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Book of Abstracts

INORGANIC CHEMISTRY CONFERENCE10th 10a CONFERÊNCIA DE QUÍMICA INORGÂNICA DA SPQ

11-12 April 2014 | Costa da Caparica | Portugal

Proceedings of the 10th Inorganic Chemistry

Conference – Sociedade Portuguesa de

Química

Caparica - Almada, Portugal

11th – 12th April 2014

II

Book of Abstracts of the 10th Inorganic Chemistry Conference of the Portuguese Chemical Society Editors: Ana Marta Diniz, Andreia Ruivo, A. Jorge Parola Cover design: Violeta Pereira, FCT-UNL ISBN PDF Version: 978-989-98541-2-3 Printage: 125 usb flash drive Caparica, Portugal, 2014

III

TABLE OF CONTENTS

COMMITTEES .............................................................................................................................................. IV

PREFACE ....................................................................................................................................................... V

ORGANIZING INSTITUTIONS AND SPONSORS ............................................................................................... VI

DETAILED PROGRAMME ............................................................................................................................. VII

ALBERTO ROMÃO DIAS PRIZE ........................................................................................................................ 1

PLENARY LECTURES ....................................................................................................................................... 3

KEYNOTES ..................................................................................................................................................... 7

ORAL COMMUNICATIONS ........................................................................................................................... 13

POSTER WITH FLASH COMMUNICATIONS .................................................................................................... 32

POSTERS ...................................................................................................................................................... 42

AUTHOR INDEX ......................................................................................................................................... 109

PARTICIPANTS LIST .................................................................................................................................... 113

IV

COMMITTEES

Organizing Chair

• A. Jorge Parola, Universidade Nova de Lisboa

Scientific Committee


• Ana Cristina Freire, Universidade do Porto

• Ana Margarida Martins, Universidade de Lisboa

• Carlos Geraldes, Universidade de Coimbra

• Carlos Lodeiro-Espiño, Universidade Nova de Lisboa

• César Laia, Universidade Nova de Lisboa

• Isabel Gonçalves, Universidade de Aveiro

• João Rodrigues, Universidade da Madeira

• Joaquim Marçalo, Universidade de Lisboa

• José J. G. Moura, Universidade Nova de Lisboa

• Teresa Avilés, Universidade Nova de Lisboa

Local Organizing Committee


• Adrian Fernández-Lodeiro, Universidade Nova de Lisboa

• Ana Marta Diniz, Universidade Nova de Lisboa

• Andreia Ruivo, Universidade Nova de Lisboa

• Carlos Lodeiro, Universidade Nova de Lisboa

• César Laia, Universidade Nova de Lisboa

• Cristina Nuñez-González, Universidade Nova de Lisboa

• João Carlos Lima, Universidade Nova de Lisboa

• Sandra Gago, Universidade Nova de Lisboa

• Vitor Rosa, Universidade Nova de Lisboa

V

PREFACE

Dear Colleagues and Friends,

It is a great pleasure to welcome you to the 10th Inorganic Chemistry Conference of the Portuguese Society of Chemistry (SPQ), held in Costa da Caparica, from April 11th to 12th 2014. We hope that the scientific programme we have put together will be of great interest to all of you.

The Inorganic Chemistry Conference of SPQ has a long-standing tradition in bringing together scientists working in all areas of Inorganic Chemistry, mainly those with a larger expression in Portugal. The scientific programme is composed of (tentative) thematic sessions on Bioinorganic, Materials, Organometallic and Coordination Chemistry, comprising 3 plenary lectures, 5 invited keynote lectures, 18 oral communications and two poster sessions with over 70 posters, 9 of which were selected for 5 min flash presentations.

The award ceremony of the Alberto Romão Dias Prize will close this conference with a golden key. The Alberto Romão Dias Prize was created by SPQ to recognize a chemist, who by his scientific action and leadership has decisively contributed to the advancement of inorganic and organometallic chemistry in Portugal. It has been awarded, in its second edition, to Carlos Crispim Romão, full professor and head of the Organometallic Chemistry Lab at ITQB, Universidade Nova de Lisboa.

We hope that besides excellent and inspiring science, this meeting will also allow you to catch up with old friends and enable you to meet new people. In order to facilitate this we organized the coffee breaks in the same room – a room with a view! – where all posters are exposed during the two days of the conference.

We wish you a stimulating meeting.

On behalf of the Scientific and Organizing Committees,

Jorge Parola

Caparica, 2014

VI

ORGANIZING INSTITUTIONS

SPONSORS

VII

DETAILED PROGRAMME

Alberto Romão Dias Prize

Alberto Romão Dias Prize

2

Awarded to: Carlos C. Romão, ITQB-António Xavier, Universidade Nova de Lisboa “My (Privileged) Way Through Organometallic Chemistry” The Alberto Romão Dias Prize was created by the Portuguese Chemical Society (SPQ) to recognize a chemist, who by his scientific action and leadership has decisively contributed to the advancement of inorganic and organometallic chemistry in Portugal. The Prize is awarded every two years during the Inorganic Chemistry Conference organized by the Inorganic Chemistry Division of SPQ. The Prize, now in its second edition, was awarded this year by the Portuguese Chemical Society to Carlos Crispim Romão, full professor and head of the Organometallic Chemistry Lab at ITQB, Universidade Nova de Lisboa. The name of Carlos Crispim Romão was proposed by a group of professors and researchers in the area and approved unanimously by the jury composed by Maria José Calhorda (President of SPQ and former awardee), António Jorge Parola (President of the Inorganic Chemistry Division at SPQ), Ana Margarida Martins, João da Costa Pessoa and Rita Delgado.

Plenary Lectures

Plenary

4

PL1 – BREAKING N2: THE ENZYME NITROGENASE AND WHAT WE CAN LEARN FROM IT

Oliver Einsle

Institute for Biochemistry, Albert-Ludwigs-Universität Freiburg, Freiburg im Breisgau,

Germany The element nitrogen is an essential constituent of all classes of biological macromolecules. In nature, the highly inert dinitrogen gas, N2, forms a natural sink for 99 % of all [N] cycling through the biosphere, so that nitrogen supply becomes a growth-limiting factor. Only a single enzymatic reaction is able to tap into the atmospheric reservoir, the one of the two-component metalloenzyme Nitrogenase.

In the Nitrogenase system, a 240 kDa component, the MoFe protein, contains two large and unique iron-sulfur clusters, the [8Fe:7S] P-cluster that serves as an electron transfer center, and FeMo cofactor, the active site of N2 reduction (Fig- ure right). FeMo cofactor is a heteronuclear metal site of composition [Mo:7Fe:9S:C]:homocitrate that is assembled ex situ and only inserted into apo-nitrogenase as a complete entity. The exact binding mode of substrate to the cluster, the site of binding, the electronic state of the individual metals and the overall reactivity of the center in the context of the enzyme are under heavy debate, but astounding progress was made in recent years and will be presented and discussed. Nitrogenase has obvious relevance as the biological equivalent of the industrial Haber-Bosch process that today produces fertilizers that allow us to feed a major part of the world population, but at a cost of increasing nitrogen pollution. Harnessing the catalytic capacities of this enzyme thus holds the promise to move towards a new type of sustainable agriculture that is significantly more energy-efficient and environmentally friendly that current strategies.

[1] Einsle, O. (2014). Nitrogenase FeMo cofactor: an atomic structure in three simple steps. J. Biol.Inorg. Chem., in press. [2] Einsle, O., Tezcan, F. A., Andrade, S. L. A., Schmid, B., Yoshida, M., Howard, J. B. & Rees, D. C. (2002). Nitrogenase MoFe-protein at 1.16 Å resolution: A central ligand in the FeMo-cofactor. Sci- ence 297, 1696-1700. [3] Spatzal, T., Aksoyoglu, M., Zhang, L. M., Andrade, S. L. A., Schleicher, E., Weber, S., Rees, D. C.& Einsle, O. (2011). Evidence for Interstitial Carbon in Nitrogenase FeMo Cofactor. Science 334,940-940. [4] Spatzal, T., Einsle, O. & Andrade, S. L. (2013). Analysis of the Magnetic Properties of Nitrogenase FeMo Cofactor by Single-Crystal EPR Spectroscopy. Angew. Chem. 52, 10116-10119. [5] Einsle, O., Andrade, S. L., Dobbek, H., Meyer, J. & Rees, D. C. (2007). Assignment of individual metal redox states in a metalloprotein by crystallographic refinement at multiple X-ray wavelengths. J. Am. Chem. Soc. 129, 2210-2211.

Plenary

5

PL2 –TRANSITION METAL DITHIOLENE COMPLEXES AS KEY BUIDING BLOCKS FOR CONDUCTING AND MAGNETIC MATERIALS

Manuel Almeida

Centro de Ciências e Tecnologias Nucleares, Instituto Superior Técnico, E.N. 10, P-2695-066 Bobadela LRS, Portugal

Bis-1,2-dithiolene transition metal complexes have been at the centre of many studies over the last decades owing to a unique combination of functional properties, vivid redox behaviour, diversity of molecular geometries and magnetic moments which with the capacity to develop specific intermolecular interactions confer them an enormous interest in different fields such as conducting and magnetic materials, dyes, and nonlinear optics, among others. The electronically delocalized core of these square planar complexes, comprising the central metal, four sulfur atoms and the C=C units, accounts for a rich electrochemical behaviour that often undergoes more than one reversible redox processes. Depending on both the metal and the ligand, different stable oxidation states are possible ranging from dianionic to cationic and including, in some cases, partially oxidized states. Partially oxidised states of these complexes in the solid state are associated with conducting, metallic or even superconducting properties. In this presentation we will review of such complexes illustrating with examples developed in our group the diversity of structures and properties and their applications in molecular systems with conducting and magnetic functionalities.

Acknowledgements: Work partially supported by FCT contract PTDC/QEQ-SUP/1413/2012.

Plenary

6

PL3 - COORDINATION POLYMER NANOPARTICLES (CPPS) AND THEIR GROWTH @ SURFACES

F. Novio,1,2 F. Nador, 1,2 K. Knuw, 1,2 M. Guardingo, 1,2 M. Borges, 1,2 D. Ruiz-Molina1,2

1ICN2 - Institut Catala de Nanociencia i Nanotecnologia, Campus UAB, 08193 Bellaterra (Barcelona), Spain

2CSIC - Consejo Superior de Investigaciones Cientificas, ICN2 Building , Campus UAB ,08193 Bellaterra (Barcelona), Spain

[email protected]

Miniaturization of coordination polymers to the nanoscale represents a unique opportunity to amass a novel class of highly customizable functional materials that marry the rich diversity, chemistry and properties of coordination complexes to the advantages of nanomaterials. The new structures, which exhibit well-defined and dispersed morphologies, can allow for a proper correlation with their functionality, and therefore, enable the rational design of new generations of CPPs targeting specific desired properties. In this presentation I will give a brief introduction to the rational designed developed in our group for the fabrication of such functional nanostructures through a simple precipitation/coordination polymerization mechanism. Following this approach, we have reported the fabrication of “smart” nanoscale coordination polymer particles (CPPs) whose properties and functions can be significantly changed in a controlled manner by external stimuli, or shown how CPPs can be used for encapsulating and delivering drugs with anticancer efficacy. In addition, the same CPPs have been directly synthesized on surfaces. For this, AFM tips have been used to directly deliver less than femptoliter droplets of precursor solutions containing the organic bridging ligands and the metal ion building blocks to a given surface. Delivered droplets act as nanoreactors that confine the coordination polymerization and/or crystallization process to yield the desired coordination based nanoarchitectures on surfaces. Upon controlling the incubation conditions, control over their size and morphology is modulated. These results open new avenues for all the possible applications that can be derived from the implications of CPPs on surfaces.

