methanol and n-hexane. The fatty acid analysis was performed by GC-MS system.

Results: The fatty acid composition of analyzed fish showed species-specific differences. Rainbow trout samples contained higher average levels of PUFA (42% of total FA) compared to catfish species (30% of total FA). Catfish species presented higher omega 6PUFA than trot. All analyzed species showed significant higher amounts of docosahexaenoic acid (DHA omega-3, up to 15.17%) compared to eicosapentaenoic acid (EPA omega-3, up to 5%). The Omega-3/omega-6 and PUFA/SFA ratios were within the range recommended by WHO/FAO.

Conclusion: All of analyzed freshwater fish species are excellent sources of unsaturated FA. Moreover cultivated rainbow trout are better dietary sources of omega 3 and omega 6 PUFA compared to catfish species. The consumers awareness of what is the nutrition quality based on fatty acid composition of analyzed species might help to increase the consumption of aquaculture fish in Bulgaria.


99

P44Spectrophotometric determination of Butafosfan in veterinary

medicinal products

Maria Yurkevych*, Maria Smolinska, Hryhorii Tesliar

State Scientific-Research Control Institute of Veterinary Medicinal Products and Feed Additives,Donetska street, 11, 79019 Lviv, Ukraine

*[email protected]

The modern market offers a lot of veterinary medicinal products that improve energy metabolism in animals. Among them there is a group of products containing butafosfan � 2-(butylamino) propan-2-ylphosphinic acid (CAS RN 17316-67-5), synthesized by the specialists of "Bayer" company in 1926. Butafosfan enhances the biosynthesis of proteins, activates the most of the functions of liver hepatocytes, increases nonspecific resistance and facilitates bone tissue formation. Finished medicinal forms of butafosfan are produced mainly as combinations with other active ingredients. Such combined medicinal products are used in veterinary medicine in many treatment schemes and with prophylactic purpose. Aiming at quality control of butafosfan-containing medicinal products different methodological approaches are used, including butafosfan content in veterinary medicinal products determined by potentiometric titration, high performance liquid chromatography (HPLC) and gas chromatography. These control methods are quite expensive.

Based on the known literature data the authors developed a method for spectrophotometric determination of butafosfan for phosphorus content in it, namely, the optimal conditions of sample combustion and analytical reaction passage were selected.

The proposed method of quantitative spectrophotometric determination of butafosfan is based on its previous "wet combustion" in the medium of concentrated sulfuric acid at the temperature of about 300°C for 30 min., and further combustion using ~ 32% hydrogen peroxide. After cooling to room temperature and neutralization by sodium hydroxide for phenolphthalein formed phosphate reacts with 0.125% solution of ammonium molybdate in medium of 0.125 M sulfuric acid and 3% solution of ascorbic acid as deoxidant during 1 hour at 30°C. Stained analytical form, known as "molybdenum blue", is characterized by maximum absorbance at 830 nm, color intensity and butafosfan concentration in tested solution is subject to Lambert-Beer law. Metrological characteristics of method are determined: linear range is 0.3 � 9.0 mg/L, the lower limit of determined concentrations is Cmin = 0.40 mg/L, the limit of detection CN = 0.13 mg/L, the linear determination coefficient constitutes R2 = 0.9998.

The used method of butafosfan determination is expressively cheap, it can be used as a routine method in analytical laboratories and allows to determine butafosfan content in veterinary medicinal products with necessary accuracy. Results of obtained analyzes using methods developed for the determination of phosphorus content in butafosfan are consistent with the results obtained as a result of potentiometric titration and HPLC.

http://www.ncbi.nlm.nih.gov/sites/entrez?cmd=search&db=pcsubstance&term=%222%2d(butylamino)propan%2d2%2dylphosphonic%20acid%22%5bSynonym%5d%203082402%5bstandardizedcid%5d

http://www.ncbi.nlm.nih.gov/sites/entrez?cmd=search&db=pcsubstance&term=%222%2d(butylamino)propan%2d2%2dylphosphonic%20acid%22%5bSynonym%5d%203082402%5bstandardizedcid%5d

http://www.ncbi.nlm.nih.gov/sites/entrez?cmd=search&db=pcsubstance&term=%2234691%2d05%2d9%22%5bSynonym%5d%203082402%5bstandardizedcid%5d


100

P45Determination of Iron and Silicon content in industrial slag and

determination of Sodium and Silicon content in alkaline solutions

Christina Tzvetkova1*, Galia Gentscheva1, Nikolay Marinkov1,Ivan Dimitrov1, Yoanna Kostova2

1Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, 1113 Sofia, Bulgaria2Institute of Metal Science, Equipment and Technologies � Acad. A. Balevski� with Hydroaerodynamics centre,

67 "Shipchenski prohod" Str., Sofia, Bulgaria

*[email protected]

A slag, containing as main ingredients iron silicate, magnetite and silicate glass is waste of the pyrometallurgical production of copper. This slag might be used as an unconventional source for production of silica gel, in this way its utilization could have a positive impact on the environment avoiding the deposition of dangerous wastes and protection of soils and waters in industrial zones.

Separation of iron and silicate phases might be performed after treatment of the oxidized slag with alkaline solution. As a result utilization of both phases could be achieved �materials with various properties might be fabricated. However despite of the developmentson the slag treatment with different reagents there is no systematic data on the ways of interactions of the multi component glassy phase with alkaline solutions. The purpose ofanalytical procedures presented in this study is to collect data on the composition ofintermediate and final products of such treatments and thus to clarify the effects of parameters: temperature, reagent composition and process timing.

Analytical procedure has been developed for microwave digestion and ICP-AESdetermination of Fe and Si in the activated slags after their treatment with alkaline solutions. The concentration of Fe was further confirmed by FAAS.

The concentration of Si leached in alkaline solution of the slug is determined by usingtwo independent measurement methods: spectrophotometry and ICP-AES. The difference between data obtained is less than 5%, thus confirming their validity.

ICP-AES determination of Na was used to control its concentration in the alkaline solution.

Initial data for the possibilities to recover Si from the slags by using different alkaline solutions (NaOH and mixtures of NaOH+Na2CO3) for treatment, under different chemical parameters have been obtained.

AcknowledgementThe authors are grateful for financial support of Project DFNI E02-1/2014 of National Science Fund, Bulgarian Ministry of Education and Science.


101

P46Physicochemical parameters and mineral composition ofpumpkin and melon seeds and oils obtained from them

Galia Gentscheva1*, Irina Karadjova2, Krastena Nikolova3,Albena Predoeva4, Zhana Petkova5, Ginka Antova5

1Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences,Acad. Georgi Bonchev Str., Bl.11, 1113 Sofia, Bulgaria

2Faculty of Chemistry and Pharmacy, Sofia University, 1 J. Boucher Blvd., 1164 Sofia, Bulgaria3University of Food Technologies, 26 Maritza Blvd., 4002 Plovdiv, Bulgaria

4Research Institute of Forensic Science and Criminology, POBox 934, 1000 Sofia, Bulgaria5Plovdiv University � P. Hilendarski� , Department of Chemical Technology,

24 Tzar Assen Str., 4000 Plovdiv, Bulgaria

*[email protected]

Elemental composition of seeds of pumpkin: Cucurbita pepo, Cucurbita moschata andCucurbita maxima and melon: Honeydew. Dessert 5 and Hybrid 1 and oils obtained from them were determined. The seeds were previously air-dried and ground to powder. The oils were prepared by extraction with n-hexane in Soxhlet. A microwave assisted decomposition of the seeds and oils in closed vessels using a mixture of nitric acid and hydrogen peroxide was applied as sample preparation procedure. The quantitative determination of trace elements was achieved by ICP-MS measurements under optimized instrumental parameters. Low limits of detection ensured by ICP-MS permits determination of most of the elements of interest. Additionally, the high concentration of the elements like Fe, Ca, Mg have been confirmed by FAAS.

The distribution of essential (Ca, Mg, K, Na, B, Al, Cr, Mn, Fe, Co, Cu, Zn) and toxic (Ni, As, Cd, Hg, Tl, Pb) elements in the system seed/oil was described. Discussion on the migration of different elements from seeds to respective oils is presented. Additionally several physicochemical parameters and their changes in seeds and oils are studied. The color parameters and chlorophyll content was detected in melon species (0.02 − 0.04 ppm) but in pumpkin species these pigments were not observed. In Cucurbita maxima and melon species Hybrid 1 higher quantities of β-carotene were established � 1222.33 ppm and 35.97 ppm, respectively. Luminosity has been investigated for three different sorts from pumpkin and melon seed oils. The pigments investigated are connected with some fluorescent maxima in visible region. The four main fluorescence peaks connected respectively with the presence of tocopherols at λ = 346 nm and 384 nm, of oxidation products at λ = 514 ÷ 520 nm, of chlorophyll at λ = 675 ÷ 678 nm and of pigments at λ = 620 nm and 700 nm have been studied.


102

P47Determination of air pollution with heavy metal in Polog Region,

Republic of Macedonia

Angja Kjulumoska-Gjorgjievska1, Trajče Stafilov1,2, Katerina Bačeva2, Robert � ajn3, Irina Karadjova4

1Institute of Chemistry, Faculty of Science, Sts. Cyril and Methodius University, POB 162,1000 Skopje, Macedonia

2Research Center for Environment and Materials, Macedonian Academy of Sciences and Arts, Krste Misirkov 2, 1000 Skopje, Republic of Macedonia

3Geological Survey of Slovenia, Dimičeva ulica 14, 1000 Ljubljana, Slovenia4Faculty of Chemistry and Pharmacy, University of Sofia "St. Kliment Ohridski", 1 James Bourchier Blvd.,

1164 Sofia, Bulgaria

The purpose of the study was to determine the atmospheric pollution with heavy metals in the Polog Region, Republic of Macedonia. For this purpose moss biomonitoring technique was used for determination of traces of 22 elements (Ag, Al, As, Ba, Ca, Cd, Co, Cr, Cu, Fe, Hg, K, Li, Mg, Mn, Na, Ni, P, Pb, Sr, V and Zn). A total of 43 moss samples were collected from predetermined sampling locations during the summer 2011. The samples were prepared with microwave digestion of dried and cleaned moss samples by using HNO3 and H2O2 and then analyzed by the application of atomic emission spectrometry with inductively coupled plasma (ICP-AES). At last data processing with multivariate statistical methods was performed over the retrieved result set of element distributions, producing 5 element correlation factors (F1, F2, F3, F4 and F5), where F1 associates elements: Cr, Li, V, Co, Fe, Al, Ni and As; F2 associates elements: K, P and Mg; F3 associates elements: Hg, Pb, Cd and Zn; F4 associates elements: Ag and Cu and F5 associates elements: Ba, Sr and Mn. A spatial distribution maps were prepared for each element according to its determined distribution from analyzed samples.

AcknowledgementThis work was supported by the Macedonian Academy of Science and Arts and Bulgarian Academy of Science, Project: � Application of atomic absorption spectrometry in trace elements analysis� .


103

P48Luminescence method for determination of abiraterone acetate

residues on the surface of manufacturing equipment

Ganna Fedosenko*, Inna Leonenko, Yulia Scrypynets, AllaYegorova

A.V. Bogatsky Physico-chemical Institute of the National Academy of Sciences of Ukraine,86 Lustdorfskaya doroga, Odessa, 65080, Ukraine

*[email protected]

In pharmaceutical industries, it is very important to remove drug residues from the equipment and areas used. The cleaning procedure must be validated, so special attention must be devoted to the methods used for analysis of trace amounts of drugs. A rapid, sensitiveand specific luminescence methods were developed for the quantitative determination of abiraterone acetate in cleaning validation swab samples.

