Cover Picture

Vol. 26, No. 8, August, 2015

ISSN 0103-5053JBCSJournal of the Brazilian Chemical Society

Luteinizing hormone (LH) can be used by athletes to take illicit advantage in sport activities, therefore it is analyzed in anti-doping control by immunoassay. Since LH is an endogenous substance, the urinary excretion profile of the hormone in Brazilian male athletes was established in order to allow the inference of a possible abuse in sports. Details are presented in the Article Urinary Excretion Profile of Luteinizing Hormone in Brazilian Athletes by Patrícia D. O. Sardela, Vinícius F. Sardela, Henrique M. G. Pereira and Francisco R. Aquino Neto on page 1599.

Contents

Communication1533 S y n t h e s i s o f 4 - A r y l s e l a n y l p y r a z o l e s T h ro u g h

Cyclocondensation Reaction Using Glycerol as SolventJosé E. R. Nascimento, Daniela H. de Oliveira, Paola B. Abib, Diego Alves, Gelson Perin and Raquel G. Jacob

Graphical AbstractWe describe here a simple method to synthesize 4-arylselanylpyrazoles by reaction of α-arylselanyl-1,3-diketones with arylhydrazines using glycerol

as solvent at 60 °C under N2 atmosphere. This is a direct cyclocondensation reaction performed with α-arylselanyl-1,3-diketones and arylhydrazines

bearing electron-withdrawing and electron-donating groups affording the corresponding 4-arylselanylpyrazoles in moderate to good yields

SI online

J. Braz. Chem. Soc.iv

1551 Selective Hydrogenolysis of Glycerol to 1,2-Propanediol Over Bimetallic Cu-Ni Catalysts Supported on γ-Al2O3

Satyanarayana M. Pudi, Prakash Biswas, Shashi Kumar and Biswajit Sarkar

Graphical AbstractCu-Ni(1:1)/γ-Al2O3 catalyst exhibited a maximum glycerol conversion of 71.6% with 92.8% selectivity to 1,2-propanediol at 210 °C and 4.5 MPa

hydrogen pressure. The superior performance was attributed to the strong interaction between Cu and Ni, small particle size, and high acidic

strength of the catalyst

1573 A Fast Chromatographic Method for Determination of Daidzein and Genistein in Spiked Water River Samples Using Multivariate Curve ResolutionEdilene D. T. Moreira, Licarion Pinto, Adriano A. Gomes, Héctor C. Goicoechea and Mário C. U. Araújo

Graphical AbstractSimultaneous quantitation of daidzein and genistein in river water

samples using high performance liquid chromatography-diode array detection (HPLC-DAD) and extend multivariate curve resolution-

alternative least square (MCR-ALS) calibration

Articles1542 Metal-Modified Mesoporous Silicate (MCM-41) Material:

Preparation, Characterization and Applications as an AdsorbentAlejandra S. Diez, Mariana Alvarez and Maria A. Volpe

Graphical AbstractThe preparation of pure and Metal-MCM-41 was carried out in water/

surfactant/silicate mixtures. The presence of acidic sites favoured the phenol adsorption over Al-MCM-41 at low pH

1565 New Terpenoids from Croton limae (Euphorbiaceae)Antonio H. Sousa, José N. Silva Junior, Maria L. S. Guedes, Raimundo Braz-Filho, Letícia V. Costa-Lotufo, Ana J. Araújo, Edilberto R. Silveira and Mary A. S. Lima

Graphical AbstractAn asymmetrical dimer of a kaurane diterpene and monoterpene and

four novel diterpenes were isolated from the roots of Croton limae along with other known compounds. The kaurane diterpene exhibited cytotoxic

activity against HCT-116, OVCAR-8 and SF-295 cancer cell lines

1583 Maleic Anhydride as a Compatibilizer and Plasticizer in TPS/PLA BlendsSamuel H. Clasen, Carmen M. O. Müller and Alfredo T. N. Pires

Graphical AbstractImmiscible thermoplastic starch/poly(lactic acid) grafted with maleic

anhydride (TPS/PLA-g-MA) blend and in detail the hydrogen bond between the TPS matrix and PLA-g-MA domains, due to the use of MA as

a compatibilizer

SI online

vVol. 26, No. 8, 2015

1599 Urinary Excretion Profile of Luteinizing Hormone in Brazilian AthletesPatrícia D. O. Sardela, Vinícius F. Sardela, Henrique M. G. Pereira and Francisco R. Aquino Neto