References of our recent work on nanoparticles: (a) J. Am. Chem. Soc. 2014, submitted, (a) Adv. Health. Mat.. 2014, submitted (c) Chem. Eur. J. 2013, 19, 17508, (d) Coord. Chem. Rev. 2013, 257, 2839– 2847, (e).Chem. Commun., 2011, 47, 5175, Chem. Commun., 2010, 46, 4737, (f) Angew. Chem. Int. Ed. 2009, 48, 2325 . (g) Angew. Chem. Int. Ed., 2008, 47, 1857, (2008). References of our recent work @ surfaces: (a) Nanoscale, 2013, 5, 12565-12573; (b) Sci. Rep. 2013 3 : 1708 | DOI: 10.1038/srep01708; (c) Chem. Soc. Rev., 2012,41, 258-302; (d) Langmuir 2012, 28, 12400; (e) Small 2012, 8, 1465; (f) Chem. Commun., 2011, 47, 5175. (g) App. Phys. Lett. 2011, 99, 032504; (h) Adv. Mater. 2010, 22, 352.

Keynotes

Keynotes

8

K1 - THE ORANGE PROTEIN: A PROTEIN CONTAINING A HETEROMETALLIC CLUSTER INVOLVED IN A NOVEL CELL

DIVISION SYSTEM

M.S.P. Carepo1, A.G. Wedd2, J.J.G Moura1, I. Moura1, Sofia R. Pauleta*1

1REQUIMTE/CQFB, Dep. Química, FCT-UNL, Campus da Caparica, 2829-516 Caparica, Portugal. 2School of Chemistry, Bio21 Molecular Science and Biotechnology Institute,

University of Melbourne, Parkville, Australia *[email protected]

A comparative analysis of genomes from anaerobic and aerobic microorganisms using the Cluster of Orthologous Groups of proteins (COG) database allowed the identification of 33 COGs that are specific to anaerobic organisms with five containing uncharacterized conserved proteins, which are believed to play a crucial role in anaerobiosis. We have recently shown that members of one of these 5 COGs, COG1433, in the model sulphate reducing anaerobic bacterium Desulfovibrio vulgaris Hildenborough (DvH) form a complex in vivo, the Orange Protein complex, that is proposed to be involved in positioning the septum during cell division [1]. Moreover, the co-occurrence of the genes encoding the ORP complex in the genome of delta-proteobacteria is conserved, suggesting that this novel molecular system might have a similar function in these organisms. The Orange Protein (ORP) is a small protein containing a heteronuclear Mo-Cu cluster not covalently bound to the polypeptide chain. This protein has been isolated from D. gigas [2] and D. desulfuricans, and is heterologously expressed in E.coli for NMR studies as apo-protein [3]. Reconstitution of the metal cluster was studied either by addition of the pre-synthesized cluster or by its synthesis in the presence of the apo-protein, upon addition of copper sulphate and thiomolybdate or thiotungstate [4]. NMR studies clearly show that there is a protein assisted metal reconstitution of the heterometallic cluster. The over-all solution structures of the apo and reconstituted ORP are similar and the mapping of the chemical shift differences between them was used to elucidate which region of the polypeptide chain is involved in the binding of the metal cluster. These results give insights into the metal binding mode of chaperons involved in the synthesis of the nitrogenase metal cofactor. Acknowledgments: SRP thanks to Fundação para a Ciência e a Tecnologia (FCT) for the financial support (FCT-ANR/BBB-MET/0023/2012). This work was also been financed by National funds by FCT under the project PEst-C/EQB/LA0006/2013. SRP is an Investigador FCT. [1] Fiévet, A. et al., J. Bacteriol. 2011, 193, 3207-19. [2] Bursakov, S.A. et al., JIB 2004, 98, 833-7. [3] Pauleta, S.R. et al., Biomol. NMR Assignm. 2007, 1, 81-3. [4] Carepo, M.S. et al., JBIC 2007, 12, S73.

Keynotes

9

K2 - MULTI-ELECTRON REACTIVITY OF TA(V) COMPLEXES SUPPORTED BY REDOX-ACTIVE LIGANDS

Rui F. Munhá1, Ryan A. Zarkesh1 and Alan F. Heyduk*1

1Department of Chemistry, University of California, Irvine, 92697, USA

Email: [email protected]

The design and preparation of new d0 early-transition metal complexes incorporating redox-active ligands is noteworthy owing to the ability of these systems to promote new stoichiometric and catalytic transformations.1,2 This reactivity derives from the cooperativity established between an early-transition metal ion that is strongly Lewis acidic and a redox-active ligand that can accommodate multi-electron redox changes. This presentation will describe the synthesis and characterization of a family of tantalum complexes incorporating a redox-active, tris(amide) ligand platform, designated (NNN) (1, Scheme 1). In particular, synthetic strategies were developed to change the electronic and steric profiles of the (NNN) scaffold, allowing a comprehensive study on the influence of substituent groups on the properties and reactivity of the corresponding tantalum complexes.

. [1] R. F. Munhá, R. A. Zarkesh, and A. F. Heyduk, Dalton Trans., 2013, 42, 3751. [2] A. I. Nguyen, K. J. Blackmore, S. M. Carter, R. A. Zarkesh, and A. F. Heyduk, J. Am. Chem. Soc., 2009, 131, 3307.

Keynotes

10

K3 - GOLD(I) SUPRAMOLECULAR ASSEMBLIES IN WATER

Elisabet Aguiló1, Raquel Gavara2, Artur J. Moro2, João Carlos Lima2, Laura Rodríguez1

1 Departament de Química Inorgànica, Universitat de Barcelona, Barcelona, Spain.

e-mail: [email protected] 2 REQUIMTE, Departamento de Química, CQFB, Universidade Nova de Lisboa, Monte de

Caparica, Portugal.

The assembly of three-dimensional compounds using metal coordination presents both challenging and interesting applications in the area of chemical nanosciences. Related to this, Au(I) complexes present the advantage to use both classical supramolecular interactions (e.g. stacking) together with the establishment of Au(I)···Au(I) bonds. Moreover, the studies of Au(I) complexes containing phosphine and alkynyl units which can have a wide range of emission wavelengths have gained much attention in the last years and very interesting properties have been described in this area.[1] We have recently observed the formation of supramolecular assemblies with the [Au(ethynyl-R)(phosph)] (phosph = PTA, DAPTA; R = pyridine, coumarin) water soluble complexes that conduce to the formation of luminescent hydrogels.[2-4] Moreover, new recent findings have shown that slight modifications on the chemical structure of these complexes can modulate the supramolecular assembly and obtain very different topologies: vesicles, rods and hydrogels with interesting luminescent properties (Figure 1).

Figure 1: Hydrogel (A), nanorod (B) and vesicle (C) supramolecular organizations of the gold(I)

complexes characterizated by FM (left), SEM (middle) and Cryo-TEM (right). [1] Lima, J.C.; Rodríguez, L. Chem.Soc. Rev. 2011, 40, 5442. [2] Gavara, R.; Llorca, J.; Lima, J.C.; Rodríguez, L. Chem. Commun. 2013, 49, 72. [3] Aguiló, E.; Gavara, R.; Lima, J.C.; Llorca, J.; Rodríguez, L J. Mat. Chem. C. 2013, 1, 5538. [4] Arcau, J.; Andermark, V.; Aguiló, E.; Gandioso, A.; Moro, A.; Cetina, M.; Lima, J.C.; Rissanen, K.; Ott, I.; Rodríguez, L. Dalton Trans. 2014, 43, 4425.

P

N

NN Au C C N

Me

R3P Au C C N MeI

PR3 = PTA (C), DAPTAA

P

N

NN Au C C N

O

O

B

Keynotes

11

K4 - HIGHLY EFFECTIVE GROUP 4 AND 13 METAL COMPLEXES FOR THE PRODUCTION OF TAILOR-MADE BIOMATERIALS

THROUGH POLYMERIZATION CATALYSIS

Frédéric Hild1, Charles Romain1, Samuel Dagorne1

1Institut de Chimie de Strasbourg - CNRS - Université de Strasbourg 1, rue Blaise Pascal, 67000 Strasbourg, France, email: [email protected]

The ring-opening polymerization (ROP) of cyclic esters, such as lactide, and cyclic carbonates, such as trimethylene carbonate (TMC), is of current importance due to the biodegradability and biocompatibility of the resulting materials (for instance, poly(lactide), PLA, and polycarbonates such as PTMC). In this area, discrete ligand-supported complexes of Lewis acidic and oxophilic metals may be suitable candidates as ROP initiators of cyclic esters and carbonates and may mediate such a polymerization process in a controlled (and possibly stereocontrolled) manner for the production of tailor-made and narrow disperse (and possibly stereoregular) polymeric materials.1 Over the past few years, we have designed and synthesized several families of groups 4 (Ti, Zr) and 13 (Al, Ga) metal complexes for the highly effective and/or stereoselective polymerization of bio-sourced cyclic esters/carbonates (Scheme 1).2-6 The synthesis, structural characterization and polymerization performances of these organometallic derivatives will be discussed, along with ligand design/catalysis correlations.

Scheme 1. Production of polylactic acid (PLA) and poly(trimethylene carbonate) via ROP catalysis [1] Platel, R. H.; Hodgson, L. M.; Williams, C. K. Polym. Rev. 2008, 48, 11 [2] Hild, F.; Neehaul, N.; Bier, F.; Wirsum, M.; Gourlaouen, C.; Dagorne, S. Organometallics 2013, 32, 587 [3] Romain, C.; Heinrich, B.; Bellemin-Laponnaz, S.; Dagorne, S. Chem. Commun. 2012, 48, 2213. [4] Azor, L.; Bailly, C.; Brelot, L.; Henry, M.; Mobian, P.; Dagorne, S. Inorg. Chem. 2012, 51, 10876. [5] Alves, L. G.; Hild, F.; Munhá, R.; Veiros, L. F.; Dagorne, S.; Martins, A. M. Dalton Trans. 2012, 41, 14288. [6] Hild, F.; Brelot, L.; Dagorne, S. Organometallics 2011, 30, 5457.