Abiraterone acetate (17-(Pyridin-3-yl)androsta-5,16-dien-3b-yl acetate) is a novel anticancer agent which directly affects the androgen biosynthesis pathway by inhibiting CYP17 (17α-hydroxylase/C17,20-lyase).

The luminescence method has been developed for quantitative determination of abiraterone acetate (AA). The method is based on the measurement of the native fluorescence of the drug in ethanol at emission 350 nm after excitation at 253 nm (Fig.). The relative fluorescence intensity-concentration plot was linear over the range of 0.05 � 7.0 μg/ml.

Figure: Fluorescence spectra of different concentration of AA.

The proposed method was validated as per ICH guidelines. The following validation characteristics were addressed: specificity, accuracy, precision, limit of detection and quantification, linearity range and robustness. Cotton swabs, moisten with extraction solution (90% methanol and 10% water), were used to remove any residue of drug from stainless steel, glass and silica surfaces, and give recoveries > 80% at four concentration levels.


104

P49Investigation of thermal and analytical properties of azobenzene-

imine liquid crystal by capillary gas chromatography

Sebih Saïd1*, Athman Fatiha1, Boudah Soulimane1

USTHB, Faculté de Chimie, Laboratoire de Chromatographie BP 32 El-Alia Bab-Ezzouar Alger, Algerie

*[email protected]

Thermal and analytical properties of azobenzene-imine laterally substituted have been investigated by capillary gas chromatography. The thermal properties of the nematic liquid crystal, such as thermal stability and transition temperature, were studied by differential scanning calorimetry and thermal polarized optical microscopy. The chromatographic separation abilities of the mesogenic compounds were studied using fused silica capillary column.

The variation of logarithm of the capacity factors (ln K) with the reciprocal absolute temperature (1/T) show the temperature transition between 325 and 337 K. Separations of some aromatic constituents of essential oils at temperatures below, during and above the transition are reported. The azobenzene-imine liquid crystal stationary phase presented in this work exhibits two transition temperatures at 337 and 325 K. The two transitions are clearly apparent when PAHS are used as solutes. Interesting analytical performances were obtained notably in separation of volatile aroma compounds and derivatives phenols.


105

P50Separation properties of a new liquid crystal in capillary gas

chromatography

Boudah Soulimane*, Sebih Saïd

USTHB, Faculté de Chimie, Laboratoire de Chromatographie BP 32 El-Alia Bab-Ezzouar Alger, Algerie

*[email protected]

The 4-methoxybenzoate of 4-(4-((2-hydroxy-4-methoxyphenyl) methylene amino) phenylazo)-3-(4-pentylcyclohexylcarboxy) phenyl was synthesized and successfully coated on two fused silica capillary column.

The characterization was performed with 1H NMR and mass spectrometry. The thermal properties were established by differential scanning calorimetry (DSC). The optical characterization of the liquid crystal was made by using polarizing optical microscopy.

The chromatographic experiments show that this nematic liquid crystal possess good separation abilities for many different kinds of solute. Typical separations are observed for aromatic and polyaromatic hydrocarbons positional isomers.


106

P51Chemical composition and antioxidant activity of Chenopodium

ambrosioides (L.) essential oils growing wild in Algeria

Keddad Amina1,2, Aoumeur Baaliouamer2*, Mohammed Hazzit3

1Centre de Recherche Scientifique et Technique en Analyses Physico-Chimiques (CRAPC), Algiers, Algeria2Université des Sciences et de la Technologie Houari Boumediene (USTHB), Faculté de Chimie, Laboratoire

d� Analyse Organique Fonctionnelle, Bab Ezzouar, Alger, Algeria3Ecole Nationale Supérieure Agronomique (ENSA), Département de Technologie des Industries Agricoles et

Alimentaires, El Harrach, Alger, Algeria

*[email protected]

Two samples of essential oils from the aerial parts of Chenopodium ambrosioides (L.) in flowering stage from two different regions in Algeria (Birkhadem and Khemis El Khechna), were isolated by hydro-distillation (HD) and investigated using both apolar (CP-sil-5 CB) and polar (DB Wax) capillary GC and GC/MS techniques.

A total of 21 compounds were indentified representing 91.2% and 91.7% of the oils from Birkhadem and Khemis El Khechna, respectively. The main components of the volatile oils were cis-ascaridol (82 � 74.9%), p-symene (2.9 � 8.5%), carvacrol (3.9%) and γ-terpinene (0.6 − 62.4%).

The antioxidant potential of the samples was evaluated using the 2, 2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging method. In comparison with butylated hydroxytoluene (BHT), which was used as positive control, all samples showed a relatively weak antioxidant capacity.

AcknowledgementThe authors are grateful for financial support by the Faculty of Chemistry, University of Sciences USTHB.


107

P52Investigation of the interaction of complex silicates from an

industrial slag with alkaline solutions

Nikolay Marinkov1, Ivan Penkov2, Stoyko Gyurov2, Yoanna Kostova2, Daniela Kovacheva1

1Institute of General and Inorganic Chemistry, BAS, 11 Acad. G. Bontchev Str., Sofia, Bulgaria2Institute of Metal Science, Equipment and Technologies � Acad. A. Balevski� with Hydroaerodynamics centre,

67 "Shipchenski prohod" Str., Sofia, Bulgaria

[email protected]

The pyrometallurgical copper slag has a complex chemical composition, structure, and strong mineral crystallization ability. For these reasons, the data available of the solubility of silica in an alkaline solution and subsequent neutralization with mineral acid cannot be directly applied to the processes of interaction of the slag with alkaline solutions.

The aim of the present work is studying the processes of the interaction of oxidized slag with NaOH solutions. Three parameters of the reaction have been chosen to be varied: the concentration of NaOH solution, the time of interaction and the temperature of interaction. The degree of the silicon extraction and the phase composition of the residual solid mass were determined by means of atomic absorption (AAS), emission spectrum with inductively coupled plasma (OES-ICP) and UV-VIS spectrometry as well as powder X-ray diffraction. The morphology of the solid residua was studied by Scanning electron microscopy (SEM).

New data were obtained for the phase transformation during reaction, morphology and the type of silicon-containing phases, chemistry of dissolution of the composite glassy phase. The resulting data can be used to create new environmentally friendly processes of recycling slag, and for preparation of micro and nano-size, amorphous silicon dioxide (silica) with low density and large surface area.

AcknowledgementThe authors are grateful for financial support of Project DFNI E02-1/2014 of National Science Fund, Bulgarian Ministry of Education and Science.


108

P53Spectral studies and thermal transformations of

KMg2H(PO4)2.15H2O as potential proton conductor

Violeta Koleva1, Viktor Stefov2,4, Metodija Najdoski2,4, Adnan Cahil3,4

1Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, Sofia, Bulgaria2Institute of Chemistry, Faculty of Natural Sciences and Mathematics, Sts. Cyril and Methodius University,

Skopje, Republic of Macedonia3Pedagogical Faculty, Sts. Cyril and Methodius University, Skopje, Republic of Macedonia

4Research Cеnter for Environment and Materials, Macedonian Academy of Sciences and Arts, Skopje,Republic of Macedonia

[email protected]

Acid sulphate and selenate salts containing H(XO4)2 dimmers such as M3H(XO4)2

(M= K, Cs, Rb, NH4; X= S, Se), have attracted considerable attention mainly due to their superprotonic conductivity. The key feature of the superproton conductivity is the hydrogen bond network since the electric charge is transported by protons in a hopping process between the different hydrogen bonds. For phosphate salts only few examples of this type salts like Na3MgH(PO4)2 and K3CaH(PO4)2 are known.

The present research is devoted to KMg2H(PO4)2.15H2O that is another representative containing H(PO4)2 dimmers. Except of its crystal structure, nothing else is known for this salt. Our interest was provoked by the fact that the crystal structure provides open channels which would ensure a continuous pathway for movement of the water molecules, thus giving rise to proton conductivity.

Large plate KMg2H(PO4)2.15H2O crystals with micrometer sizes (200 ¥ 500 ¥ 20 mm) were prepared by a modified precipitation method. The phase purity was confirmed by XRD and EDS analyses. The crystals have a triclinic symmetry with a = 6.2908 Å, b = 12.2451 Å, c

= 6.5551 Å, a = 93.64∞, b = 89.14∞, g = 94.73∞. It was observed that the crystals are trichroic and exhibit three colors when were oriented in different ways in respect to the polarized light. The infrared spectrum of KMg2H(PO4)2.15H2O was recorded at room temperature for the first time and interpreted in respect to the internal PO4 and H2O vibrations, and the hydrogen

bonds present. The thermal behavior of Mg2KH(PO4)2.15H2O was examined up to 1000∞C by simultaneous TG/DTA/Mass spectrometry analysis. It is established that the two processes,

dehydration and dehydration-condensation, occur simultaneously to 400∞C and cannot be

separated. The thermally induced phase transformations above 400∞C were studied by XRD and IR spectroscopy.

AcknowledgementThe financial support of the Bulgarian Academy of Sciences and Macedonian Academy of Sciences and Arts is gratefully acknowledged.


109

P54New approach for appraisal of chemical conformity of AISI 316 L

steel bars using SDAR-OES measurements

Ion Pencea, Catalin Eugen Sfat, Ramona-Nicoleta Turcu, Mihai Cojocaru, Mihai Branzei, Alecs Andrei Matei

University � Politehnica� of Bucharest, Meatllic Material Science and Physical Metalurgy Department, 313 Spaiul Independentei Blvd., 500036, Bucharest, Romania

[email protected]

The AISI 316 L steel grade is the most used metallic biocompatible medical devices and related fields. A batch of AISI 316 bars, of about 30 mm in diameter and 1 m in length was produced for orthopedical implant manufacture. According to ASTM F138 the chemical composition of 316 L grade has to fulfill some constrains as maximum concentration values (critical levels) of some elements e.g. C < 0.03%; S < 0.01%; Si < 0.75% or both side critical levels e.g. 17% < Cr < 19%, 14 < Ni < 18 etc.

To prove that an elemental concentration of a bar complies to specified limits with a certain level of confidence (99% desired) it is mandatory to assess the measurement uncertainty taking into account all significant factors of the uncertainty budget e.g. equipment, sample heterogeneity etc. Thus, the maximum concentration level criterion for a concentration is fulfilled, with a confidence level, if:

c+U < cmax (1)

while both side critical levels implies:

cmin < c-U< c+U< cmax (2)where: c is the measured average concentration; U − the expanded uncertainty of the c with a specific level of confidence; cmin and cmax are the lower and upper critical levels.

When more than 3 elemental concentrations have to be measured with a specific U then the most adequate technique that can be used is spark discharge in Argon - optical emission spectrometry (SDAR-OES) due to its very high ratio between performance and costs. In this regard, we used a SpectroMAXx SDAR-OES equipment to appraise the conformity of the above mentioned AISI 316 bars. Ten AISI 316 disks of about 30 mm in diameter and 15 mm thicker were prelevated at equal distance from bars. The disk surfaces were sparked 10 times on each face. The aquired data were statistical tested for outliers, critical values and bias. ANOVA technique was used to discriminate between cross-section (� in bottle� ) and among cross-sections (� among bottle� ) chemical variances. The same multivariate analyses have been applied to estimate the correlation among the measurand values.

The novelty addressed in the paper consists in a robust procedure for discriminating the cross-section chemical heterogeneity from longitudinal one. In this regard a new measurement uncertainty procedure has been developed for SDAR-OES method.