Graphical AbstractLuteinizing hormone (LH) is included on the World Anti-Doping Agency

prohibited list. Since LH is an endogenous substance, it is necessary the establishment of the urinary excretion profile of the hormone in Brazilian

athletes in order to allow the inference of a possible abuse in sports

1617 Chromatographic and Calculation Methods for Analysis of the Lipophilicity of Newly Synthesized Thiosemicarbazides and their Cyclic Analogues 1,2,4-Triazol-3-thiones Anna M. Hawrył, Łukasz P. Popiołek, Mirosław A. Hawrył,

Ryszard S. Świeboda and Milena A. Niejedli

Graphical AbstractThe newly synthesized thiosemicarbazide derivatives were analyzed by reversed phase high performance liquid chromatography (RP-HPLC) and

reversed phase thin layer chromatography (RP-TLC) methods. The log PHPLC and log PTLC parameters were determined based on the Organisation

for Economic Co-operation and Development (OECD) guidelines

1608 Surface Modification and Spectroscopic Characterization of TiO2 Nanoparticles with 2-Aminoethyl Dihydrogen PhosphateEffat Iravani, Sareh A. Allahyari, Zahra Shojaei and Meisam Torab-Mostaedi

Graphical AbstractAmino functionalization of nano TiO2 particles with monoester phosphate

through strong covalent interactions

1591 Pal ladium Nanopart ic les Supported on Poly(N -vinylpyrrolidone)-Grafted Silica as an Efficient Catalyst for Copper-Free Sonogashira and Suzuki Cross-Coupling ReactionsBahman Tamami, Fatemeh Farjadian, Soheila Ghasemi, Hamed Allahyari and Motahareh Mirzadeh

Graphical AbstractPalladium nanoparticles supported on polyvinylpyrrolidone grafted silica

was prepared. The catalyst exhibited excellent activity in Sonogashira and Suzuki coupling reactions

SI online

SI online

1625 Synthesis of Triacetin and Evaluation on Motor Claudia V. Lacerda, Maria J. S. Carvalho, Alice R. Ratton, Itânia P. Soares and Luiz E. P. Borges

Graphical AbstractThe use of triacetin, produced from glycerol and acetic acid, as an

additive for diesel oil and biodiesel contributes to a reduction in the emission of pollutants into the atmosphere, as shown by the results of a

test engine experiment

J. Braz. Chem. Soc.vi

1642 Separation and Preconcentration of Trace Amounts of Lead from Water Samples Using Solvent-Assisted Dispersive Solid Phase Extraction Reyhaneh Rahnama and Raofeh Ghadiri

Graphical AbstractThis paper describes a new approach for the preconcentration of lead by

solvent-assisted dispersive solid phase extraction (SADSPE) from water samples prior to analyzing by flame atomic absorption spectrometry (FAAS)

1656 The Inhibition of Sodium Oleate for Pitting Corrosion of Aluminum Alloy 2024 in 0.1 mol L-1 NaCl SolutionYu Zuo, Shiwen Wang, Yuming Tang and Yong Zhou

Graphical AbstractSodium oleate suppressed the tendency of pitting initiation and reduced

the pitting corrosion sensitivity of Al alloy 2024 in 0.1 mol L-1 NaCl solution. The C17H33COO− groups adsorbed on the surface of Al alloy by chemical

adsorption effect, which promoted oxidation of the Al alloy surface

1648 Spurious Phosphorus Pyramidalization Induced by Some DFT FunctionalsCarina F. Pupim, Nelson H. Morgon and Alejandro Lopez-Castillo

Graphical AbstractThe observed pyramidalization of phosphorus atoms in resonance

structures is due to a spurious error introduced by some density functional theory (DFT) functionals. The optimized geometries of boron

and phosphorus (BP-systems), as calculated using electron correlation (e.g., MP2 and CC), exhibit D3h symmetry (i.e., a flat molecular

structure). However, C1 symmetry can instead be obtained when employing certain exchange-correlation (XC) functionals

1632 Non-Enzymatic Amperometric Determination of Glucose by CuO Nanobelt Graphene Composite Modified Glassy Carbon ElectrodeSreeramareddygari Muralikrishna, Kempahanumakkagari Sureshkumar, Zhou Yan, Carlos Fernandez and Thippeswamy Ramakrishnappa

Graphical AbstractOne pot synthesis of CuO nanobelt decorated graphene oxide (GO) as well as conversion to CuO nanobelt decorated reduced GO (rGO) and

used for electrochemical sensing of glucose has been reported

1664 Characterization and Distribution of Pyrogenic Carbon in a Fraction of Archaeological Black Earth from CaxiuanãMilena Carvalho Moraes, Vanda Porpino Lemos, Dorsan Santos Moraes and Cláudio Nery Lamarão

Graphical AbstractThe study of pyrogenic carbon (PyC) in the archaeological black

earth (ABE) profile was based on the O/C atomic ratio, determined by scanning electron microscopy combined with energy dispersive

spectroscopy (SEM/EDS)