Keynotes

12

K5 - HIGHLY EFFICIENT WATER OXIDATION CATALYSIS WITH ORGANOMETALLIC IRIDIUM COMPLEXES

Zoel Codolà1, João M. S. Cardoso,2 Beatriz Royo2, Miquel Costas1, Julio Lloret-Fillol1

1Departament de Química, Universitat de Girona, Campus Montivili, 17071, Girona, Spain. 2Instituto de Tecnologia Química e Biologica, Universidade Nova de Lisboa, Av. da

República, EAN. 2780-157 Oeiras, Portugal. [email protected]

Water oxidation is one of the biggest scientific and technological challenges towards the realization of artificial photosynthesis (Eq. 1, Figure 1). For decades, scientist have been trying to imitate and understand nature by creating not only biomimetic Mn-based water oxidation catalysts (WOC) but also molecular Ru-based catalysts. More recently, Ir, Co, Fe, Cu and Ni metals have also been found to be catalytically active in WO [1]. However, understanding the elemental details of the WO reaction is under continuous debate. We describe here an exceptional water oxidation catalyst, the iridium organometallic complex [Cp*Ir(NHC)Cl2] (Cp* = 5-C5Me5; NHC = N-heterocyclic carbene) which displayed turnover frequencies (TOFs) of 17.000 h-1 and turnover numbers (TONs) close to 400.000, the largest ever reported for a metal-catalyzed WO reaction, Figure 1 [2]. We will also present our investigations aimed to understand the nature of the active species. 1H NMR, ESI-HRMS, UV, and DLS experiments will be discussed.

N

N

IrXXPh

N

N

IrIIPh

X = Cl, I, OTf CATALYSTS Figure 1: Iridium Organometallic Catalysts for Water Oxidation.

Acknowledgements: We gratefully acknowledge FCT of Portugal project PTDC/QEQ-QIN/0565/2012, the European Research Foundation for project FP7-PEOPLE-2010-ERG-268445 (J.L.-F.), REC-2009-StG-239910 (M.C.) and MICINN project CTQ2009-08464 (M.C.) for financial support. J.M.S. Cardoso thanks FCT for a PhD grant (SFRH/BD/66386/2009) and J.L.-F thanks MICINN for a Ramon y Cajal contract. [1] R. Cao, W. Lai, P. Du, Energy Environ. Sci. 2012, 5, 8134. [2] Z. Codolà, J. M. S. Cardoso, B. Royo, M. Costas, J. Lloret-Fillol, Chem. Eur. J. 2013, 19, 7203.

Oral communications

Oral Communications

14

OC1 - DESIGN OF NOVEL HIGH-PERFORMANCE IRON OXIDE NANOPARTICLES FOR APPLICATION AS

CONTRAST AGENTS IN MRI

Clara Pereira1, André M. Pereira2, Mariana Rocha1, Cristina Freire1 and Carlos F. G. C. Geraldes3

1REQUIMTE, Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade

do Porto, 4169-007 Porto, Portugal 2IFIMUP-IN – Instituto de Nanociência e Nanotecnologia, Departamento de Física e

Astronomia, Faculdade de Ciências, Universidade do Porto, 4169-007 Porto, Portugal 3Departamento de Ciências da Vida, Faculdade de Ciências e Tecnologia, and Centro de

Química de Coimbra, Universidade de Coimbra, 3001-401 Coimbra, Portugal [email protected]

Superparamagnetic iron oxide nanoparticles are a class of magnetic nanomaterials that has been revolutionizing a myriad of applications such as in biomedicine, catalysis and environmental remediation [1]. Among iron oxides, magnetite (Fe3O4) and maghemite (γ-Fe2O3) nanoparticles occupy a pivotal position owing to their nanoscale dimensions, high saturation magnetization, non-toxicity and biocompatibility [1,2]. The aqueous coprecipitation process continues to be one of the prime choices for the production of these nanomaterials since it is eco-sustainable, less time consuming, cost effective and easily scalable [3]. Nevertheless, the development of new routes for the design of iron oxide nanoparticles which enable the control of the particles size and magnetic properties continues to be a challenging target, especially for the design of functional magnetic probes for theranostics and imaging applications. This work reports the fabrication of a new generation of water-dispersible superparamagnetic iron oxide nanoparticles combining high colloidal stability, reduced particle size and improved magnetic properties, by a new one-step coprecipitation process. Through the use of different polyfunctional alkanolamines as alkaline agents we were able to fine-tune the particle size (from 4.8 to 9.0 nm) and saturation magnetization (up to 65.1 emu g-1). Relaxometry studies were performed in order to evaluate the performance of the magnetic nanomaterials as potential contrast agents for magnetic resonance imaging (MRI). All the iron oxides presented promising relaxometric properties, reaching a maximum value of transverse relaxivity of 300 mM-1 s-1 (at 25 ºC, 20 MHz, 0.47 T). Finally, a relation between relaxivity – particle size – saturation magnetization was established. Acknowledgements: This work was funded by FCT and FEDER through grant no. PEst-C/EQB/LA0006/2011. The authors acknowledge Operation NORTE-07-0124-FEDER-000067 – NANOCHEMISTRY and the Portuguese National NMR Network (RNRMN) supported by FCT. M.R. thanks FCT for a grant. The authors thank Prof. P. Tavares and MSc. L. Fernandes from UME-UTAD for the XRD measurements.

[1] Laurent, S. et al. Chem. Rev. 2008, 108, 2064–2110. [2] Reddy, L. H. et al. Chem. Rev. 2012, 112, 5818−5878. [3] Pereira, C. et al. Chem. Mater. 2012, 24, 1496−1504.

Oral Communications

15

OC2 - GD3+ COMPLEXES CONJUGATED TO THE PITTSBURG COMPOUND B AS POTENTIAL MRI MARKERS OF -AMYLOID

PLAQUES: IN VITRO AND IN VIVO STUDIES

André F. Martins,1,2 David Dias,2,3 J-F Morfin,1 Douglas Laurents,4 Eva Toth1 and Carlos F.G.C. Geraldes2

1Centre de Biophysique Moléculaire, CNRS, Orléans, France

2Department of Life Sciences and Coimbra Chemistry Center, University of Coimbra, Coimbra, Portugal ([email protected])

3Department of Chemistry, University of Cambridge, Cambridge, UK 4Instituto de Química Física “Rocasolano”, C.S.I.C., Madrid, Spain

In an effort towards the visualization of -amyloid plaques by T1-weighted MR imaging for detection of Alzheimer’s disease (AD), we report the synthesis and in vitro characterization of stable, non-charged Gd3+ complexes of three different DO3A-monoamide derivatives conjugated to the Pittsburgh compound B (PiB), a well-established marker of A amyloid plaques. [1,2] The ligands L1, L2 and L3 differ in the nature and size of the spacer linking the macrocyclic chelator and the PiB targeting moiety, which affects their lipophilicity; the water/octanol partition coefficients, log POct/H2O, of the complexes varying from -0.15 to +0.32. Given their amphiphilic behavior, the complexes form micelles in aqueous solution (cmc = 1.00-1.49 mM). The parameters determining relaxivity, including water exchange rate and rotational correlation times, were assessed for the monomeric and micellar form by a combined 17O NMR and 1H NMRD study. They are largely influenced by the aggregation state and the hydrophobic character of the linkers. The analysis of the rotational dynamics for the aggregated state in terms of local and global motions using the Lipari-Szabo approach indicate highly flexible, large aggregates. Upon binding of the complexes to human serum albumin (HSA) or to the Aβ1-40 amyloid peptide in solution, their relaxivity undergoes a four- and two-fold relaxivity increase, respectively (40 MHz). Proton Relaxation Enhancement studies confirmed moderate interaction of GdL1 and GdL3 to HSA, with KA values varying between 250 and 910 M-1. We also describe the interaction of these Gd3+ complexes with the A1-40 peptide in the aggregated and monomeric forms using a series of different biophysical techniques. These include studying their affinity and mode of binding to immobilized or aggregated A1-40 by Surface Plasmon Resonance (SPR) and Saturation Transfer Difference (STD) NMR, leading to moderate in vitro affinities (KD ~ 67-170 M). The group epitope mapping (GEM) for the corresponding La3+ complexes, obtained by STD NMR, shows that the complexes interact with A1-40 aggregates mainly through the benzothiazole ring and the attached methoxy group. Their interaction with the 15N-labeled A1-40 peptide monomer was studied at the atomic level using 1H−15N HSQC NMR. The assessment of their effect on the secondary structure and aggregation process of A1-40 was studied by Circular Dichroism (CD), ThT Fluorescence, Dynamic Light Scattering (DLS) and Transmission Emission Microscopy (TEM). This study suggests that the Gd3+-L1,2 complexes interact weakly with the peptide monomer, but much more strongly with aggregates. They do not affect its self-association in the same way. They promote the early formation of α-helical or -sheet ordered structures, depending on their nature and concentration. As a consequence, they show inhibition or promotion of the formation of amyloid fibrils. These studies give important clues to improve the targeted specificity and affinity of this type of multimodal imaging probes. Preliminary in vivo biodistribution and PET imaging studies of 111In3+ and 68Ga3+ labeled L1 in an AD mouse model will also be presented. Acknowledgements: We acknowledge financial support of the F.C.T. Portugal, the French-Portuguese PESSOA project and the European Action TD1004 “Theragnostics Imaging and Therapy”. [1] Martins, A.F.; Morfin J.-F.; Kubíčková A, et al., ACS Med. Chem. Lett. 2013, 5, 436–440. [2] Martins, A.F.; Morfin J.-F.; Geraldes, C.F.G.C.; Tóth, É.,J. Biol. Inorg. Chem, in press.

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OC3 - RESIZING OF GOLD NANORODS BY IN SITU CHEMICAL OXIDATION USING PERSULFATE:

MORPHOLOGICAL AND SPECTROSCOPIC STUDIES

Sara Fateixa1, Maria Rosário Correia2, Tito Trindade1

1Department of Chemistry-CICECO, Aveiro Institute of Nanotechnology, University of Aveiro, Portugal

2Department of Physics-I3N, University of Aveiro, 3810-193 Aveiro, Portugal [email protected]

Surface Enhanced Raman Scattering (SERS) is a vibrational spectroscopic technique that provides valuable information about the nature and orientation of molecular species adsorbed at metal surfaces and on the adsorbate–metal interaction mechanism [1, 2]. In order to achieve a better Raman signal from the SERS substrate, the morphological characteristics of the metallic nanostructures can be manipulated [3, 4]. In this report we demonstrate that SERS spectroscopy can be used to monitor the oxidation of colloidal gold nanorods (NRs) during a chemical etching process [5]. Hence, the Au NRs were collected at different stages of oxidation promoted by the presence of K2S2O8 and their sensitivity as SERS substrates was evaluated, using the anion diethyldithiocarbamate (DTC) as molecular probe. The studies were performed using the excitation lines at 1064 nm and 632.8 nm. This study demonstrated that the sensitivity of the Au NRs as SERS substrates decreased as their A.R. decreased, which is explained due to competition of CTAB (stabilizer) and DTC for the surface of NRs. The spectroscopic studies (SERS and visible absorption) performed were complemented by morphological analysis using TEM. It is noted that this process involves distinct adsorption behavior of the two DTC tautomers at the metal surface.

Figure 1: SERS spectra of diethyldithiocarbamate using colloidal Au NRs treated with aqueous

K2S2O8, at variable reaction times.

Acknowledgements: S. Fateixa thanks Fundação para a Ciência e Tecnologia (FCT/FEDER) for the grant SFRH/BPD/93547/2013. The authors thank FCT (PTDC/CTM-NAN/120668/2010; Pest-C/CTM/LA0011/2011), RECI/FIS-NAN/0183/2012(FCOMP-01-0124-FEDER-027494) and PEst-C/CTM/LA0025/2013 projects FSE and POPH for funding.