AcknowledgementThe work has been funded by the Sectoral Operational Programme Human Resources Development 2007-2013

of the Ministry of European Funds through the Financial Agreement POSDRU/187/1.5/S/155536.


110

P55Effect of some pollutants on the environment of Erbil City

Pakhshan I. Azez

Shkar School, Directory of Education, Erbil, Kurdistan Region, Iraq

[email protected]

Decades of research have provided the scientific foundation for understanding the role of the environment in disease. For many pollutants, scientists know with some certainty that exposure to these pollutants, at sufficiently high concentrations, can cause a variety of health effects. For other pollutants, where scientific evidence is less conclusive, scientists can only establish an � association� between exposure and health problems. Some effects on health may be short-term and reversible, such as irritated eyes from smog. Other effects, such as emphysema, heart disease, and cancer are chronic or even fatal. Some effects may appear shortly after exposure. Others, such as cancer, may require long time before the disease appears. In many cases, pollution probably is just one of several factors� including diet, exercise, alcohol consumption, and genetic make-up� that influence whether an exposed person will ever become sick. Further complications reveals the fact that several segments of the population may be at higher risk for damage or disease from environmental pollutants. Potentially sensitive groups include children; older Americans; people with existing health problems such as diabetes, respiratory disease, or heart disease; and persons with compromised immune systems, including those who have HIV/AIDS or are undergoing cancer chemotherapy. Many studies on people have demonstrated an association between environmental exposure and certain diseases or other health problems. Examples include radon and lung cancer; arsenic and cancer in several organs; lead and nervous system disorders; disease-causing bacteria such as E. coli O157: H7 (e.g., in contaminated meat and water) and gastrointestinal illness and even death; particulate matter and aggravation of heart and respiratory diseases. The effect of some pollutants is suggested to study their effects on the environment of Erbil City.


111

P56Platinum(II, III) and platinum(II) complexes of the nitrogen ligands pyridine-2-amine and pyridine-4-amine � synthesis,

spectroscopic characterization and properties

Silviya Chakarova*, Galina Gencheva

Sofia University St. Kliment Ohridski, Faculty of Chemistry and Pharmacy, 1 James Bourchier Blvd.,1164 Sofia, Bulgaria

*[email protected]

The presented study is dedicated to synthesis of high� oxidation mixed-valence platinum-based polynuclear complexes with N,N-containing ligands. The polynuclear platinum(II, III) complexes with 2 or 3 metal centres, have entered focus of interest in view of developing novel anticancer agents with improved toxicological profile. This study deals with the possibilities of the chelating ligands pyridine-2-amine (2-AP) and pyridine-4-amine (4-AP) for obtaining of stable and water soluble platinum coordination compounds.

Two mixed-valence platinum polynuclear complexes � Complex I (C20H24N8Pt4Cl9xH2O, blue) and Complex II (C20H24N8Pt3Cl6OHxH2O, green), respectively, have been synthesized during the interaction of PtCl4

2- and 2-AP in alcohol-aqueous solution (M:L=1:1) and a mononuclear platinum(II) complex with composition C10H12N4PtCl2,

(yellow) have been prepared in aqueous solution using 4-AP (M:L=1:1). It was found that the resulting polymeric structures correlate with the mutual arrangement of the donor functional groups in the structure of the ligands (Fig. 1).

The coordination reactions were monitored and controlled by potentiometry, UV/Vis and NMR spectroscopy. The solid state structure of the compounds and their solutions chemistry have been characterized using IR, EPR and NMR spectroscopy.

Fig. 1. Modes of coordination of 2-AP and 4-AP


112

P57Fuzzy descriptor fingerprint study based on gas chromatographic

data. І. Biodiezel fuels.

Marina Moskovkina1*, Ivan Bangov1, Zilia Mustafa2, Rumjana Milina2

1Konstantin Preslavski Shumen University, Faculty of Natural Sciences, General Chemistry Chair,115 Universitetska Str., 9712 Shumen, Bulgaria

2Central Research Laboratory, Faculty of Natural Science, Prof. Assen Zlatarov University,62 San Stefano Str., Burgas 8001, Bulgaria

*[email protected]

Descriptor fingerprints have been proposed and developed by our research team in a series of previous papers for application to QSAR and QSPR studies. Here we introduce a new type of descriptor fingerprints, fuzzy descriptor fingerprints, based on the fuzzy logic theory. A fuzzy fingerprint represents a class or cluster of objects having similar nature. Initial studies of the potential of fuzzy fingerprints to describe some physical properties were performed for the set of 98 biodiesel fuels. Since biodiesel is a mixture of Fatty Acid Methyl Esters (FAME), its properties depend on the chemical structure of the individual FAME and their contents (FAME profile). We have obtained the FAME profiles of biodiesel by chromatographic methods providing valuable multi-component information. So, FAME profiles appear to be an instrument for a selection of feed-stock to produce fuels with certain properties for investigations and for fuel spillage and remedial actions in the environment.

AcknowledgementThe authors are grateful for the financial support of Project № RD-03-255/09.03.2015 of University of Shumen � Konstantin Preslavsky� and Project DFNI IO7/1 of the National fund Scientific Investigations.


113

P58Fuzzy descriptor fingerprints study based on gas

chromatographic data. ІI. Lavender oils.

Marina Moskovkina1*, Ivan Bangov1, Zilia Mustafa2, Rumjana Milina2

1Konstantin Preslavski Shumen University, Faculty of Natural Sciences, General Chemistry Chair, 115 Universitetska Str., 9712 Shumen, Bulgaria

2Central Research Laboratory, Faculty of Natural Science, Prof. Assen Zlatarov University, 62 San Stefano Str., Burgas 8001, Bulgaria

*[email protected]

A novel descriptor fingerprint approach toward chromatographic separation process depiction was carried out for a set of 44 lavender oils. The aromatic properties of the oils assessed by the method of fuzzy descriptor fingerprints were compared with those obtained from a subjective grading regarded for essential products. The purpose of this work was to apply the method to the perception of the different essences in lavender oils. It is known that the lavender oil is a mixture of many compounds. It includes more than 200 components. All these components of essential oil of individual branches or descendants are more or less influenced by heredity, which carry, the specific soil and climatic conditions, time of harvest, the kind of distillation of essential oil, etc. Evaluation of lavender oil is reflected in the standards of the countries concerned, based on organoleptic, physical and chemical indicators. The smell assessment is based on organoleptic analysis made by tasting. There are some experienced men, named � nozes� , who carry out this task. Hence, our task was to make an attempt to study the creation of a � computer nose� based on the composition of oil, and exploring the method of fuzzy descriptor fingerprints. Similar approach could be applied to testing of other products, such as wines, tobaccos, etc.

AcknowledgementThe authors are grateful for the financial support of Project № RD-03-255/09.03.2015 of University of Shumen � Konstantin Preslavsky� and Project DFNI IO7/1 of the National fund Scientific Investigations.


114

P59Application of High-Resolution Transmission Electron

Microscopy (HR-TEM) for advanced characterization of archaeological artefacts

Georgi Lalev1*, Zornitza Glavcheva2

1School of Chemistry, Cardiff University, Cardiff CF10 3AT, UK2Institute of Organic Chemistry with Center of Phytochemistry, BAS, Sofia, Bulgaria

*[email protected]

High-resolution transmission electron microscopy (HRTEM) and energy dispersive X-ray spectroscopy (EDS) analysis were carried out as a complementary techniques to differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR) and Attenuated Total Reflectance Fourier transform infrared spectroscopy (ATR FTIR) in order to provide a profound picture of the analised samples obtained from Thracian tomb wall paintings at Alexandrovo, Bulgaria (dating back to the fourth century BC). The current work provides a glimpse of the ingenious construction and painting techniques used in Thracian tomb at Alexandrovo. The results suggest presence of various nano-materials.

HR-TEM and EDS study reveals the presence of nano-size Au, TiO2 and CeO2

particles in certain areas of the red plinth. The presence of these nanomaterials in the sample is not intentional, however it is believed that this could be a factor contributing to the optical effects and well preservation of the wall paintings used in the Thracian tomb at Alexandrovo.


115

P60Characterization of pyridinecarboxylic acid derivatives in ruderal

plants under manganese stress

Umran Seven Erdemir1*, Hulya Arslan2, Gurcan Guleryuz2, Seref Gucer1

1Department of Chemistry, Faculty of Arts and Sciences, Uludag University, 16059, Bursa, Turkey2Department of Biology, Faculty of Arts and Sciences, Uludag University, 16059, Bursa, Turkey

*[email protected]

Niacin is a type of water soluble vitamin that is widely distributed in animals and vegetables [1,2]. For its antioxidant properties, it is known to reduce oxidative reactions in foods [3], Also it is converted into NAD (nicotinamide adenine dinucleotide) and NADH (nicotinamide adenine dinucleotidic acid), which behave as coenzymes for many redox enzymes in the cell [1].

In this study, niacin profiles in Verbascum olympicum Boiss were screened by Beckman Coulter P/ACE MDQ capillary electrophoresis. Seeds of V. olympicum were collected from the alpine belt of Uludağ Mountain and cultivated in Hoagland� s nutrient medium in a growth chamber with the addition of MnSO4. Plants were harvested on several days, and total niacin was extracted from freeze-dried samples. The separations were performed at +25 kV and 25ºC at 254 nm by capillary electrophoresis. The results were used together with the elemental results to evaluate the possible transport characteristic by this vitamin.

AcknowledgementThis work was supported by the Commission of Scientific Research Projects of Uludag University [Project No KUAP(F)-2014/20].

References[1] Tanaka, S., K. Kodama, T. Kaneta, and H. Nakamura. 1995. Journal of Chromatography A 718: 233� 237.[2] Pfuhl, P., U. Karcher, N. Haring, A. Baumeister, M. A. Tawab, and M. Schubert-Zsilavecz. 2005. Journal of Pharmaceutical and Biomedical Analysis 36: 1045� 1052.[3] Saccani, G., E. Tanzi, S. Mallozzi, and S. Cavalli. 2005. Food Chemistry 92: 373� 379.


116

P61FTIR spectroscopic investigation of Thracian wall paintings from

tombs and monumental buildings

Zornitza Glavcheva1*, Dorotea Guirdzhiiska2, Denitsa Yancheva1, Evelina Velcheva1, Bistra Stamboliyska1, Valentin Todorov3

1Institute of Organic Chemistry with Center of Phytochemistry, Bulgarian Academy of Sciences, Sofia, Bulgaria2Sofia University � Sv. Kliment Ohridski� , Department of Archaeology, Sofia, Bulgaria

3National Academy of Art, Faculty of Applied Arts, Sofia, Bulgaria

*[email protected]

In the field of art and archaeology the multilayered structure of the objects is a complex and complicated issue for analysing. Fourier Transform Infrared (FTIR) spectroscopy is a reliable analytical technique to study both organic and inorganic materials. FTIR spectroscopy has been widely applied in conservation field. The main advantage of this spectral method is the speed, easy access to the analysis and the requirement for very small sample amount which is very important factor when studying artworks and archaeological sites.

In this work, the results of FTIR investigation of samples from Thracian tombs and monumental buildings wall-paintings (4th-3th century BC), located in Bulgaria are presented. The FTIR analyses of the samples were carried out by using both transmittance and reflectance techniques. It was concluded that the main inorganic components of the paint layer (plaster, pigments, binder, etc.) were slaked lime, river sand, natural red and yellow ochre, charcoal black, calcite, etc. The study of organic components in the samples is also an object of this investigation. The presence of beeswax was proven in some case studies. The obtained results give useful information for scientists and conservators.