SI online

SI online

viiVol. 26, No. 8, 2015

1684 Simultaneous Determination of Catecholamines and Metanephrines in Urine by Liquid Chromatography Electrospray Ionization Tandem Mass Spectrometry: Successful Clinical ApplicationMaria E. R. Diniz, Leandro S. Vilhena, Breno P. Paulo, Tatiana C. C. Barbosa and Elvis C. Mateo

Graphical AbstractIn this study diphenylboronate was used in basic pH for complexation

of analytes, subsequent liquid-liquid extraction with ethyl acetate and its simultaneous analysis by liquid chromatography tandem mass

spectrometry (LC-MS/MS)

1702 A Computational Protein Structure Refinement of the Yeast Acetohydroxyacid SynthaseJéssica C. M. Ierich, Guedmiller S. Oliveira, Ana C. A. Vig, Adriano M. Amarante, Eduardo F. Franca, Fábio L. Leite and Yvonne P. Mascarenhas

Graphical AbstractA full atomic description of the yeast acetohydroxyacid synthase (AHAS)

was obtained by applying computational modeling protocols and molecular dynamics techniques. The refined model proposed will be useful for

biosensor developing and other theoretical/experimental studies

1692 Bulk Atmospheric Deposition of Major Ions and Dissolved Organic Nitrogen in the Lower Course of a Tropical River Basin, Southern Bahia, BrazilTaiana G. Araujo, Marcelo F. L. Souza, William Z. de Mello and Daniela M. L. da Silva

Graphical AbstractThe atmospheric role in the biogeochemical cycles: atmospheric

deposition as an important pathway of nutrients and other compounds to aquatic ecosystems

1674 Simultaneous Determination of Environmental Contaminants with Different Volatilities in Tap Water Samples Using a New Approach to Single-Drop Microextraction ProcedureJosias Merib, Adriana N. Dias, Vanessa Simão and Eduardo Carasek

Graphical AbstractTap water samples were submitted to a new microextraction mode for the single-drop microextraction (SDME) procedure. This new approach

was applied for the determination of compounds with huge differences in their volatilities in a single assay, with good extraction efficiency

1710 CuO Nanofibers Immobilized on Paraffin-Impregnated Graphite Electrode and its Application in the Amperometric Detection of GlucoseÍcaro A. Simon, Natália G. Medeiros, Ketlin C. Garcia, Rosane M. D. Soares, Aline T. Rosa and Jacqueline A. Silva

Graphical AbstractCopper oxide nanofibers synthesized by electrospinning technique and

subsequent thermal treatment, were used to modify paraffin-impregnated graphite electrode for a sensitive non-enzymatic glucose detection

SI online

SI online

J. Braz. Chem. Soc.viii

1718 Influence of the Lipid Phase Removal on the Quantification of Cu, Fe and Zn Bound to Proteins from Golden Flaxseed (Linum usitatissimum L.)Deyse de Brito Marthe, Rodinei Augusti and Letícia Malta Costa

Graphical AbstractOrganic solvents were used to remove lipid phase in the golden flaxseed

samples previously to the analyses of Cu, Fe and Zn bound to proteins

Short Report1725 Dinor Casearin X, a New Cytotoxic Clerodane Diterpene from

Casearia sylvestrisDiego D. Bou, Augusto L. dos Santos, Carlos R. Figueiredo, Camyla F. Farias, Alisson L. Matsuo, Rodrigo O. S. Kitamura, Leila Gimenes, João H. G. Lago and Patricia Sartorelli

1730 Multivariate Analysis of Perfumes by Ultraviolet SpectrophotometryClêrton L. Gomes, Ari Clecius A. Lima, Manuela C. L. Cândido, Abel. B. R. Silva, Adonay R. Loiola and Ronaldo F. Nascimento

1737 Prediction of Phase Separation Using a Modified Regular Solution Theory and the SMD Continuum Solvation ModelJosefredo R. Pliego Jr.

Graphical AbstractThis paper describes the isolation and chemical characterization of a

new clerodane-type diterpene, named dinor casearin X, from leaves of Casearia sylvestris, which exhibited cytotoxic activity against HL-60 cells (IC50 0.51 ± 0.11 mg mL-1). Additionally, the four known casearins A, B, G

and J were also identified

Graphical AbstractA method for detecting adulteration in perfumes by ultraviolet (UV) spectroscopy and multivariate analysis is proposed. Classification of

perfumes was accomplished with spectroscopic data using chemometrics analysis techniques such as principal component analysis (PCA), soft

independent modeling of class analogy (SIMCA) and linear discriminant analysis (LDA)

Graphical AbstractA new definition of b and fast prediction of phase separation

SI online

SI online