[1] Kneipp, J.; Kneipp, H.; Kneipp, K., Chem. Soc. Rev. 2008, 37, 1052–1060 [2] Sharma, B.; Frontiera, R. R.; Henry, A.; Ringe, E.; Van Duyne, R. P., Materials Today 2012, 15, 16-25. [3] Orendorff, C. J.; Gole, A.; Sau, T. K.; Murphy, C. J., Anal. Chem. 2005, 77, 3261-3266. [4] Link, S.; Mohamed, M. B.; El-Sayed, M. A., J. Phys. Chem. B 1999, 103, 3073-3077. [5] Fateixa, S.; Correia, M. R.; Trindade, T.; J. Phys. Chem. C 2013, 117, 20343-20350.

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OC4 – POLYOXOMETALATES AS EFFECTIVE CATALYSTS FOR OXIDATIVE DESULFURIZATION OF MODEL FUEL OIL

Diana Julião1, Baltazar de Castro1 and Salete S. Balula1

1REQUIMTE, Department of Chemistry and Biochemistry, Faculty of Sciences, University of

Porto, 4169-007 Porto, Portugal

The emissions of sulfur compounds resulting of combustion of transportation fuels are a major source of environmental pollution contributing to increase the global warming and acid rain. Therefore to minimize the negative effects of this pollutant, many countries implemented more stringent regulations for sulfur in fuels [1]. The actual process applied in refining petroleum industry is the hydrodesulfurization (HDS) that operates under severe conditions and it is ineffective in removing refractory sulfur compounds. Consequently, new processes capable to produce deep desulfurization of fuels have been investigated. Oxidative desulfurization (ODS) is one of the most promising desulfurization processes because requires mild conditions (low pressure and temperature), without using hydrogen and the refractory sulfur compounds, such as dibenzothiophene (DBT), 1-benzothiophene (1-BT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) can be easily oxidized and removed by extraction or others appropriate methods [2]. The ionic liquids (ILs) have been applied as extraction solvents and these have present better performance than the conventional organic and flammable solvents. ILs are denominated as “green solvents” due to their proprieties, such as no volatility and their capacity of recyclability [3]. The combination of ILs as extraction solvents and the use of hydrogen peroxide as sustainable oxidant has showed to form successful ODS processes, mainly when polyoxometalates (POMs) are used as catalyst to oxidize the refractory sulfur components in fuels [4]. POMs are a valuable class of inorganic compounds that have attracted great attention because of their fascinating structural diversity that can be modulated to achieve the best performance [2]. In the present communication, Keggin-type polyoxometalates with different structures will be presented: monosubstituted [PW11Zn(H2O)O39]

5- and sandwich-type [Zn(H2O)2(PW9O34)2]

10-. These compounds were characterized through different techniques: FT-IR, FT-Raman, 31P RMN, elementary analysis and thermogravimetry. Furthermore, the application of these POMs as efficient catalyst for the desulfurization of a model oil from fuel will be presented. The recyclability of the liquid-liquid ODS system will be demonstrated using the IL 1-butyl-3-methylimidazolium hexafluorophosphate and H2O2 as oxidant. Acknowledgments: to FCT for the financial support through the strategic project Pest C/EQB/LA0006/2011 (REQUIMTE) and the R&D project PTDC/EQU-EQU/121677/2010.

[1] Zhu, W.; Huang, W.; Li, H.; Zhang, M.; Jiang, W.; Chen, G.; Han, C. Fuel Processing Technology 2011, 92, 1842-1848. [2] Wang, R.; Zhang, G.; Zhao, H. Catalysis Today 2010, 149, 117-121. [3] Xu, J.; Zhao, S.; Chen, W.; Wang, M.; Song, Y-F. Chemical European Journal 2012, 18, 4775-4781. [4] Ribeiro, S.; Barbosa, A. D. S.; Gomes, A. C.; Pillinger, M.; Gonçalves, I. S.; Cunha-Silva, L.; Balula, S. S. Fuel Processing Technology 2013, 116, 350-357.

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OC5 - POLYOXOMETALATES@MOFS COMPOSITES: EFFICIENT AND VERSATILE HETEROGENEOUS

CATALYSTS FOR SUSTAINABLE OXIDATIVE SYSTEMS

Carlos M. Granadeiro, Susana Ribeiro, Salete S. Balula, Luís Cunha-Silva

REQUIMTE & Department of Chemistry and Biochemistry, Faculty of Sciences, University of Porto, 4169-007 Porto, Portugal

Polyoxometalates (POMs) are inorganic clusters which are well-known efficient homogeneous catalysts and have been extensively used in various oxidative reactions.[1] The need to heterogeneize these effective catalysts for recovery and recycling purposes has led to an increasing effort to immobilize POMs in suitable solid supports. Porous metal-organic frameworks (MOFs), in particular MIL-101 type materials, provide a chemically robust and thermal resistant support containing a mesoporous structure with accessible cages and tunnels that allows the introduction of large inorganic species.[2,3] In this work, we have prepared several composite materials through the immobilization of different POMs within the MIL-101(Cr) framework (POMs@MIL-101). The characterization data obtained (vibrational and solid-state NMR spectroscopies, electron microscopy, EDX, elemental and textural analyses) confirmed the incorporation of the POMs in MIL-101(Cr) and the structural preservation of both components. The POMs@MIL-101 composites were tested as heterogeneous catalysts in olefins oxidation and in oxidative desulfurization processes exhibiting high efficiency in both catalytic systems.

Figure 1: Polyoxometalates immobilized in MIL-101(Cr) for oxidative catalysis. Acknowledgements: The authors are grateful to the Fundação para a Ciência e a Tecnologia (FCT, MEC, Portugal) for general financial support by the strategic project no. Pest-C/EQB/LA0006/2011 (to REQUIMTE), the R&D projects PTDC/CTM/100357/2008 and PTDC/EQUEQU/121677/2010 and the fellowship SFRH/BPD/73191/2010 (to CMG). [1] Mizuno, N.; Yamaguchi, K.; Kamata, K. Coord. Chem. Rev. 2005, 249, 1944-1956. [2] Bromberg, L.; Diao, Y.; Wu, H.; Speakman, S.A.; Hatton, T.A. Chem. Mater. 2012, 24, 1664-1675. [3] Granadeiro, C.M.; Barbosa, A.D.S.; Silva, P.; Almeida Paz, F.A.; Saini, V.K.; Pires, J.; Castro, B.; Balula, S.S.; Cunha-Silva, L. Appl. Catal., A 2013, 453, 316-326.

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OC6 – THERMAL EFFECTS ON THE MAGNETOSTRUCTURAL TRANSITION ON THIN FILM OF Gd5Si1.3Ge2.7

A. L. Pires1,2, J. H. Belo2, I. T. Gomes2, R. L. Hadimani3,4, D.L. Schlagel4, T.A. Lograsso4,5, D.C. Jiles3,4, A. M. Pereira2, A. M. L. Lopes1,2, J. P. Araújo2

1CFNUL - Centro de Física Nuclear da Universidade de Lisboa, Av. Prof. Gama Pinto, 2,

1649-003 Lisboa, Portugal. 2IFIMUP and IN - Institute of Nanoscience and Nanotechnology, Departamento de Física e Astronomia da Faculdade de Ciências da Universidade do Porto, Rua do Campo Alegre,

687, 4769-007 Porto, Portugal. 3Department of Electrical and Computer Engineering, Iowa State University, Ames, Iowa

50011, USA 4Ames Laboratory, US Department of Energy, Iowa State University, Ames, Iowa 50011,

USA 5Division of Materials Science and Engineering, Ames Laboratory, Ames, Iowa 50011, USA

In the advent of the nanomaterials, it becomes important not only to establish the production conditions but also predict the changes the nanomaterials undergo with different conditions (such as temperature, magnetic field and others thermodynamic parameters) depending on the type of application [1]. For refrigeration systems based on magnetocaloric thin films it becomes necessary to study the influence of thermal cycles in order to simulate their behavior in a real device. In this work we investigated the influence of the thermal cycling of a Gd5Si1.3Ge2.7 thin film on its microstructure, magnetic phase transition and magnetic entropy value. The Gd5Si1.3Ge2.7 thin film was deposited on a SiO2-covered Si substrate by a femtosecond pulsed laser. This study was performed by immersing the Gd5Si1.3Ge2.7 thin film in liquid nitrogen up to 450 cycles. In each cycle, the film was immersed in a bath for 30-60 seconds in order to ensure thermal equilibrium with the bath and then removed to rest in air, for 60 seconds. The characterization of the sample shows that there are morphological changes with the thermal cycling that may be attributed to the consecutive thermal shocks. The magnetization curves show two magnetic transitions, one of first and other of second order. It is observed that the thermal cycling does not affect the high temperature (249 K) magnetic transition, whereas the lower temperature transition (197 K), which corresponds to a magnetostructural transition, shows major differences. In fact, there is a clear decrease (16.2%) on the thermal hysteresis after the 450 cycles, showing a change on the phase transition dynamics. This decrease in the hysteresis occurs because of the reduction of the amount of phase undergoing the magnetostructural transition. Consequently this decrease of the magnetostructural transition affects the magnetocaloric effect (MCE). Hence, the thermal cycling causes a 19% decrease of the MCE peak value (-∆Smmax occurs at 193 K) because of the O(II) phase arresting. Nonetheless, we see that the metastability decreases when we increase the number of cycles. So, the MCE value shows a tendency to stabilize and reach an equilibrium state, which is crucial for future applications. Acknowledgements: The authors acknowledge to FCT for financial support in the project PTDC/CTM-NAN/115125/2009. [1] Ryan A. Booth et al, "The magnetocaloric effect in thermally cycled polycrystalline Ni-Mn-Ga," Journal of Applied Physics, vol. 111, no. 7, p. 07A933, 2012.

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OC7 - THE PORTUGUESE INORGANIC CHEMISTRY NOMENCLATURE BEYOND OSSO DE CABRITO

AND BICO DE PATO

M.C. Magalhães1, A. Machado2, B.J. Herold3, J. Cardoso1,4, J. Marçalo3, J.A.L Costa1, M.H. Garcia3, O. Pellegrino5, O.A. Serra6, R.B. Faria7, R.T. Henriques3

1Universidade de Aveiro and CICECO, Aveiro, Portugal. [email protected] 2 Universidade do Porto, Porto, Portugal

3 Universidade de Lisboa, Lisboa, Portugal 4 Universidade de Cabo Verde, Cabo Verde

5 Instituto Português da Qualidade, Caparica, Portugal 6 Universidade de São Paulo, Ribeirão Preto, Brasil

7 Universidade Federal do Rio de Janeiro, Rio de Janeiro, Brasil

The book Nomenclature of Inorganic Chemistry, IUPAC Recommendations 2005 is being translated by a team of Portuguese and Brazilian chemists nominated by their IUPAC national adhering organizations, together with a lecturer from the Universidade de Cabo Verde and a representative of the Portuguese Institute for Quality. This translation in one version, for both variants of the Portuguese language, is a challenging task as it did not occur in the previous translations of the Inorganic Nomenclature to Portuguese, and it is nearing completion. These 2005 recommendations introduced some important changes in relation to previous versions. The changes were aimed firstly to systematize and simplify the three systems of inorganic nomenclature currently in use: compositional, substitutive and additive. Secondly, the changes aimed to make the inorganic nomenclature more logical and consistent with the organic nomenclature, as part of the IUPAC commitment to this harmonization task, taken in recent years. In these recommendations changes were introduced:

in the names of some cations; in the suffixes used for construction of systematic names for anions; in the ordering of chemical elements in the chemical formulae; in the names of some anionic ligands in (formal) coordination entities; in the ordering of the ligands in the formulae for (formal) coordination entities; in the additive names of polynuclear entities; in the formalism for addition compounds, and other compounds treated as such; in the ordering of enclosed marks.