AcknowledgementThe authors are grateful for financial support by the National Science Fund of Bulgaria (Contract K02-15).


117

P62Rosmarinic acid and essential oil production potentials of in vitro

propagated plantlets of Thymus leucotrichus Hal.

Tuba Yapar Bekircan1, Ahmet Yaar2, Münevver Sökmen3*, Ezgi Demir3,Atalay Sökmen1

1Department of Biology, Faculty of Science, Karadeniz Technical University, 61080 Trabzon, Turkey2Faculty of Pharmacy, Karadeniz Technical University, 61080 Trabzon, Turkey

3Department of Chemistry, Faculty of Science, Karadeniz Technical University, 61080 Trabzon, Turkey

*[email protected]

As an important aromatic plant, Thymus leucotrichus was successfully produced by in vitro tissue culture using various cytokinins (kinetin, 2-iP and BAP) and cytokinin − like thidazuron as plant growth regulators (PGRs) at four different concentrations. The micropropagated plantlets were individually evaluated for their rosmarinic acid and essential oil production potentials. Methanol extracts from plantlets were individually prepared and rosmarinic acid content was determined by using HPLC. Of all sixteen lines were examined, the highest Rosmarinic acid content (RAC) was obtained from those being grown on Murashige and Skoog Basal Medium supplemented with 0.1 thidazuron (TDZ) (with a value of 0.36 mg/g dry biomass). The essential oil contents of all cell lines were also analyzed by using Headspace-GC-MS. The essential oil content was completely different and variable depending upon the PGR content; gamma terpinene, thymoquinone, myrcene, limonene, camphene and alpha-phellandrene being the major constituents.


118

P63A new rotator-mixer-assisted liquid-liquid microextraction for the

determination of phenols in water samples

Hasan Çabuk*, Şevket Ata

Bülent Ecevit University, Faculty of Arts and Sciences, Department of Chemistry, Zonguldak, Turkey

*[email protected]

In this study, a new sample enrichment method, termed rotator-mixer-assisted liquid-liquid microextraction combined with high-performance liquid chromatography with ultraviolet detection was developed for the determination of selected priority phenols in environmental water samples. In this approach, a binary solvent system of water sample and low-density extraction solvent (1-dodecanol) was mixed at 80 rpm for 8 min with a 360° vertical rotation in the absence of a disperser solvent. Fine organic droplets were formed during continuous end-over-end action and the mass transfer of the analytes was accelerated between organic and water phase. After extraction, the phase separation was performed by centrifugation and the enriched analytes in the floated extractant phase were determined. A series of parameters that influence extraction efficiency such as the kind and the volume of the extraction solvent, the ionic strength, pH of the aqueous sample, the rotation speed and time were investigated systematically. Under the optimized conditions, the limits of detection and limits of quantification for the phenols were in the ranges 0.3 − 0.6 ng mL-1 and 1.0 − 2.1 ng mL-1, respectively. Relative standard deviations based on five replicate extraction of 25 ng mL-1 of each phenol were less than 5.3% for intra-day and 8.3% for inter-days precision. This method has been successfully applied to analyze the real water samples at two different spiked concentrations and satisfactory recoveries were achieved.

AcknowledgementThe authors wish to thank Bülent Ecevit University for the opportunity and support to carry out this research.


119

P64Hesperidin-dsDNA interaction based on electrochemically

reduced graphene oxide and poly-(2,6-pyridine dicarboxlic acid) modified glassy carbon electrode

Gözde Aydoğdu Tığ, E. Özlem Bolat, M. Barış Koçer, Şule Pekyardımcı*

1Ankara University, Faculty of Science, Department of Chemistry, 06100 Tandogan, Ankara, Turkey

*[email protected]

In recent years, electrochemical investigations of antitumor flavonoids with double stranded DNA (dsDNA) have attracted much more attention. Interaction of DNA with small molecules results in various changes in the DNA structure such as DNA damage, intercalation, covalent binding, electrostatic interaction, and groove binding. Hesperidin (Hesp) is a citrus biflavonoid, which commonly exists in many plants. Hesp has several advantages in drug design such as anti-tumor, anti-oxidant, and anti-inflammatory.

In this study, poly-(2,6-pyridine dicarboxylic acid (PPDC) and electrochemically reduced graphene oxide (ERGO) modified GCE (PPDC/ERGO/GCE) was fabricated and this electrode was used for the electrochemical monitoring of interaction between the dsDNA and Hesp for the first time. The surface morphology of the developed film was characterized by SEM technique. Electrochemical behavior of PPDC/ERGO/GCE was investigated by usingcyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) and compared with those of the bare GCE. The dsDNA/PPDC/ERGO/GCE electrode was prepared by adsorption of dsDNA upon the modified surface and the binding of Hesp with dsDNA was investigated via DPV method. The decrease in the guanine oxidation peak current at +0.8 V was used as an indicator for the interaction in 0.5 mol L−1 ABS (pH 4.8), containing 0.02 mol L−1 NaCl. The experimental parameters such as dsDNA concentration, Hesp concentration, dsDNA adsorption time, interaction time were optimized. Under the optimum conditions, the guanine oxidation peak currents were linearly proportional to the concentrations of Hesp in the range of 0.00082 − 0.082 mmol L-1 and detection limit was found to be 0.00024 mmol L-1. In order to obtain more information about the interaction between dsDNA and Hesp, UV-VIS spectrophotometry and viscosity measurements were also performed. Furthermore, the reproducibility, repeatability, stability and applicability of the analysis to human serum samples were also studied. The fabricated biosensor is applicable for the investigation of DNA-Hesp interaction.

AcknowledgementThis work was supported by the Ankara University Scientific Research Fund (Project No: 14L0430004).


120

P65PVC - membrane potentiometric sensor for the determination of

isoproterenol

Gulsah S. Kanberoglu1*, Suat Ekin1, Fatih Coldur2, Osman Çubuk2,Cihan Topcu2, İbrahim Isildak3

1Yüzüncü Yıl University, Faculty of Sciences, Department of Chemistry, 65080 Van, Turkey2 Erzincan University, Faculty of Sciences, Department of Chemistry, Erzincan, Turkey

3Yıldız Teknik University, Faculty of Chemistry − Metalurgical, Department of Bioengineering, Istanbul, Turkey

*[email protected]

4-[1-Hhydroxy-2-[(1-methylethyl)-amino]ethyl]-1,2- benzenediol named isoproterenol (ISP) is a catecholamine drug widely used in the treatment of allergic emergencies such as styptic, bran-chiol asthma, status asthmatic, cardiac-arrest, glaucoma, and ventricular bradycardia. ISP has positive inotropic and chronotropic effects on the heart. Its inotropic and chronotropic effects elevate systolic blood pressure, while its vasodilatory effects tend to lower diastolic blood pressure. The adverse effects of isoproterenol are also related to the drug� s cardiovascular effects. İsopreterenole can produce an elevated heart rate (tachycardia), which predisposes patients to cardiac dysrhythmias.

In the present study, a novel isoproterenol-selective potentiometric electrodes based on various ion associations of isoproterenol were developed. The most suitable membrane composition which has the best potentiometric characteristics was examined under steady-state conditions. The membrane composed of (w/w) 3.0% isoproterenol-tetraphenylborate(TPB) ion pair, 32.0% poly (vinylchloride) (PVC), 64.0% 2-nitrophenyloctylether (NPOE) and 1.0% KTPClPB was determined as the membrane with the best analytical properties. On the condition of pH=2.3 − 3.6, the fabricated electrode exhibited linear responses over the concentration range of 1×10-1 − 5.0×10-5 M isoproterenol solutions (R2 = 0.9979) with a sensitivity of 53.6 mV/decade, detection limit of 3×10-5 M and short response time of 15 s.


121

P66Photocatalytic inactivation of Staphylococcus aureous in water

using TiO2 modified with Nickel phthalocyanine

İlknur Altın1*, Cansu Albay1, Melek Koç1, İsmail Değirmencioğlu1,Rıza Bayrak2, Münevver Sökmen1

1Karadeniz Technical University, Faculty of Science, Chemistry Department, 61080 Trabzon, Turkey2Sinop University, Vocational School of Health Services, Department of Medical Laboratory Techniques,

57000 Sinop, Turkey

*[email protected]

Microorganisms cause great harm to the environment and human health. Prevention of infectious diseases from pathogen microorganisms is very important in food industry, healthcare and drinking water. Photocatalytic oxidation (PCO) is gaining popularity in recent years for its microbial disinfection. Briefly, when a photocatalyst absorbs a photon of energy equal to or greater than its band gap, highly oxidative radicals such as .OH, O2 and H2O2 are produced in the presence of light. These radicals can attack microorganism cell membranes and release K+, RNA, proteins and other components which cause the cells to die eventually. These PCO processes are limited in application due to the disadvantages such as electron-hole recombination and low absorption in visible region. Therefore, many approaches have been used to enhance PCO activity including doping metal/non-metal, coupling with other semiconductors and loading photosensitizer. Among these strategies, dye photosensitization has been proved to be an effective way to enhance the visible light photocatalytic activity of TiO2 in water treatment. From environmental point of view, metallo-phthalocyanine sensitized TiO2 nanoparticles could be very effective visible-light photocatalyst for microbial disinfection.

In this study, peripherally or non-peripherally substituted Nickel phthalocyanine (NiPc) sensitized TiO2 nanocomposite material had been successfully prepared by wet chemical process. The antibacterial activity of as-obtained products was determined using Staphylococcus aureous (S. aureos) as a biological indicator. The composite material showed excellent photocatalytic activity for the degradation of S. aureous under near visible light irradiation.


122

P67Enhanced photocatalytic degradation of 4-chlorophenol in the

presence of a new photocatalyst material

İlknur Altın1*, Cansu Albay1, Melek Koç1, İsmail Değirmencioğlu1,Rıza Bayrak2, Münevver Sökmen1

1Karadeniz Technical University, Faculty of Science, Chemistry Department, 61080 Trabzon, Turkey2Sinop University, Vocational School of Health Services, Department of Medical Laboratory Techniques,

57000 Sinop, Turkey

*[email protected]

TiO2 has been reported as one of the most efficient photocatalyst because of its excellent properties such as high stability, non-toxicity, economical and high catalytic activity. The application of the TiO2 photocatalyst in waste water treatment process has been reported to remove various organic pollutants, such as phenolic compounds. It is well known that modifiation with certain organic species is very effective way to increase the photocatalytic activity. In addition, it is found that a rapid separation of photo-generated electron-hole pairs can be promoted due to the formation of more electron transfers between the modifiers and TiO2, which leads to increase photocatalytic efficiencies.

In this work, we report that the surface modification of TiO2 with iron phthalocyanine (FePc) induce rapid separation of electron-hole pairs as compared to the neat TiO2. Thephotocatalytic degradation of 4-chlorophenol (4-CP) was investigated in the presence of FePc modified TiO2 (FePc/TiO2). It was found that the FePc/TiO2 composite photocatalyst had an improved performance on the photocatalytic degradation of 4-CP under near visible light irradiation.