Some examples will be presented, in order to illustrate the differences in relation to the recommendations still in use in Portuguese. Advantage was taken, of this book, to suggest updated Portuguese names for a few number of chemical elements. On the other hand, not all the proposed changes in the English edition, from previous editions, were considered in the Portuguese version; for instance there were certain complications in the endings of names in English, which made no sense in Portuguese.

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OC8 - SYNTHESIS OF NOVEL PT/RU OR RU/FE METALLODENDRIMERS FOR

NONLINEAR OPTICAL APPLICATIONS

Manuel G. Jardim1, João Rodrigues1, José C. Mesquita1, Kari Rissanen2, Jochen Campo3, Wim Wenseleers3

1CQM - Centro de Química da Madeira, MMRG, Universidade da Madeira,Portugal 2Nanoscience Center, Department of Chemistry, University of Jyväskylä, Finland

3 Physics Department, University of Antwerp, Belgium [email protected]; [email protected]

Metal-containing dendrimers may provide an attractive strategy for the enhancement of electronic, photo-optical and biological properties of simple organic dendrimers [1]. We are particularly interested in building metallodendritic donor-acceptor systems with a threefold symmetrical core. For this purpose and making use of the electron-deficient nature of s-triazine cores and the electronic donor ability of the chosen metal moieties, we aim to build-up new redox-active heterometallic dendrimers with improved non-linear optical properties (NLO). Recently we have presented a divergent route for the preparation of homometallic and heterobimetallic dendrimers (G0–G2) based on a 2,4,6-tris(4-ethynyl)phenyl-1,3,5-triazine core (TEPT). In these dendrimers the peripheral functionalization of TEPT with [PtCl(PEt3)2] or [Pt(PEt3)2((C≡CC5H4)Fe(C5H5))]

[1d] moieties leads to a significant increase of the first hyperpolarizability response of the free core. We now wish to present our latest results in the synthesis and characterization of novel hybrid Pt/Ru or Ru/Fe metallodendrimers having as a core the [(HC≡C-C6H4-(C≡C-C6H4)n)3-1,3,5-C3N3] (n = 0, 1). The synthetized compounds have been fully characterized (e.g. NMR, UV/Vis, CV, FTIR, MS, EA) and the molecular first hyperpolarizability (β) was measured by hyper-Raleigh Scattering. A substantial increase in the first hyperpolarizability response was observed upon metallation of the free cores. Acknowledgements: The Portuguese Fundação para a Ciência e a Tecnologia (FCT) is acknowledged for funding through the research project PTDC/QUI/64202/2006, the NMR and MS Portuguese Networks (PTNMR-2013, RNEM-2013), the pluriannual base funding of CQM (PEst-OE/QUI/UI0674/2011-2013) and the Ph.D. scholarship granted to M.G. Jardim (SFRH/BD/65036/2009). The support of VidaMar Resorts is also gratefully acknowledged. [1] (a) Ornelas, C.; Ruiz, J.; Rodrigues, J.; Astruc, D. Inorg. Chem. 2008, 47, 4421. (b) Rodrigues, J.; Jardim, M.G.; Figueira, J.; Gouveia, M.; Tomás, H.; Rissanen, K. New J. Chem. 2011, 35, 1938. (c) Astruc, D.; Boisselier, E.; Ornelas, C. Chem. Rev. 2010, 110, 1857. (d) Maiti, S. K.; Jardim, M. G.; Rodrigues, J.; Rissanen, K.; Campo, J.; Wenseleers, W. Organometallics 2013, 32, 407.

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OC9 - HYBRID SILICA NANOPARTICLES AS MULTIFUNCTIONAL MATERIALS

Ana Sofia Rodrigues, Tânia Ribeiro, José Paulo S. Farinha, Carlos Baleizão

CQFM - Centro de Química-Física Molecular and IN - Institute of Nanoscience and Nanotechnology, Instituto Superior Técnico, 1049-001 Lisboa, Portugal

[email protected]

Silica nanoparticles (SiNP) have been extensively used as supports or carriers in catalysis, nanomedicine and imaging. Their characteristics can be tuned during the synthesis to obtain a wide range of particle diameters (20-500 nm) and to incorporate molecules such as catalysts, drugs, or fluorophores. These molecules can be physically entrapped inside the core or covalently attached to the silica network during the synthesis procedure. In particular, Mesoporous Silica Nanoparticles (MSNs) have emerged in the last years has exceptional supports/nanocontainers for molecules and polymers, due to the well-defined and controllable particle porous structure, opening a new range of applicability’s not achieved by standard SiNPs (ordered pore system of 2-4 nm diameter, pore volumes above 1 mL/g). The preparation of hybrid MSNs requires the presence of an organic molecule (with two terminal trialkoxysilanes in the moiety) during the synthesis, which becomes aligned with the pores, thus impervious to aggregation and self-quenching effects. This communication will focus on our recent efforts in the development of functional hybrid SiNPs and MSNs, for applications such as “smart” nanocontainers,[1] advanced coatings [2] and NIR imaging.[3]

Figure 1: Hybrid MSN “smart” nanocontainers (A), and hybrid SiNPs for advanced coatings (B) and

NIR imaging (C). Acknowledgements: This work was partially supported by Fundação para a Ciência e a Tecnologia (FCT-Portugal) and COMPETE (FEDER) within projects PTDC/CTM-NAN/2354/2012 and RECI/CTM-POL/0342/2012. A.S.R. and T.R. also thank FCT for Ph.D. grants (SFRH/BD/89615/2012; SFRH/BD/64702/2009). [1] Rodrigues, A. S.; Ribeiro, T.; Fernandes, F.; Farinha, J. P. S.; Baleizão, C. Microscopy and Microanalysis 2013, 19, 1216-1221. [2] Ribeiro, T.; Fedorov, A.; Baleizão, C.; Farinha, J. P. S. J. Colloid Interface Sci. 2013, 401, 14-22. [3] Ribeiro, T.; Raja, S.; Rodrigues, A. S.; Fernandes, F.; Farinha, J. P. S.; Baleizão, C. RSC Advances 2013, 3, 9171-9174.

A B C

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OC10 - IRIDIUM Cp* COMPLEXES BASED ON ABNORMAL CARBENES: SYNTHESIS, REACTIVITY AND CATALYSIS

Ana Petronilho and Martin Albrecht

Center for Synthesis and Chemical Biology, University College Dublin, Belfield Campus, Dublin, Ireland. [email protected]

N-heterocyclic carbenes (NHCs) have arised in the last years as powerfull ligands emplied widely in relevant catalytic processes.[1] With the arise of the first abnormal carbenes,[2] reports on their increased -donating properties with respect to their normal congeners[3] suggests that their application in catalysis can improve the catalytic activity of known systems based on normal NHCs, however, their stability is limited.[4] Typical methodologies for the synthesis of abnormal carbenes include, among others, the use of protecting groups at C(2) such as phenyl or methyl substituents. However, this methodology may induce the formation of side products, due to the non-inertness of the protecting groups. Alternatively, the replacement of the C(2) atom with a nitrogen atom to form a triazole provides an easily accessible methodology for both ligand synthesis, based on click chemistry, and for abnormal carbene generation.

Figure 1: Iridium complexes of bearing imidazolylidene (1) and triazolylidene (2) ligands .as catalysts

for hydrosilylation of ketones. In this communication we will report on the synthesis of abnormal carbenes derived from imidazoles and triazoles and their stability and application as catalysts for hydrosilylation of ketones will be discussed.

[1] Diez-Gonzalez, S. (Ed.), N-heterocyclic carbenes; From laboratory curiosities to efficient synthetic tools (RSC Catalysis Series, Cambridge, UK), 2011. [2] a) Schuster, O.; Yang, L.; Raubenheimer, H.; Albrecht, M., Chem. Rev. 2009, 109, 3445. [3] a) Heckenroth, M.; Neels, A.; Garnier, Michael G.; Aebi, P.; Ehlers, Andreas W.; Albrecht, M., Chem. Eur. J. 2009, 15, 9375. [4] a) D. Canseco-Gonzalez, A. Gniewek, M. Szulmanowicz, H. Müller-Bunz, A. Trceziak, M. Albrecht, Chem. Eur. J. 2012, 18, 6055. b) D. Canseco, A. Petronilho, T. Ooi, M Albrecht, J. Am. Chem. Soc., 2013, 13193.

O

R3SiH

R3SiO

[Ir]

I II 1

ClIr

N NN

BF4

ClIr

NN

NN

OTf

2

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OC11 - IMINOPYRROLYL SODIUM SALTS: SYNTHESIS, STRUCTURAL CHARACTERISATION AND THEIR REACTIVITY

TOWARDS NICKEL, COBALT, IRON, COPPER AND ZINC HALIDES

Clara S. B. Gomes, M. Teresa Duarte, Pedro T. Gomes

Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal. e-mail: [email protected]

2-Iminopyrrole ligand precursors are of great interest in the areas of organometallic and coordination chemistry because of their high versatility and tunability, being mainly used as polymerization catalysts [1]. In this communication, we report the synthesis and structural characterisation of a series of sodium salts bearing 2-(N-aryl-formimino)pyrrolyl or 2-(N-aryl-formimino)phenanthro[9,10-c]pyrrolyl ligands, in which these chelating ligands encompass an increasing bulkiness of the aryl substituent at the iminic nitrogen (C6H5; 2,6-Me2C6H3; 2,4,6-Me3C6H2 and 2,6-iPr2C6H3) [2]. The reaction of two equivalents of these precursors with different Ni(II), Co(II), Fe(II), Cu(I) and Zn(II) halides afforded bis(iminopyrrolyl) or bis(iminophenanthro[9,10-c]pyrrolyl) complexes with different geometries around the metal centres [3]. Furthermore, the zinc derivatives showed luminescent properties with a large enhancement of the fluorescence emission of the bis(phenanthropyrrolyl) complexes when compared to the emission of their ligand precursors or the bis(pyrrolyl) analogues.

Figure 1: Syntheses of bis(iminopyrrolyl) Ni, Co, Fe, Cu and Zn complexes. Acknowledgements: We thank the Fundação para a Ciência e Tecnologia, Portugal, for financial support (Projects PTDC/EQU-EQU/110313/2009, PTDC/QUI/65474/2006, PEst-OE/QUI/UI0100/2013 RECI/QEQ-QIN70189/2012) and for a fellowship to C.S.B.G. (SFRH/BPD/64423/2009). [1] For example: (a) K. Mashima et al. J. Organomet. Chem. 2005, 690, 4414 and references cited therein; (b) S. D. Ittel et al. Chem. Rev. 2000, 100, 1169; (c) V. C. Gibson et al. Chem. Rev. 2003, 103, 283. [2] C. S. B. Gomes et al. Dalton Trans. 2010, 39, 736. [3] (a) C. S. B. Gomes et al. J. Organomet. Chem. 2013, in press, DOI : 10.1016/j.jorganchem.2013.10.053 ; (b) C. S. B. Gomes et al. Inorg. Chem. 2009, 48, 11176.