123

P68Silisium phthalocyanine sensitized TiO2 nanomaterials

İlknur Altın*, Zekeriya Bıyıklıoğlu, Münevver Sökmen

1Karadeniz Technical University, Faculty of Science, Chemistry Department, 61080 Trabzon, Turkey

*[email protected]

Removal of dye pollutants from textile paper and other industries has attracted great attention in water purification. Conventional methods including adsorption, biological treatment, precipitation and reverse osmosis have been widely used for the removal of dye pollutants. Recently, heterogeneous photocatalysis process, which involves semiconductors such as TiO2 and ZnO is emerging as a key technology to meet the need of clean water due to the advantages over other methods, such as simple treatment procedure under ambient temperature and pressure, no requirements of additional oxidant chemicals apart from air. Among of all semiconductors, TiO2 has been proven to be the promising photocatalyst because of its high photocatalytic activity and photosensitivity. However, its application is significantly limited by the electron-hole recombination and the high cost of the UV illumination.

The main objectives of this work are: (i) to prepare silisium pthalocyanine (SiPc) sensitized TiO2 catalyst thin film by sol-gel method and (ii) to investigate the photocatalytic degradation of methylene blue (MB) under near UV-vis light irradiation using SiPc/TiO2

photocatalyst. The as-prepared nanomaterials were characterized by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDX), X-ray diffraction (XRD) and atomic force microscopy (AFM).


124

P69Structural, spectroscopic and electrochemical studies of sulfathiazole - zinc(II) complex with diethylenetriamine

Ahmet Bulut1*, Filiz Öztürk1, İclal Bulut2

1Ondokuz Mayıs University, Faculty of Arts and Sciences, Department of Physics, Samsun, Turkey2Ondokuz Mayıs University, Faculty of Arts and Sciences, Department of Chemistry, Samsun, Turkey

*[email protected]

A mixed ligand sulfathiazole (4-amino-N-(1,3-thiazol-2-yl) benzene sulfonamide, (Hstz)-zinc(II) complex with dien (diethylenetriamine) has been synthesized and its structural, spectroscopic as well as electrochemical properties have been studied. The single crystal XRD analysis indicated that the compound crystallizes in the monoclinic space group Pc with Z =4. The sulfathiazole anion acts as a monodentate ligand through the thiadiazole N atom contiguous to the deprotonated sulfonamido group. The metal centre adopts a near regular trigonal-bipyramidal geometry.

The absorption bands of the complex were compared with the related structures and the most important features of its IR spectrum were also discussed. The analysis of powder EPR spectrum of Cu2+doped Zn(II) complexes at room temperature has led to that the ground state wave function of the unpaired electron of copper ion is dx

2-y2.

The Square Wave and Cyclic voltammetric techniques have been used to investigate the electrochemical behaviour of Zn(stz)2dien complex. The SWV and CV of Zn(II) ions, stz and dien were recorded seperately in aqueous media. A reduction peak observed at -1.336 V in the SWV of the solution containing 6×10-5 M Zn(II) + 4×10-4 M stz was attributed to reduction of Zn(II)-stz complex. The reduction for Zn(II)-dien complex peak was observed at -1.196 V. When the dien was added to the Zn(II) and smz mixture, the current of peak at -1.336 V decreased and its peak potential shifted to -1.124 V. The CV of this peak has indicated that the reduction is irreversible. Consequently Zn(II) forms a mixed complex with smz and dien. It was observed that the voltammogram is in aggrement with the voltammogram of the solution which is obtained by dissolving the solid [Zn(stz)2dien]∙3H2O complex in methanol: water mixture 50%.

AcknowledgementThe authors are grateful for financial support of Project Number PYO.FEN.1904.12.019 of Ondokuz mayıs University.


125

P70Study of binary complexes of Cu(II), Ni(II) and Co(II) with

nitrofurantoin by voltammetry

İclal Bulut1*, Vahide Pehlivan1, Ahmet Bulut2, Mehtap Yağan Aşcı1

1Ondokuz Mayıs University, Faculty of Arts and Sciences, Department of Chemistry, Samsun, Turkey2Ondokuz Mayıs University, Faculty of Arts and Sciences, Department of Physics,Samsun, Turkey

*[email protected]

Nitrofurantoin as an antimicrobial drug is widely recommended for the treatment of urinary tract infection [1]. Nitrofurantoin possess many binding sites for metal ions such as the imidazole carbonyl group, the C=N, the oxygen furan ring and the oxygen of the nitro group [2]. Any information on its coordinating properties is important to understand the role of especially the trace metal ions in biological systems.

In the present study, electrochemical behaviour of nitrofurantoin being a synthetic antibiotic agent has been investigated by cyclic (CV) and square-wave voltammetry (SWV) techniques in the absence and the presence of metal ions (M(II); Cu(II), Ni(II) and Co(II)) at a hanging mercury drop electrode (HMDE). The SWV of nitrofurantoin has given two reduction peaks at -0.596 and -1.488 V in 0.04 M Britton� Robinson (B� R) buffer (pH 8). These peaks at -0.596 and -1.488 V are attributed to the reduction of the nitro group to produce the hydroxylamine derivative and to irreversible reduction of the azomethine (imine) group, respectively. The results have shown that all the metal ions form the binary complexes with nitrofurantoin. Cu(II)-nitrofurantoin complex was recognized by a cathodic peak at �0.820 V, whereas Ni(II)-nitrofurantoin complex was reduced at more positive potential (-1.048 V) than that of the hydrated Ni(II) ions (-1.296 V). The indication of Co(II)-nitrofurantoin complex was a well-developed cathodic peak that was obtained at -1.376 V in pH 8. The electrochemical studies clearly indicated that the nitrofurantoin serves as a catalyst in the reduction of Co(II) and Ni(II) ions. The analytical results indicated a 1:1 (M:L) stoichiometry for metal(II)-nitrofurantoin complexes. The binding constants for metal(II)-nitrofurantoin was also calculated and binding affinity of metal ions increases in the sequence:

Co < Ni < Cu. The interactions of cobalt, nickel and copper with nitrofurantoin in aqueous solution were also studied by UV-VIS spectroscopy. The results clearly indicated that the nitrofurantoin coordinate to metal ions, which is in accordance with the results of the voltammetric study.

AcknowledgementThe authors are grateful for financial support of Project Number PYO.SMY.1904.09.001 of Ondokuz mayıs University.

References[1] Delgado J.N., Remer W.A., Textbook of Organic Medicinal and Pharmaceutical Chemistry, 9th Ed. (1991). J. Lippincott Co. p.157.[2] Khallow, K.I., Sciences &Technologie A. 22 (2004) p.p.103-106.


126

P71The investigation of electrochemical behavior of diphenylamine on

the glassy carbon electrode surface

Burcu Yavuz*, Zafer Yazicigil

Selcuk University, Faculty of Science, Department of Chemistry, 42030 Konya, Turkey

*[email protected]

The modified electrodes are given targeted properties with the modification of a conductive substrate and these electrodes have different properties from unmodified substrate. Also it is known that; electrochemical behaviors of electrodes can change with some kind of materials which are absorbed to electrode surface. In this study; the electrochemical behavior of diphenylamine on the glassy carbon (GC) electrode surface in aqueous media and non-aqueous media was investigated with cyclic voltammetry (CV). Pt wire, Ag/AgCl/KClsat and GC electrode were used as counter, reference and working electrodes, respectively. In order to provide aqueous media for the modification procedure, Britton Robinson (BR) buffer solution with pH = 7.0 was chosen. Electrochemical charactarization was realized with CV technique in the presence of redox probes as potassium hexacyanoferrate(III) and Ferrocene in the suitable conditions of their own potencial range, scan rate and solvent. The results were compared with the results of bare GC. We still doing some experiments with different parameters about eletrochemical behaviours of diphenylamine.


127

P72Synthesis of poly(2,2� -dithiodianiline) chelating polymer and

determining adsorption properties of Gold(III) ions

Ümit Can Erim1*, Mustafa Gülfen2, Ali Osman Aydın2, Rabia Edibe Parlar1

1İstanbul Medipol University, School of Pharmacy, Department of Analytical Chemistry,34810 Beykoz, İstanbul, Turkey

2Sakarya University, Faculty of Arts and Sciences, Department of Chemistry, 54187 Esentepe, Sakarya,Turkey

*[email protected]

Approximately millions of tons of heavy precious metals from industrial manufacturing are added every year to our nation� s wastewater streams, which makes cleanup a high priority. These metals are extremely toxic to the majority of living organisms, and their waste results in lost opportunities for commercial applications. Heavy metals are typically reclaimed from the wastewaters through precipitation with chemical agents, adsorption onto activated carbon, ion-exchange resins, or membrane filtration processes. Recently, the use of chelating polymers for remediation of water and soil has attracted much attention due to its high selectivity, its stability in aqueous environments, and its recovery efficiency. Poly(2,2� -dithiodianiline) (PDTDA) is one of the chelating polymers which are used to recover precious metals because of its amine groups and � S-S- disulphide bonds.

In this work, PDTDA synthesised with ammonium persulfate oxidising reagent in acidic aqueous environment. Polymer was characterized by FTIR, thermal analysis, potentiometric titration and used for the adsorption of Au(III) ions. In the adsorption studies,effects of acidity, temperature and the concentration of Au(III) were examined. The effects of acidity and initial concentrations on the adsorption of Au(III) ions was examined by batch technique. The optimum acidity level to achieve maximale adsorption of gold ions was found to be 3 M HCl. It was found that PDTDA has Au(III) adsorption capacity (q(m)) of 49.75 mg/g polymer. The adsorption data fitted better to the Langmuir isotherm then the Freundlich isotherm. The Delta G degrees, enthalpy (Delta H degrees), entropy (Delta S degrees) and the activation energy (E-a) of the adsorption were calculated.


128

P73Investigation of electron transfer properties of graphene oxide and

reduced graphene oxide electrodes

Hilal Incebay1,2, Zafer Yazicigil1*

1Selcuk University, Faculty of Science, Department of Chemistry, 42030 Konya, Turkey2Nevsehir Hacı Bektas Veli University, Faculty of Science and Lecture, Department of Chemistry,

50300 Nevsehir, Turkey

*[email protected]

Studies on Graphene based systems have been expanded quickly although the substance was isolated firstly in 2004. Thus, graphene has been in various applications in wide range from material to medical sciences all over the world. Different techniques and methods have been emerged but the most common technique is top down approach, where graphene is synthesized from graphite. In this study graphene oxide (GO) and reduced graphene oxide (rGO) nanoparticles were synthesized by Hummers method and characterizated by Fourier transform infrared spectroscopy, X-ray diffraction spectroscopy, scanning electron microscopy, thermogravimetric differential thermal analysis, cyclic voltammetry, electrochemical impedance spectroscopy and contact angle. GO and rGO respectively were coated on glassy carbon (GC) electrodes and subsequently obtained GO/GC and rGO/GC surfaces were characterizated by cyclic voltammetry. GO/GC and rGO/GC surfaces were investigated in the point of the permeation of redox probes such as neutral ferrocene, cationic rutenium (Ru(NH3)6

3+) and anionic ferrocyanide (Fe(CN)6-4) in order to

discuss about the electron transfer abilities. The results indicated that redox reactions were under diffusion control in all probes.

AcknowledgementWe are grateful for this work was financially supported by Selcuk University Research Foundation under the project number 13201024.


129

P74Investigation of fluorescence properties of Zinc(II) complex

2-chloro-4,6-N,N'-bis(2-hydroxybenzyl)-1,3,5-triazine

Ziya Erdem Koç

Selcuk University, Science Faculty, Department of Chemistry, 42075 Konya, Turkey

[email protected]

An important class of compounds consists of substituted s-triazine derivatives which have anticancer, antitumor, antiviral and antifungal activity. These compounds have been used in the treatment of depression and hence gained a considerable importance. These are valuable bases for estrogen receptor modulators and also used as bridging agents to synthesize herbicides and in the production of drugs or polymers [1,2].

In this study, the triazines obtained by the condensation reaction to the 2-chloro-4,6-diamino-1,3,5-triazine and 2-hydroxybenzaldehyde with bidirectional (dipodal) Schiff base ligand [2-Chloro-4,6-N,N'-bis(2-hydroxybenzyl)-1,3,5-triazine (cdatsal)], population consists of Zn2+ ion complex fluorescent properties were investigated [3,4].

Fluorimetric determination of parameters for the DMF solvent is prepared with the appropriate concentration of my solution, the spectra were taken at 10 Nm intervals and emission wavelengths replaced and the emission wavelength were determined. Then Zn2+

with 2-chloro-4,6-N,N'-bis(2-hydroxybenzyl)-1,3,5-triazine complex that will create the most suitable conditions of pH, complex formation period, the temperature and the concentration of cdatsal has been designated. Determined optimum excitation and emission wavelengths were determined under the conditions of the complex cdatsal-Zn2+ most appropriate. Under the optimum conditions determined for the Zn2+ were assigned by drawing calibration curves for the range of lower to be able to observe and their detection limits were determined.

References[1] K., Srinivas, U. Srinivas, and et all, Bio. & Med.Chem. Let., 15, 1121, (2005).[2] Z.E. Koc, H. Bingol, A.Saf, E. Torlak, A. Coskun, J. Hazard. Mater.183, 251, (2010).[3] Z. E. Koc, H. I. Ucan, J. Macromol. Sci. A, 45, 1072, (2008).[4] K, Pavel, Z. Sindelar and R. Klicka, Trans. Met. Chem., 23, 139, (1998).


130

P75Elemental analysis, FTIR, UV spectroscopic and microbiological

studies of bis (N'-(dipyridin-2-ylmethylene)-4-methylbenzenesulfonohydrazone)Ni(II) complex

Murat Çınarlı1, Hatice Öğütcü2*, Hümeyra Bati3, Güleray Agar4,M. Yunus Emre Karaman2

1Central Research and Application Laboratory, Ahi Evran University, 40100 Kirsehir, Turkey2Ahi Evran University, Faculty of Arts and Science, Department of Biology, Kırşehir, Turkey

3Ondokuz Mayis University, Department of Chemistry, Faculty of Science, 55139 Samsun, Turkey4Atatürk University, Faculty of Science, Department of Biology, Erzurum, Turkey

*[email protected]

Arylhydrazone complexes of transition metal ions are known to provide useful models for ellucidation of the mechanisms of enzyme inhibition by hydrazine derivatives and for their possible pharmacological applications [1]. Sulfonamides and sulfonyl hydrazones have been shown to be active in several pharmacological tests, demonstrating antibacterial, antitumor, diuretic, antiviral, antinociceptive activity, specific enzyme inhibition such as carbonic anhydrase, c-secretase HIVprotease, metalloproteinase, and hormone regulation among others [2,3]. In this work, the structure of the bis [(N'-(dipyridin-2-ylmethylene)-4-methylbenzenesulfonohydrazone]Ni(II) has been investigated by using elemental analysis, FTIR, UV-VIS spectrophotometric methods. This novel compound has been examined for antibacterial activity against pathogenic strains Enterobacter aerogenes sp., Listeria monocytogenes 4b ATCC19115, Staphylococcus aureus ATCC25923, Escherichia coliATCC1280, S Salmonella typhi H NCTC901.8394, Staphylococcus epidermis sp., Micrococcus luteus ATCC9341, Shigella dysenteria type 2 NCTC2966, Bacillus cereusRSKK-863. An antifungal susceptibility test was used by Candida albicans Y-1200-NIH, Tokyo.

References[1] Ray A, Banerjee S, Sen S, Butcher RJ, Rosair GM, Garland MT, Mitra S (2008). Two Zn(II) and one Mn(II) complexes using two different hydrazone ligands: spectroscopic studies and structural aspects. Struct. Chem., 19: 209� 217.[2] Y. Ozawa, N. Sugi, T. Nagasu, T. Owa, T. Watanabe, N. Koyanagi, H. Yoshino, K. Kitoh, K. Yoshimathu, Eur. J. Cancer 37 (2001) 2275� 2282.[3] L.M. Lima, E.G. Amarante, A.L.P. Miranda, C.A.M. Fraga, E.J. Barreiro, Pharm. Pharmacol. Commun. 5 (1999) 673� 678.


131

P76Extracellular biosynthesis of ZnO nanoparticles from Zn(NO3)2

and their characterization

Abdussamed Yasin Demir1, Mehmet Karadayi2*, Medine Gulluce2,Ozlem Baris2, Hatice Ogutcu3, Burak Alaylar1, Guleray Agar2

1Institute of Natural and Applied Sciences, Atatürk University, Erzurum, Turkey2Department of Biology, Faculty of Science, Atatürk University, Erzurum, Turkey

3Department of Biology, Faculty of Science and Art, Ahi Evran University, Kırşehir, Turkey

*[email protected]

Recently synthesis of zinc oxide (ZnO) nanoparticles has attracted a great interest due to their unique photocatalytic, electrical, electronic, optic and several biological properties, which has enabled development of various synthesis methods including chemical, physical and biological processes. Furthermore biosynthesis of these nanoparticles has gained more attention because of high biocompatibility of the products in various health applications. However, required complex purification steps of biological production methods have remained as a challenge and recent research efforts have focused on extracellular biosynthesis of nanoparticles to develop more suitable methods. Thus, the aim of the present study was determined as extracellular biosynthesis of ZnO nanoparticles from Zn(NO3)2 feedstock by using Rhodococcus K85 strain. For this purpose, the bacterial strain was growth on TSA plates. The bacterial colonies collected with a sterile inoculation loop and transferred into mineral salt basal (MSB) solution to reach 0.5 OD at 600 nm. Then, 5 ml of the prepared culture was inoculated in MSB supplemented with Zn(NO3)2 solution and incubated at 25°C for 3 days at 120 rpm. In the end of the incubation period, nanoparticles were collected after centrifugation, washing and drying steps, respectively. Characterization of the synthesized nanoparticles was done by using SEM and EDAX analytical methods. According to the results, ZnO nanoparticles were successfully biosynthesized in an extracellular manner by using Rhodococcus K85 strain. The average sizes of the nanoparticles were in the range of 132.1 − 399 nm.

As a conclusion, the present study showed that the bacterial Rhodococcus K85 strain is capable of extracellular biosynthesis of ZnO nanoparticles from Zn(NO3)2 feedstock, but optimization studies are still needed to develop more controllable synthesis methods that allow tuning sizes of nanoparticles.


132

P77The effect of CaCO3 amount to physical and chemical properties

of film in blown film applications

Tansu Yazgoren*, Zafer Yazicigil, Hatice Ulusan

Selcuk University, Faculty of Science, Department of Chemistry, 42030 Konya, Turkey

*[email protected]

In this study, the effect of amount of filler masterbatch contains 70% CaCO3 to the physical properties of film which is prepared from different mixtures of filler masterbatch and HDPE by blown film application was determined. 30%, 50% and 70% filler masterbatch were fed with HDPE to the blown film apparatus, then MFI and humidity values were measured. After this treatment, elongation rate and tensile strength of the film were studied separately. Zi-Mak Group blown film extruder was used to produce the film. Instron-Ceast MF-20 was used for determining of MFI and Brabender Aquatrac-3E was used to determine humidity of the film. It was found that MFI values was increased with increasing of filler masterbatch ratio. It was also seen that increase in filler masterbatch also increased humidity. Elongation rate and tensile strength of the film was decreased by increasing filler masterbatch.


133

P78Microporous activated carbon prepared from cherry stones using

microwave activation with zinc chloride

Taner Erdogan*,Fatma Oguz Erdogan

Kocaeli University, Kocaeli, Turkey

*[email protected]

Activated carbons are one of the most commonly used adsorbents because of its good adsorption properties. They have a very broad range of applications in different industries which include gas purification, removing of organic pollutants from drinking waters as well as waste waters, several medical applications, hydrogen storage, dye adsorption and as catalyst support owing to their surface area, pore structure, thermal stability and low acid/base reactivity. In this study, activated carbon samples were prepared with ZnCl2 activation by microwave energy in a short time. Compared with conventional heating techniques, microwave heating has the advantages of interior heating, higher heating rates, saving energy, and greater control of the heating process. Optimized parameters were radiation power of 300 W, radiation time 5 min, and zinc chloride/carbon ratio 1:1 and impregnation time 20 h, respectively. The surface characteristics of the activated carbon prepared under optimized conditions were examined by pore structure analysis, scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR). The results showed that radiation time and radiation power were the greatest impact factor on surface area and micropore volume of the activated carbon prepared with ZnCl2. The highest surface area of the activated carbon was 1965 m2/g by radiation time 5 min and microwave radiation of 300 W.

AcknowledgementThe authors are grateful for financial support of Project Numbers 2011/062 and 2014/113 HDP of Kocaeli University.


134

P79Preparation of activated carbon from waste cherry stones by

KOH and NaOH activations for hydrogen sorption

Fatma Oguz Erdogan*, Taner Erdogan


*[email protected]

Hydrogen is an ideal alternative to fossil fuels from an environmental point of view because its combustion does not generate pollutants such as hydrocarbons, sulphur oxides, carbon monoxide, nitrogen oxides and particles. Hydrogen storage has been studied in a large variety of activated carbons and a wide range of pressures. Activated carbons can be prepared from various waste biomass sources such as waste cherry stones, waste tea, apricot stones, almond shells and coal. In this study activated carbons were prepared with KOH and NaOH activation by microwave energy in a short time and they were characterized in terms of surface area, pore size distribution, pore volume, SEM and FTIR analysis. Results of the hydrogen sorption experiments of activated carbon samples have showed that the highest surface area was obtained at the activation temperature of 300°C using KOH. The obtained samples were compared according to their hydrogen sorption capacities.



135

P80Adsorption of textile dye from aqueous solutions with MCM-41

Fatma Oguz Erdogan*, Taner Erdogan


*[email protected]

Porous solids are of scientific and technological interest because of their ability to interact with atoms, ions and molecules. MCM-41, one member of the mesoporous molecular sieves M41S family, possesses a high specific surface and regular hexagonal array of cylindrical pores, which is largely used in shape selective catalysis, selective adsorption and separation processes, chemical sensors, as well as nanotechnology. Moreover, its large specific surface area and nanometer-sized pore sizes (from 20 to 100 Å) also offer a special environment for chemical separations of large molecules such as dyes. In this study, our objective is to examine the possible effect of interactions between large dyes and MCM-41 on the pore structure of MCM-41 and the potential of MCM-41 for the removal of textile dyes from wastewater by measuring the adsorption data of Disperse Yellow 211 (DY 211). The fitness of both Langmuir and Freundlich adsorption model on describing the equilibrium isotherms of DY 211 was examined. The suitability of both pseudo-second-order kinetic model and the intraparticle diffusion model for the description of the kinetic data was investigated, from which the adsorption mechanism was examined.



136

P81Estimation of the Al-10Fe-3V-1Si matrix contribution to the

SDAR-OES measurement uncertainty

Alecs Andrei Matei1*, Ion Pencea2, Catalin Eugen Sfat2, Mihai Branzei2, Ramona Nicoleta Turcu2, George Stanciu1

1Center for Microscopy-Microanalysis and Information Processing, University POLITEHNICA of Bucharest, Splaiul Independentei 313, sector 6, Bucharest, Romania

2Materials Science and Engineering Faculty, University POLITEHNICA of Bucharest,Splaiul Independentei 313, sector 6, Bucharest, Romania

*[email protected]

The Al-10Fe-3V-Si master alloy is the precursor of the nanostructured ribbons for automotive and aeronautical applications. The elemental concentrations of such a master alloy have to fulfil smaller tolerances. Thus, the exactness of the elemental analysis is a critical step in the process of manufacturing of such ribbons.