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OC12 – DINUCLEAR ZINC–N-HETEROCYCLIC CARBENE COMPLEXES FOR EITHER THE CONTROLLED RING-OPENING

POLYMERIZATION OF LACTIDE OR THE CONTROLLED DEGRADATION OF POLYLACTIDE UNDER MILD CONDITIONS

Christophe Fliedel1,2, Diogo Vila-Viçosa3,

Maria José Calhorda3, Samuel Dagorne2, Teresa Avilés1

1REQUIMTE, Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, 2829-516 Caparica (Portugal)

2Institut de Chimie de Strasbourg, CNRS-Université de Strasbourg 1 rue Blaise Pascal, 67000 Strasbourg (France)

3 Departamento de Química e Bioquímica, CQB, Faculdade de Ciências, Universidade de Lisboa, Campo Grande, Ed. C8, 1749-016 Lisboa (Portugal)

[email protected]

We describe the synthesis of new Zn–NHC alkoxide complexes [(NHC)ZnCl(OBn)] for use as ROP initiators for lactide polymerization. These complexes are readily accessible in two steps from the corresponding imidazolium salts. The ZnII alkoxide species were found to mediate either the ROP of lactide to produce chain length-controlled polylactide (PLA) or, in the presence of an alcohol source the controlled degradation of PLA through extensive transesterification reactions to afford methyl lactate as the major product [1]. The NHC-Zn catalysts were also found to efficiently polymerize trimethylene carbonate (TMC) leading to well-defined poly-TMC. The production of PTMC/PLA block-co-polymers was also accessible by the use of these robust initiators [2].

Figure 1: ROP of rac-lactide initiated by NHC-Zn alkoxide complexes and PLA degradation

Acknowledgements: We are grateful to the Fundação para a Ciência e Tecnologia (FCT), Portugal for funding project PTDC/QUI-QUI/099873/2008 and fellowship SFRH/BPD/73253/2010 (C.F.). [1] Fliedel, C.; Vila-Viçosa, D.; Calhorda, M. J.; Dagorne, S.; Avilés, T. ChemCatChem, 2014, DOI : 10.1002/cctc.201301015. [2] Fliedel, C.; Mameri, S.; Dagorne, S.; Avilés, T. Appl. Organomet. Chem., 2014, accepted.

Oral Communications

26

OC13 - TOWARDS THE UNDERSTANDING OF RADICAL REACTIONS: EXPERIMENTAL AND COMPUTATIONAL STUDIES OF

TITANIUM(III) DIAMINE BIS(PHENOLATE) COMPLEXES

Sónia Barroso1, Filipe Madeira1, M. José Calhorda2 and Ana M. Martins1

1Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av.

Rovisco Pais 1049-001 Lisboa, Portugal. Email: [email protected] 2Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade de Lisboa,

Campo Grande, Ed. C8 1749-016 Lisboa, Portugal.

Radical reactions of titanium(III) [Ti(L)Cl(S)] (S = THF, 1; S = py, 2; L = Me2N(CH2)2N(CH2-2-O-3,5-tBu2-C6H2)2) are described [1]. Reactions with the neutral electron acceptors TEMPO and PhN=NPh led to [Ti(L)Cl(TEMPO)] (4) and [Ti(L)Cl2] (9), respectively. 9 was also formed when [Ti(L)Cl(S)] was oxidized by [Cp2Fe][BPh4], but the [Cp2Fe][PF6] analogue yielded [Ti(L)ClF] (8). The reactions of [Ti(L)Cl(S)] with O2 gave [Ti(L)Cl]2(µ-O) (3) that was shown to be a thermodynamically favorable transformation (DFT, G = -123.6 kcal∙mol-1). [Ti(L)(CH2Ph)(S)] (S = THF, 5; py, 6) are not stable in solution for long periods and in diethyl ether gave 1:1 co-crystals of [Ti(L)(CH2Ph)2] (7) and [Ti(L)Cl]2(µ-O) (3). The oxidation of [Ti(L)(2-{CH2-2-(NMe2)-C6H4})] (10) led to a complex mixture. Recrystallization of this mixture under air led to a 1:1 co-crystal of two coordination isomers of 3 displaying a coordination mode of the ligand never observed before.

Acknowledgements: The authors thank the FCT for funding (SFRH/BPD/7394/2010, Pest-OE/QUI/UI0100/2013 and PEst-OE/QUI/UI0612/2011). [1] S. Barroso, J. Cui, J. M. Carretas, A. Cruz, I. C. Santos, M. T. Duarte, J. P. Telo, N. Marques, A. M. Martins, Organometallics 2009, 28, 3449-3458. [2] S. Barroso, F. Madeira, M. J. Calhorda, M. J. Ferreira, M. T. Duarte, A. M. Martins, Inorg. Chem. 2013, 52, 9427-9439.

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OC14 – INNOVATIVE METAL BASED IONIC LIQUIDS

Branco, Luís C.; Forte, A.; Gago, S.; Laia, C.A.T; Pina, F.

REQUIMTE, Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, 2829-516 Caparica, Portugal ; email: [email protected]

Ionic Liquids (ILs) as functional materials based on the dissolution of task-specific molecules (organic, inorganic or polymeric materials) or incorporating these molecules as cation or anion units have been reported in last years1. Adequate combination of the peculiar properties of ILs (high chemical and thermal stability, high ionic conductivity and very low vapor pressure) with metal complexes (as counter-ions) can be suitable for many applications. In this context, our group has developed innovative metal based ionic liquids involving electrochromic, magnetic and luminescent applications2,3. Recently, Intrinsically Electrochromic Ionic Liquids were prepared by the combination metal complexes anions (e.g. EDTA metal complexes, vanadium and tungstate oxides or ruthenium and cobalt complexes) with appropriate organic cations (e.g. imidazolium, phosphonium, sulfonium, pyridinium, ammonium and guanidinium cations)4. The most promising Room Temperature Electrochromic ILs have been used as efficient and reversible colored devices.

Figure 1- Novel smart materials based on metal ionic liquids

Magnetic and Luminescent ILs have been also developed based on different paramagnetic ions such as iron(III), manganese(II), ruthenium(II), cobalt(II), europium(III)5, dysprosium(III), gadolinium(III), terbium(III) among others. The selection of paramagnetic ion and biocompatible counter-ions can be relevant in order to investigate their potential for selective separation processes as well as biological or medical applications. Acknowledgements: The authors would like to thanks to FCT-MCTES (PTDC/CTM-NAN/120658/2010 project) and Solchemar.

[1] Ma, Z.; Yu, J.;Dai, S. Adv. Mater. 2010, 22, 261. [2] Branco, A.; Branco, L. C.; Pina, F., Chem. Commun. 2011, 2300. [3] Branco, A.; Belchior, J.; Branco, L. C.; Pina, F.RSC Adv., 2013,3, 25627. [4] Gago, S.; Cabrita, L.; Lima, J. C.; Branco, L. C.; Pina, F. Dalton Trans. 2013, 42, 6213. [5] Pereira, C. C. L.; Dias, S.; Coutinho, I.; Leal, J. P.; Branco, L. C.; Laia, C. A. T. Inorg. Chem. 2013, 52, 3755.

Magnetic and Luminescent Ionic Liquids based on Tb(III)

= 9.82 MB

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OC15 - INFLUENCE OF ACIDITY AND PORE SIZE OF SILICATES ON THE SYNTHESIS OF HINDERED

HALOGENATED MESO-ARYL PORPHYRINS

Mónica Silva1, Mário J. F. Calvete1, Auguste Fernandes2, Suse S. Bebiano2, M. Filipa Ribeiro2, Hugh D. Burrows1, Mariette M. Pereira1

1Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade de Coimbra

Rua Larga, 3004-535 Coimbra, Portugal 2IBB, Centro de Engenharia Biológica e Química, Departamento de Engenharia Química,

Instituto Superior Técnico, Av. Rovisco Pais, 1049-001 Lisboa, Portugal. [email protected]

It is well established that the pKa and type of acid (organic1,2,3,4 or solid5 - Lewis or Brønsted) are determining factors for efficient pyrrol and aldehyde condensation. There are also examples of the use of solid acids to promote ship-in-a-bottle porphyrin synthesis and of the use of these porous materials in photocatalysis6,7. However, quantitative data is lacking and, to the best of our knowledge, no attempts have been made to correlate overall meso-aryl porphyrin yields with parameters such as pore size and acidity. The validation of the influence of acidity and pore size of several silicates in order to selectively act as support for preparation of immobilized porphyrins or as catalyst for synthesis of porphyrins in solution, from one-pot synthesis methodology, is here discussed. Immobilized porphyrin yields are dependent on both the acidity and the silicates pore size, being Al-MCM-41 the best fitting solid, with Lewis acidity of 120 μmol Py/g and pore size 30 Å. On the other hand, when the goal is the synthesis of hindered meso-aryl porphyrins in solution, the best porous silicate is NaY, with Lewis acidity of 510 μmol Py/g and pore size 14 Å. This method provides an appealing efficient, reusable and scalable catalyst alternative for one-pot synthesis of meso-aryl porphyrins in high yields. Acknowledgements: We thank FCT-Portugal and QREN/FEDER (COMPETE-Programa Operacional Factores de Competitividade) for funding (PTDC/QUI-QUI/112913/2009). MS thanks FCT for a post-doc grant SFRH/BPD/34372/2007. [1] Rothemund P., J. Am. Chem. Soc. 1935, 57, 2010. [2] Adler A. D., Longo F. R., Finarelli J. D., Goldmacher J., Assour J., Korsakoff L., J. Org. Chem. 1967, 32, 476. [3] Gonsalves M. D. R., Varejão J. M. T. B., Pereira M. M., J. Heterocyclic Chem. 1991, 28, 635. [4] Lindsey J. S., Schreiman I. C., Hsu H. C., Kearney P. C., Marguerettaz A. M., J. Org. Chem. 1987, 52, 827. [5] (a) Shinoda T., Izumi Y., Onaka M., J. Chem. Soc. Chem. Commun. 1995, 1801; (b) Kishan M. R., Rani V. R., Murty M. R. V. S., Devi P. S., Kulkarni S. J., Raghavan K. V., J. Mol. Catal. A: Chem. 2004, 223, 263. [6] Silva M., Azenha M. E., Pereira M. M., Burrows H. D., Sarakha M., Forano C., Ribeiro M. F., Fernandes A., Appl. Catal. B 2010, 100, 1. [7] Corma A., Garcia H., J. Chem. Soc, Dalton Trans. 2000, 1381.