One of the most efficient spectrometric techniques for elemental analysis of metallic grades is Spark Discharge in Argon-Optical Emission Spectrometry (SDAR-OES). The adequacy of SDAR-OES for Al-10Fe-3V-Si analysis depends on lowering the measurement uncertainty (MU) below the tolerance limit. On the other hand, the decreasing of MU is hindered by the uncertainty budget factors as: equipment, operator, environment, certified reference materials (MRC), sampling and specimen heterogeneity. The operator and environmental factors are no significant factors while the matrix effect and calibration curve are of greater importance. Matrix effect addresses the spectral yield dependence on the intrinsic properties of the specimen like chemical heterogeneity, microstructure heterogeneity, cleanness, oxidizing resistance, thermal conductivity etc. The calibration curve factor is the most significant contributor to the uncertainty budget when elemental concentration is closer to the LOQ (Limit of Quantification).

To assess the contribution of the matrix to the uncertainty budget, 14 specimens of Al-10Fe-3V-1Si alloys were investigated using a SPECTROMAXx equipped with CCD detectors.

The novelties addressed in the paper consist in: 1) substantiation of the matrix contribution to the measurement uncertainty for SDAR-OES analysis of Al-Fe-V-Si alloys; 2)a robust procedure for MU estimation based on GUM approach and acquired knowledge.

For better assessing of matrix effect upon Al-10Fe-3V-1Si spectrochemical data, further investigations have to be done. Thus, microprobe technique and X-ray diffraction have to be used for investigation of the oxide formation during sparking and to establish the nature of burn-off products.AcknowledgementThe work has been funded by the Sectoral Operational Programme Human Resources Development 2007-2013 of the Ministry of European Funds through the Financial Agreement POSDRU/159/1.5/S/134398.


137

P82Synthesis and characterization of ZnO, Cu0.5Zn0.5O and

CuO thin films

Mehmet Ali Yıldırım1*, Sümeyra Tuna Yıldırım2, Aytunç Ateş3

1Department of Electrical and Electronic Engineering, Erzincan University, Turkey2Department of Analytical Chemistry, Erzincan University, Turkey

3Department of Material Engineering, Yıldırım Beyazıt University, Turkey

*[email protected]

CuxZn1-xO (x = 0, 0.50, 1) thin films were synthesized on glass substrates using Successive Ionic Layer Adsorption and Reaction (SILAR) method at room temperature. The copper (Cu) concentration (x) effect on the structural, morphological and optical properties of CuxZn1-xO thin films was investigated. The X-ray diffraction (XRD) and scanning electron microscopy (SEM) studies showed that all the films exhibit polycrystalline nature and are covered well with glass substrates. The crystalline and surface properties of the films improved with decreasing copper concentration. The energy bandgap values were changed from 3.28 to 2.02 eV depending on the copper concentration. The refractive index (n), optical static and high frequency dielectric constants (εo, ε∞) values were calculated by using the energy bandgap values as a function of the copper concentration.


138

P83Stability indicating RP-HPLC method development and validation for bosentan in pharmaceutical formulations

Mehmet Emrah Yaman*, Yucel Kadioglu, Didar Turkan, Alptug Atila

Ataturk University, Faculty of Pharmacy, Department of Analytical Chemistry

*[email protected]

A new, simple and rapid HPLC method for the determination of bosentan in pharmaceutical formulations was developed and validated. Bosentan, (4-tert-butyl-N-[6-(2-hydroxyethoxy)-5-(2-methoxyphenoxy)-2-(pyrimidin-2-yl) pyrimidin-4-yl], is a competitive oral dual endothelin receptor antagonist which is non-selective for endothelin A and B receptors. There are several analytical methods for the quantitative determination of bosentan in pharmaceuticals including spectroscopy and electrochemistry, also there are a few chromatographic methods according to literature researches.

In order to carry out this study, method parameters were optimized to be 1 mL/min flow rate, variable column temperature, a mixture of methanol-acetonitrile-water (20:50:30 v/v/v) as mobile phase. All measurements were performed on 272 nm wavelength with UV detector. The method was validated in terms of specificity, limit of quantitation (LOQ), limit of detection (LOD), linearity, accuracy, precision, stability, recovery and ruggedness. Method was linear between 0.25 − 20 µg/mL, precision and accuracy of the method was lower than 3.0% and 2.7%, respectively. LOQ and LOD values were 0.25 and 0.1 µg/mL, respectively. The method was successfully applied onto pharmaceutical formulations, which were purchased from local pharmacy store, and the method was used for identifying the stability of bosentan under degradation conditions proposed by ICH guideline. It was found that 10 µg/mL bosentan standard solution was relatively stable at acidic and basic environments (0.1 N HCl and 0.1 N NaOH) and unstable at oxidation environment (H2O2 solution (3% v/v)).


139

P84Application of chemometric methods for resolving complex drug

mixtures

Gеorgi Gergov1*, Stefan Platikanov2, Michele De Luka3 , Darvin Ivanov1,Yahya Salem Al-Degs4, Vasil Simeonov5

1Department of Chemistry, Faculty of Pharmacy, Medical University, ul. Dunav 2, 1000 Sofia, Bulgaria2Environmental Chemometrics Group, Department of Environmental Chemistry, Institute for Chemical and

Environmental Research, CID-CSIC, Jordi Girona 18, E-08034 Barcelona, Spain3Department of Pharmaceutical Sciences, University of Calabria, Via P. Bucci, 87036 Rende, Cosenza, Italy

4Chemistry Department, the Hashemite University, P.O. Box 150459, Zarqa, Jordan5Laboratory of Chemometrics and Environmetrics, Faculty of Chemistry and Pharmacy, Sofia University� St.

Kliment Ohridski� , J. Bourchier Blvd. 1, 1164 Sofia, Bulgaria*[email protected]

The standard and official analytical methods for resolution of pharmaceutical formulations aretedious, non-specific and time consuming, involve pre-treatment of the sample through complex chemical steps to eliminate the interferences commonly found, followed by individual method for each different drug. Recently spectrophotometry in particular has benefited from the combination with the chemometric procedures for the simultaneous analysis of such pharmaceutical formulations containing compounds with strongly overlapping spectra.

We have developed simple spectrophotometric method for fast analysis of quaternary druganalgesic formulations Paracofdal® (Unipharma), containing paracetamol (PAR), metamizole (MET), caffeine (CAF) and codein (COD). A two-way UV spectral data are formed by measuring absorbance under different wavelengths at a series of mixtures of drugs chosen by means of an appropriate design. First-order calibration techniques (PLS1 and PLS2) are applied because of their reliability and easy to use with available software packages for multivariate calibration. Mathematical calculations for PLS1 were carried out using MVC1® and TOMCAT® programs. Independently running PLS2 were carried out using home-made matlab® codes.

The first order calibration methods (PLS variants) need that both unknown tablets and standards have the same chemical and physical characteristics, even the eventual interferences. Second order calibration methods can compensate for potential interferences which are not included in the calibration step, in our case pharmaceutical exipients. This is universally recognized as the second order advantage. Multivariate curve resolution optimized by alternating least squares (MCR-ALS) was applied for this purpose. For quantification, the data matrices corresponding to the calibration, validation and samples matrices were disposed in a column-wise augmented matrix andsimultaneously analyzed in order to achieve the second order advantage. The effect of different preprocessing was studied. For optimization, different constraints were applied to drive the final solution towards a chemical meaning.

In the current study, a two chemometric strategy for the determination of mixtures of paracetamol (PAR), metamizole (MET), caffeine (CAF) and codein (COD) were proposed and compared. The chemometric models were tested on an external validation dataset and finally applied to simultaneous determination of the above compounds in pharmaceutical tablets.


140

P85A layer-by-layer biosensing architecture based on

polyamidoamine dendrimer and carboxymthylcellulose-modified grapheme oxide

Boryana Borisova*, Javier Ramos, Alfredo Sanchez, Paula Díez,Concha Parrado, Elena Araque, Reynaldo Villalonga, José M. Pingarrón

Department of Analytical Chemistry, Faculty of Chemistry, Complutense University of Madrid,28040 Madrid, Spain

*[email protected]

A novel nanostructured architecture for the construction of an amperometric enzyme biosensor toward catechol is described. It was based on the electrostatic layer-by-layer assembly of four-generation ethylenediamine core polyamidoamine G-4 dendrimers on glassy carbon electrodes coated with a graphene oxide-carboxymethylcellulose hybrid nanomaterial. This modified surface was further employed for the covalent immobilization of tyrosinase through a glutaraldehyde-mediated cross-linking. The enzyme electrode was used for the amperometric detection of catechol in the 2 � 400 nM range. The biosensor showed excellent analytical performance with high sensitivity of 6.3 A/M and low detection limit of 0.9 nM. The enzyme electrode retained over 93% of the initial activity after 40 days of incubation at 4ºC.


141

P86Synthesis, characterization of a new Schiff base ligand

5-hydroxysalicylidene-4-chloro-o-aminophenol and investigation of its metal complexes

Sümeyra Tuna Yıldırım

Erzincan University, Faculty of Pharmacy, Department of Analytical Chemistry, Erzincan, Turkey

[email protected]

Schiff bases are series of ligands capable of binding metal ions leading to metal complexes with interesting properties. The high stable potential of Schiff base complexes in different oxidation states increased the application of these compounds in a wide range. Some of these types of ligands and their metal complexes have been investigated because of their interesting and important properties such as their ability to reversibly bind oxygen and their use in catalysis for oxygenation. Schiff bases that have solvent dependent UV/VIS spectra can be suitable NLO materials. These ligands can be useful materials in solid phase extraction and synthesis of ionselective electrodes for the determination of anions in analytical samples. And also they are used in production of the dyestuffs, cosmetics, agriculture, production of polymers and many subsection of industry such as electronic industry and aircraft industry [1].

In this study, the ligand of 5-hydroxysalicylidene-4-chloro-o-aminophenol was synthesized by the reaction of 5-hydroxysalicylaldehyde and 4-chloro-o-aminophenol in absolute ethanol at 60oC by the catalyzed of p-toluenesulfonic acid. Later, the complexes of this ligand were prepared with Co(II), Ni(II), Cu(II) and Zn(II) in acetate forms in pure EtOH. The structures of ligands and complexes were identified using Elemental Analysis, FT-IR, 1H-NMR, 13C-NMR, UV-VIS, Magnetic Susceptibility and Thermogravimetric Analysis [2]. All of the Schiff bases were found to be bidentate ligands involving the imino nitrogen and phenolic oxygen atoms in the complexes and M:L ratio were found to be 1:2 for all the complexes. Additionally, electrical and optical properties of synthesized ligand and complexes were examined.

[LH] Ligand

References[1] P.A., Vigato and S. Tamburini, Coord. Chem. Rev. (2004), 248, 1717.[2] S. Tuna (2010), Synthesis and Characterization of Schiff Base Ligands Containing Aromatic Amine and Investigation of Their Transition Metal Complexes, PhD Thesis, Fırat University, Elazıg.