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OC16 - A DINUCLEAR COPPER(II) CRYPTATE FOR THE RECOGNITION OF GLUTAMATE

Pedro Mateus1, Rita Delgado1

1 Instituto de Tecnologia Química e Biológica, Universidade Nova de Lisboa, Av. da República, 2780–157 Oeiras, Portugal.

Amino acid neurotransmitters have received much attention in biomedical research, medical diagnostics, clinical chemistry, and the pharmaceutical industry, because they play essential roles in control and regulation of various functions in the central and peripheral nervous system.[1] Consequently, it is not surprising that over the last 30 years supramolecular chemists have strived to design receptors selective for amino acids although this task has proven extremely challenging.[2] In our on going efforts to develop artificial receptors for the recognition of amino acids, we have focused on L-glutamate, a major excitatory transmitter in the central nervous system. In this work is described how the selective binding of L-glutamate can be achieved in the presence of other competing amino acid substrates using a dinuclear copper(II) complex of a large cryptand compound.

Acknowledgements: The authors acknowledge FCT and POCI, with co-participation of the European Community funds FEDER, for the financial support under project PTDC/QEQ-SUP/2718/2012. The NMR spectrometers are part of The National NMR Facility, supported by Fundação para a Ciência e a Tecnologia (RECI/BBB-BQB/0230/2012). P. Mateus thanks FCT for the grant SFRH/BPD/79518/2011. [1] Cooper, J. R.; Bloom, F. E.; Roth, R. H. The Biochemical Basis of Neuropharmacology, 8th Ed. (2003), Oxford, Oxford University Press, Inc. [2] Steed, J. W.; Atwood, J. L.; Supramolecular Chemistry, 2nd ed.; John Wiley and Sons, Ltd: Hoboken, New Jersey, 2009.

Oral Communications

30

OC17 – ARTIFICAL NUCLEASES BASED ON NEW BIPYRIDINE-TERPYRIDINE Cu(II) COMPLEXES

Inês Rodrigues, Filipa Mendes, Elisa Palma, Isabel C. Santos, Isabel Santos, António Paulo, Sofia Gama

Centro de Ciências e Tecnologias Nucleares (C2TN), Grupo de Ciências

Radiofarmacêuticas, Instituto Superior Técnico, Universidade de Lisboa, Campus Tecnológico e Nuclear, Estrada Nacional 10 ( km 139,7), 2695-066 Bobadela, LRS-Portugal

There has been considerable interest in the recent years for the development of DNA cleaving reagents for their applications in biotechnology and medicine.1 Transition metal ions show diverse structural features, variable oxidation and spin states and redox properties in different complexes. These properties could be exploited to discover novel artificial nucleases. Among the first row transition elements, copper has got a special interest in this regard since the discovery of first chemical nuclease by Sigman et al.2 Copper has high affinity for the nucleobases and copper complexes possess biologically accessible redox properties.1 Several copper complexes have been proposed as potential anticancer substances and cancer inhibiting agents, as they demonstrate remarkable anticancer activity and show general toxicity lower than platinum compounds.3 Very recently, mixed ligand copper(II) complexes were found to exhibit prominent anticancer activity by inducing apoptosis, binding strongly and cleaving DNA.3 In order to develop novel artificial nucleases, several mixed bipyridine-terpyridine Cu(II) complexes were synthesized. The ability of the ligands and Cu(II) complexes to cleave DNA was evaluated by monitoring the conversion of supercoiled ΦX174 plasmid DNA to nicked circular and linear DNA. All the Cu(II) complexes tested present a high artificial nuclease activity. Their cytotoxic properties were also tested on A2780 and A2780cisR cell lines. All the new mixed-ligand Cu(II) complexes presented a higher cytotoxicity when compared with cisplatin, and were able to significantly overcome cisplatin resistance. Acknowledgements: The authors would like to acknowledge FCT for financial support (PTDC/QUI-QUI/114139/2009)

[1] K. Ghosh, P. Kumar, N. Tyagi, U. P. Singh, N. Goel, Inorg. Chem. Comm. 2011, 14, 489. [2] D. S. Sigman, D. R. Graham, V. Daurora, A. M. Stern, J. Biol. Chem. 1979, 254, 12269. [3] R. Loganathan, S. Ramakrishnan, E. Suresh, A. Riyasdeen, M. A. Akbarsha, M. Palaniandavar, Inorg. Chem. 2012, 51, 5512 and references therein.

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31

OC18 - INTERACTION OF THERAPEUTIC VANADIUM COMPLEXES WITH PROTEINS

João Costa Pessoa1, Gonçalo Justino,1 Isabel Correia,1 Somnath Roy,1 Eugenio Garribba,2 Marino F. A. Santos,3 Teresa Santos-Silva3

1 Centro Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco

Pais, 1049-001 Lisboa, Portugal, [email protected] 2 Dipartimento di Chimica e Farmacia, and Centro Interdisciplinare per lo Sviluppo della Ricerca Biotecnologica e per lo Studio della Biodiversità della Sardegna, Università di

Sassari, Via Vienna 2, I-07100 Sassari, Italy. 3 REQUIMTE-CQFB, Departamento de Química, Faculdade de Ciências e Tecnologia,

Universidade Nova de Lisboa, 2829-516 Caparica, Portugal

For the prospective therapeutic use of vanadium the understanding of its transport and delivery to cells is a crucial issue, and strong evidence has been given indicating that most of the vanadium in the serum is bound to transferrin (hTF) [1]. In this work we report results of geometry optimization calculations, based on the known X-ray diffraction structure of the N-lobe of hTF, to model the binding of VIVO2+ at the Fe-binding site of the N-lobe of hTF. Additionally DFT methods are used to calculate relevant EPR and ESEEM parameters. Of all calculated VIVO-hTF structures, the one that yields lower calculated heats of formation and better agreement with the EPR data is the structure that includes CO3

2− as synergistic anion; however, the one with HCO3− cannot be ruled out. In this

structure the V=O bond length is ~1.6 Å, and the V atom is also coordinated by the phenolate O atom of Tyr188 (at ~1.9 Å), the aspartate O of Asp63 (at ~1.9 Å), the His249 Nτ (at ~2.1 Å), and an Ocarbonate (at ~1.8 Å). The Tyr95 phenolic O atom is at a long distance (~3.3 Å) from the VIV center. All of the O atoms are able to establish dipolar interactions with groups of the protein. It was demonstrated that when vanadium is administered in the form of a complex, e.g. VIVO(carrier)2, where carrier is an organic compound acting as a bidentate or tridentate ligand, two types of VIVO-carrier-hTF binding have been proposed: one with VIV at the Fe-binding site, the other at surface imidazole or carboxylate groups [3]. The binding of VIVO(carrier)2 species to surface His or Asp is indeed possible and is confirmed by a X-ray diffraction study with lysozyme. However, the relevance of this type of binding to the transport and delivery of VIV to cells is not known, this being an issue also discussed in this work. Not much attention has been given to the possibility of transport of vanadium in the oxidation states +3 or +5. This communication also focus on results addressing the binding of VV- and VIII-species to transferrin. Acknowledgements: The authors thank Fundação para a Ciência e Tecnologia (FCT), PEst-OE/QUI/UI0100/2013 and PEst-C/EQB/LA0006/2011 for financial support. [1] a) Costa Pessoa, J.; Tomaz, I. Curr. Med. Chem. 2010, 17, 3701-3738. b) Kiss, T.; Jakusch, T; Hollender, D.; Dörnyei, A.; Enyedy, E.A.; Costa Pessoa, J.; Sakurai, H.; Sanz-Medel, A. Coord. Chem. Rev. 2008, 252, 1153-1162.

32

Poster with Flash Communications

Flash Communications

33

PFC1 - STRUCTURAL AND FUNCTIONAL FEATURES OF CYTOCHROME CD1 NITRITE REDUCTASE

Célia M. Silveira1,2, Humberto A. Pedroso1, Anja Wust3, Rui Almeida1, Stephane Besson1, José J.G. Moura1, Isabel Moura1, Susana Andrade3,

M. Gabriela Almeida1,4 and Smilja Todorovic2

1 REQUIMTE, Departamento de Química, CQFB, Faculdade de Ciências e Tecnologia,

Universidade Nova de Lisboa, 2829-516 Caparica, Portugal 2 Instituto de Tecnologia Química e Biológica, Universidade Nova de Lisboa,

Av. da República -EAN, 2780-157 Oeiras, Portugal 3 Institut fur Biochemie, Albert-Ludwigs-Universitat Freiburg,

Albertstrasse 21, 79104 Freiburg, Germany 4 Instituto Sup. de Saúde Egas Moniz, Monte de Caparica, 2829-511 Caparica, Portugal

[email protected]

Cytochrome cd1 nitrite reductases (cd1NiRs) are periplasmic proteins responsible for the one electron reduction of nitrite to nitric oxide. They can be isolated from denitrifying bacteria, microorganisms that utilize oxidized nitrogen compounds, such as nitrate and nitrite, as electron acceptors for energy production. cd1NiRs are homodimeric proteins that contains one heme c (the electron transfer site) and one heme d1 (the active site) per monomer. Although reaction mechanisms have been proposed for this enzyme there are still many open questions. For example, the rate limiting step of the overall reaction, the repercussion of the redox state of heme c during catalysis, the role of heme d1 in the displacement of NO are controversial topics [1-2]. In this context we are studying the mechanisms that control the electron transfer (ET) processes in cd1NiR from Marinobacter hydrocarbonoclasticus by using a toolbox of different experimental approaches. The enzyme was immobilized on silver electrodes, coated by alkanethiol based self-assembled monolayers, and probed by surface enhanced resonance Raman spectroscopy. In this way we could study the potential dependent ET processes involving hemes c and d1. Upon immobilization, the redox potential of cd1NiR was shifted to more negative potentials when compared to native RR titrations and previous reports. The interaction of cd1NiR with its physiological electron donor, cytochrome c552, was characterized by electrochemistry and molecular bioinformatics. Cyt c552 displays a reversible reaction at carbon electrodes and therefore cyclic voltammetry could be used to learn about the intermolecular ET between the two redox partners. Moreover molecular docking was used to model the complex cd1NiR - cyt c552. In parallel studies the protein’s 3D structure was determined by homology modeling and x-ray crystallography.

[1] Cutruzzola, F.; Rinaldo, S.; Castiglione, N.; Giardina, G.; Pecht, I.; Brunori, M. BioEssays 2009, 31, 885-891. [2] Rinaldo, S.; Sam, K.A.; Castiglione, N.; Stelitano, V.; Arcovito, A.; Brunori, M.; Allen, J.W.; Ferguson, S.J.; Cutruzzola, F. Biochem J 2011, 435, 217-225.