142

P87Synthesis, characterization of new Schiff base ligand containing

aromatic amines and investigation of its metal complexes

Sümeyra Tuna Yıldırım

Erzincan University, Faculty of Pharmacy, Department of Analytical Chemistry, Erzincan, Turkey

[email protected]

The coordination chemistry of nitrogen� oxygen donor ligands is an interesting area of research. A great deal of attention in this area has been focused on the complexes formed by transition metal ions with Schiff bases because of the presence of both nitrogen and oxygen donor atoms in the backbones of these ligands. Schiff base ligands may act as bidentate N,O-, tridentate N,O,O-, N,O,N-, and tetradentate N,N,O,O- which can be designed to yield mononuclear, binuclear, one-dimensional (1D), two-dimensional (2D) and three-dimensional (3D) metal� organic frameworks. They can also accommodate different metal centers involving various coordination modes thereby allowing successful synthesis of homo- and heterometallic complexes with varied stereochemistry. Schiff bases were used in medicine and pharmacy, the preparation of some drugs. We know that some schiff base ligands and their transition metal complexes have wide applications in biological field, as antidepressants, antimicrobial, antibacterial, antifungal, antitumor, anticancer, antiulcer, antitumor, antioxidant, antiphlogogistic, nematocide and other medicinal agents have been reported based on these compounds. Furthermore they are used in cosmetics, agriculture, production of polymers and many subsection of industry like plastic industry, electronic industry, textile industry, paint industry. The metal complexes with schiff bases, containing auxochrome groups, were used as dyestuffs at paint industry expressly at textile industry, becuase of their colors. Especially, when textile metarials dyeable feature was examined of the complexes of schiff base ligand obtained from substitute o-hydroxyaniline and salicylaldehyde, yellow and orange colors were found by the painting of polystyrene resins [1,2].

In this study, the ligand of 3,5-diiodosalicylidene-p-aminoacetophenoneoxime and its complexes were synthesized and their structures were characterized by spectroscopic techniques.

References[1] Sharma, P. K., Handa, R. N. and Dubey, S. N. � Synthesis and Characterization of Some Transition Metal Complexes of N-(2-Hydroxy-1-Naphtylidene) Amino Acids � , Synth. React. Inorg. Met. Org. Chem., (1996), 26(7), 1219.[2] Adamantia K., Giannis S. P., Catherine P., Synthesis and Structure of N-Salicylidene-o-aminophenolato Gallium(III) Complexes, Polyhedron (2009), 28, 3279-3283.


143

P88Silver nanoaprticles grafted on submicron silica as a sobrent for

Mercury speciation in surface waters

Tanya Yordanova1,2*, PenkaVasileva2

1Department of AnalyticalChemistry,2Laboratory of Nanoparticle Science and Technology, Department of General and InorganicChemistry

Faculty of Chemistry and Pharmacy, University of Sofia � St. KlimentOhridski� , Bulgaria

*[email protected]

The European Water Framework Directive (WFD) establishes a framework for the protection of ground and surface waters. Its final objective is achieving at least � good water status� for all waters, by 2015, which means good ecological and chemical status. Extremely low Environmental quality standard is adopted for Hg, priority pollutant, defining chemical status of water body due to its high toxicity. Analytical procedure should ensure determination of as low as 0.015 µg/L with uncertainty no more than 50%. Preliminary separation and concentration which allows simultaneous Hg speciation is a good decision for such analytical challenge. The present study describes successful preparation and application ofsilica supported silver nanoparticles for mercury speciation and determination in surface waters. For this purpose, silicon dioxide core spheres (Dav = 370 nm) are prepared using the modified Stöber method and subsequently functionalized with terminal amine groups. Preformed by green synthesis method starch-stabilized silver (Dav = 14 nm) or gold (Dav = 11 nm) nanoparticles are grafted on the surface of amine-functionalized silica submicrospheres via colloid mixing.

Simple, fast and low cost analytical procedure is developed for easy and highly sensitive speciation and quantification of Hg ions using AgNPs decorated silica nanosorbent. Optimal conditions for selective quantitative sorption of Hg(II) by using AgNPsgraphted silica (pH, sorbent amount, sorption time) are defined. Under these conditions degree of sorption of methyl mercury is less than 1%. Analytical procedure (quantification limits 0.01 µgL-1) is developed for Hg speciation and determination in surface waters using ETAAS or CV AAS as instrumental methods and applied for Black sea waters.

A possible mechanism of mercury speciation is proposed on the based of TEM observations and analysis of SAED patterns of the aggregated masses formed after the addition of 1 ppm Hg (II) solution to silver colloid or SiO2/Ag nanocomposite sorbent.

AcknowledgementThe author Tanya Yordanova (young scientist) is grateful for financial support of Bulgarian Ministry of Education and Science.


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Name Author index

T. Abdelkrim P29H. Abdolmohammad-Zadeh O2H. Acıdereli P10, P38G. Agar P75, P76U. K. Ahmed O14H. Ahmed P29S. Akman O5, P14, P15, P18S. Aktaş P17A. H. Aktaş P26, P28M. Akyüz O7, P35B. Alaylar P76C. Albay P66, P67Y. Al-Degs P84Th. S. Al-Ghabsha O15İ. Altın P66, P67, P68G. İ. Altındağ O3K. Amina P51J. Angarska P43P. Angelov P2M. Angelova P25R. E. Anlı P31G. Antova P46R. Apak O13M. Arabadji IL4E. Araque P85H. Arslan P60M. Y. Aşcı P70Ş. Ata O7, P35, P63O. Y. Ataman IL8A. Ateş P82A. Atila P83T. Aydemir O3F. Aydın P12A. O. Aydın P72M. Ayranov P32P. I. Azez P55

A. Baaliouamer P51K. Bačeva P27, P47R. Balkanska P11I. Bangov P57, P58


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O. Baris P76H. Bati P75R. Bayrak P66, P67A. Baysal O5, P36T. Y. Bekircan P62H. Belayachi P39M. Belhakem P39M. Berber P35Z. Bıyıklıoğlu P68E. Ö. Bolat P64S. Bora IL8B. Borisova P85S. Bourahla P39A Bozhinova P25M. Branzei O9, P54, P81Z. Bratanova P20, P22A. Bulut P69, P70İ. Bulut P69, P70

H. Çabuk P35, P63A. Cahil P53A. Canals O10S. Candir O11S. Chakarova P56A. Chebotarev IL4, P21M. Chochkova P7M. Çınarlı P75M. Cojocaru O9, P54F. Coldur P65O. Çubuk P65

I. Dakova P7, P22İ. Değirmencioğlu P66, P67E. Demir P62A. Y. Demir P76A. Detcheva P33P. Díez P85I. Dimitrov P45P. Dimitrova P27N. Djapic P30L. Djerahov P5, P27D. A. Dobreva P41


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H. Dočekalová IL3A. Duhan O12

I. Efimova P21S. Ekin P65E. Er P8, P40U. S. Erdemir O6, P60T. Erdogan P78, P79, P80F. O. Erdogan P78, P79, P80S. Erdoğan P10Ü. C. Erim P72N. Erk P8, P40G. Ertaş IL8

N. A. Fakhre O14A. Fatiha P49G. Fedosenko P48D. V. Filosofov P37

S. Ganeva P19K. Gavazov O10G. Gencheva P56G. Gentscheva P45, P46S. Georgieva P13A. Georgieva P13R. Georgieva P33G. Gergov P84Z. Glavcheva P59, P61F. Göde P28Ş. Güçer IL6, P60D. Guirdzhiiska P61G. Guleryuz P60M. Gülfen P72M. Gulluce P76B. Gürler O7S. Gyurov P52

M. A. Hasan O15M. Hazzit P51


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M. Imamoglu P6S. Ince O5H. Incebay P73İ. Isildak P65D. Ivanov P84

Y. Kadioglu P83Y. Kadioğlu O13G. S. Kanberoglu P65S. A. Karaca P3M. Karadayi P76M. Karadjov P27I. Karadjova P4, P7, P11, P20, P22, P46, P47M. Karakaplan P16M. Y. E. Karaman P75Z. Kavrakovski P23, P24E. Kılıç O5A. Kirilov P20S. Kırlangıç P17A. Kjulumoska-Gjorgjievska P47V. Kmetov O10, P42M. Koç P66, P67Z. E. Koç P74M. B. Koçer P64N. Kolarova-Ianeva P25S. D. Kolev IL5V. Koleva P53Y. Kostova P45, P52P. Kovacheva P32D. Kovacheva P52C. Kuznek P36

M. Lal O12G. Lalev P59I. Leonenko P48M. De Luka P84

L. Makedonski P9N. Marinkov P45, P52G. Marinov P37A. A. Matei O9, P54, P81


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A. Merdzhanova P43M. Milanova P37R. Milina P57, P58M. Mitreva P22E. Mladenova P11M. Moskovkina P57, P58Z. Mustafa P57, P58B. Mutlutürk P26

M. Najdoski P53I. Narin O11V. Nedkova P25K. Nikolova P46

H. Öğütcü P75, P76S. Öz P31N. Ozbek O4, O5, P14, P15, P18M. Ozcan O4, P16, P17, P36C. Ozcan P1F. Öztürk P69

R. E. Parlar P72C. Parrado P85V. Pavlova P20, P22V. Pehlivan P70Ş, Pekyardımcı P64I. Pencea O9, P54, P81I. Penkov P52Z. Peteva P41Zh. Petkova P46M. Petleshkova O10, P42P. Petrova P7K. Peycheva P9J. M. Pingarrón P85S. Platikanov P84O. Popovska P23, P24A. Predoeva P46

E. Raboshvil P21V. Rafajlovska P23, P24


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E. Rahimpour O2J. Ramos P85Ch. M. Rashid O14H. Razmi O1

S. Saïd P49, P50R. � ajn P47A. Sanchez P85D. Schumann P32Yu. Scrypynets P48O. Şenol O13C. E. Sfat O9, P54, P81V. Simeonov P84K. Simitchiev O10, P42S. Sivrikaya P6M. Slaveikova P32V. I. Slaveykova IL7M. Smolinska P44M. Sökmen IL1, P62, P66, P67, P68A. Sökmen P62B. Soulimane P49, P50M. Soylak IL2, P12, P34T. Stafilov P47B. Stamboliyska P61M. Stancheva P9, P13R. Stancheva P43G. Stanciu P81V. Stefanova O10, P2, P42T. Stefanova O10V. Stefov P53

G. Teke P31H. Tesliar P44G. A. Tığ P64V. Todorov P61B. Toker P8C. Topcu P65S. Tsakovski P19R.-N. Turcu O9, P54, P81D. Turkan P83M. Tuzen P34Ch. Tzvetkova P45


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D. Y. Uğur P3H. Ulisan P77H. İ. Ulusoy P10, P38S. Ulusoy P10, P38Y. E. Unsal P34

E. Varbanova P2P. Vasileva P4, P5P. Vassileva P33E. Velcheva P61O. Veleva P27R. Villalonga P85Ts. Voyslavov P11, P19S. Vutov P41

A. Yaar P62M. Yaman O8, P1M. E. Yaman P83D. Yancheva P61B. Yavuz P71T. Yazgoren P77Z. Yazicigil P71, P73, P77M. Yazıcıoğlu P31A. Yegorova P48M. A. Yıldırım P82S. T. Yıldırım P82, P86, P87A. Yılmaz IL8E. Yılmaz P12T. Yordanova P88M. Yurkevych P44

A. Zacharia IL4, P21V. Zapryanova O10, P42


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University of Sofia "St. Kliment Ohridski"Scientific Foundation (Grant No 163/2015)

Ministry of Education and Sciences

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