34

PFC2 – ENGINEERING HIGHLY EFFICIENT Eu(III)-BASED TRI-UREASIL HYBRIDS TOWARD

LUMINESCENT SOLAR CONCENTRATIONS

Mariela Nolasco1, Patrícia Vaz2, Vânia Freitas1, Patrícia P. Lima1, Paulo André3, Rute Ferreira1, Pedro Vaz4, Paulo Ribeiro-Claro2, Luís Dias Carlos1

1 Department of Physics and CICECO, University of Aveiro, Portugal, [email protected]; 2

Department of Chemistry and CICECO, University of Aveiro, Portugal; 3 Instituto de Telecomunicações and Department of Physics, Universidade de Aveiro, Portugal;4 Centre of Chemistry and Biochemistry, Department of Chemistry and Biochemistry, Faculty of Science,

University of Lisboa, Portugal

Following a computational-experimental approach, a highly luminescent europium(III) complex containing 2-thenoyltrifluoracetonate (tta-) and 5,6-epoxy-5,6-dihydro-[1,10]phenanthroline (ephen) ligands, Eu(tta)3ephen (II) was theoretically studied by DFT/TD-DFT calculations, synthesized from Eu(tta)3(H2O)2 (I) and fully characterized by high resolution mass spectrometry, TGA analysis, vibrational, UV-Vis and photoluminescence spectroscopy. For intramolecular energy transfer analysis purpose, the Ln(NO3)3(ephen)2 [Ln = Eu (III), Gd (IV)] complexes were synthesized and complexes I and III were theoretically studied. The tri-ureasil matrix was used as a support for the immobilization of complex II and two hybrid samples were synthesized as a monolith (MtU5Eu-II) and as a thin film (FtU5Eu-II), characterized and its photoluminescence properties were compared with those of complex II. The photophysical properties of complex II benefit from the synergy between the excited-states of both ligands that create efficient energy transfer pathways to optimize the Eu3+ sensitization contributing for the large emission quantum yield (Fig.1) which is one of the highest so far reported for solid lanthanide -diketonate complexes. Moreover, although the incorporation of complex II into the hybrid matrix is disadvantageous from the quantum yield standpoint, MtU5Eu-II and FtU5Eu-II exhibit the highest emission quantum yields reported so far for Eu3+- containing hybrids (Fig.1). Additionally, a significant improvement in the photostability under UV irradiation of the incorporated complex II is observed. The possibility of FtU5Eu-II to be used as luminescent solar concentrator was evaluated and an optical conversion efficiency of 9% as well as an ability to boost up to 0.5 % the Si-photovoltaic cells output were verified.

Figure 1: Schematic representation of all the synthesized and characterized materials

Acknowledgments: The authors are grateful to FCT, COMPETE and FEDER programs (Pest-C/CTM/LA0011/2013, PEst-OE/QUI/UI0612/2011, PTDC/CTMNAN/112168/2009, PTDC/CTM/ 101324/2008).

ɸ=828%

UVUVabsorptionabsorptionɸ=636%

MtU5Eu-II

ɸ=485%FtU5Eu-II

ɸ=828%

UVUVabsorptionabsorptionɸ=636%

MtU5Eu-II

ɸ=485%FtU5Eu-II


35

PFC3 - PHOTOCATALYTIC DEGRADATION OF PHARMACEUTICAL COMPOUNDS BY TIO2: AN ECOTOXICITY ASSESSMENT

Marta A. Andrade1,2, Ana Sofia Mestre1, Nuno Lapa3, Benilde Mendes3, Conchi O. Ania2, Ana Paula Carvalho1

1Dpt. Química e Bioquímica and CQB, Faculdade de Ciências da Universidade de Lisboa,

Ed. C8 Campo Grande, 1749-016 Lisboa, Portugal. 2lnstituto Nacional del Carbón (INCAR, CSIC) 33011, Oviedo, Spain.

3Dpt. Ciências e Tecnologia da Biomassa, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, 2829-516 Caparica, Portugal.

In the last few years, a considerable amount of research has been carried out in the field of advanced oxidation processes (AOPs) to be applied in the removal and degradation of emergent contaminants from wastewaters. Among AOPs, heterogeneous photocatalysis is an effective technology for the degradation of organic pollutants. Compared to other semiconductors, titanium dioxide plays a leading role as photocatalyst due to its cost effectiveness, inert nature and photostability [1]. However, most of the studies on photocatalysis do not encompass an ecotoxicity evaluation, being more focused on the degradation efficiency and mineralization of the pollutants. The possible synergic effects due to the presence of various pollutants in solution are also scarcely addressed. In this context, the aim of the present work is to study the photocatalytic degradation of pharmaceutical compounds using TiO2 as catalyst, and to assess the ecotoxicity variation associated with the process. The target molecules were ibuprofen (IBU), sulfamethoxazole (SMX) and mixtures IBU/SMX, as these compounds are medicines of great consumption, frequently detected in the environment. The results are interpreted in terms of the mineralization achieved (Total Organic Carbon) and of the ecotoxicity of the initial and final solutions obtained after the photocatalytic assays. The ecotoxicity assessment was performed by the bioluminescence inhibition of the bacterium Vibrio fischeri using the Microtox® assay. The results were expressed as the Effective Concentration for 50 % bioluminescence inhibition after 30 min of exposure (EC50-30 min). The initial solutions of IBU and SMX and their mixtures presented high EC50 values; the mixtures presented an increase of the ecotoxicity. The photodegradation assays with TiO2 proved to be effective, since high mineralization rates along with the absence of ecotoxicity of the final solutions were achieved. This study will proceed with the evaluation of the best operating conditions for the photocatalytic assays, providing a new insight on the degradation of this class of compounds, as well as on their ecotoxicity for a bacterium of the marine environment. Acknowledgements: This work was supported by FCT pluriannual programme of CQB (PEst-OE/QUI/UI0612/2013). MA and ASM thank FCT for a PhD and a Post-doc grant, respectively (SFRH/BD/71673/2010, SFRH/BPD/86693/2012). [1] Carvalho, A.P., Mestre, A.S., Andrade, M., Ania, C.O. “Ibuprofen in the aquatic environment: occurrence, ecotoxicity and water remediation technologies” in Wilton C. Carter and Brant R. Brown Ed. Ibuprofen: Clinical Pharmacology, Medical Uses and Adverse Effects. Nova Science Publishers, Inc., 2013, Ch. 1, p. 1-84. ISBN: 978-1-62618-659-0.


36

PFC4 - ACTIVITY AND DEGRADATION OF COPPER-SALAN COMPLEXES IN OXIDATIVE CATALYSIS

Pedro Adão1, Sónia Barroso1, Fernando Avecilla2, M. Conceição M. A. Oliveira1, João Costa Pessoa1

1 Centro Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovísco

Pais, 1049-001 Lisboa, Portugal 2 Departamento de Química Fundamental, Universidade da Coruña, Campus de A Zapateira,

15071 A Coruña, Spain Email: [email protected]

Copper complexes of the salen and salan class are well-known for their relative ease of preparation and use as oxidation catalysts [1]. Moreover, salan-type compounds offer increased stability towards hydrolysis [2]. Our group evaluated the potential of various copper-salan complexes in asymmetric sulfoxidation and epoxidation (see Figure 1). Besides the low to moderate catalytic activities obtained, it was observed that the copper-salan catalysts decomposed under mild conditions by oxidative dehydrogenation and subsequent hydrolysis of the ligand [3]. The catalytic activities observed could not be unambiguously attributed to the copper-salan complexes used, but instead should be mainly attributed to their respective degradation products. This should be taken into account whenever the application of copper-salan complexes in oxidative catalysis is considered.

Figure 1: Sulfoxidation and epoxidation reactions catalyzed by Cu-salan complexes.

Acknowledgements: This work was supported by Fundação para a Ciência e a Tecnologia, PEst-OE/QUI/UI0100/2013, the IST-UTL Centers of the Portuguese NMR and Mass Spectrometry Networks (REM2013, RNNMR), RECI/QEQ-QIN/0189/2012, RECI/QEQ-MED/0330/2012, grants SFRH/BD/40279/2007, SFRH/BPD/73941/2010 and SFRH/BPD/79778/2011. [1] Zhu, H.; Dai, Z.; Huang, W.; Cui, K.; Gou, S.; Zhu, C. Polyhedron, 2004, 23,1131-1137. [2] Adão, P.; Costa Pessoa, J.; Henriques, R. T.; Kuznetsov, M. L.; Avecilla, F.; Maurya, M. R.; Kumar, U.; Correia, I.; Inorg. Chem. 2009, 48, 3542-3561. [3] Taylor, M. K.; Reglinski, J.; Berlouis, L. E. A.; Kennedy, A. R. Inorg. Chim. Acta, 2006, 359, 2455-2464.


37

PFC5 - PALLADIUM/PHOSPHORUS COMPLEXES AS CATALYSTS FOR HYDROVINYLATION AND CARBONYLATION REACTIONS

Rui M. B. Carrilho, Gonçalo N. Costa, Mariette M. Pereira

Universidade de Coimbra, Departamento de Química,3004-535 Coimbra, Portugal ([email protected])

Phosphorus metal complexes are considered one of the most important classes of compounds, with widely known applications in organometallic chemistry and in homogeneous catalysis.[1] In particular, palladium-catalyzed reactions that generate new C–C bonds by incorporation of cheap and abundant carbon feedstock (such as carbon monoxide and simple olefins like ethylene), by an atom-economic mode, are among the most relevant transformations in modern chemistry. In this communication we present our recent results on the applications of palladium/phosphorus complexes as catalysts in hydrovinylation and aminocarbonylation reactions (Figure 1).

Figure 1: Palladium-catalyzed homogeneous reactions.

A set of chloro-allylpalladium/phosphite complexes have been synthesized and applied as catalytic precursors in the asymmetric hydrovinylation of styrene, achieving enantiomeric excesses up to 93%.[2] Furthermore, different Pd/phosphorus complexes were used in aminocarbonylation reactions of haloalkenes and haloarenes, providing efficient synthetic tools towards the development of distinct families of valuable carboxamides, ketocarboxamides and dicarboxamides.[3,4]

Acknowledgements: The authors are thankful to FCT for financial support (FCT/QREN/FEDER/COMPETE, PTDC/QUI-QUI/112913/2009). R.M.B.C. thanks for QREN/LUZACNE Post-Doc fellowship. [1] Calvete, M. J.; Carrilho, R. M. B.; Abreu, A. R.; Pereira, M. M. Chem. Soc. Rev. 2013, 42, 6990-7027. [2] Carrilho, R. M. B.; Costa, G. N.; Neves, A. C. B.; Pereira, M. M.; Grabulosa, A.; Bayón, J. C.; Rocamora, M.; Muller, G. Eur. J. Inorg. Chem. 2014, 1034-1041.


38

PFC6 - SULFONIC ACID FUNCTIONALIZED CLAYS: EFFICIENT AND VERSATILE SOLID CATALYSTS

A. F. Peixoto, S. M. Silva, J. P. Novais, C. Freire

REQUIMTE, Department of Chemistry and Biochemistry, Faculty of Science,

University of Porto, Portugal. [email protected]

Acids are the most important and common catalysts. However, the use of liquid acids is associated with several problems including difficulty in separation, the need for neutralization, the impossibility of reuse, etc. Thus, it remains a challenge the demand for efficient solid acid catalysts which avoid the problems associated with the liquid catalysts.[1] In recent years, the resource to clays as nanostructured solid acid catalysts to apply in several organic transformations is being growing. Clays are good alternatives within the heterogeneous catalysts because they are cheap, versatile and easily available from natural sources and can be straightforwardly functionalized to achieve the maximum catalytic activity.[2,3] In this work we selected three different clays: halloysite nanotubes (HNTs), Cloisite Na+ (cloi-Na) and Montmorilonite (K10) to be functionalized with organosilanes with the suitable reactive groups to allow the introduction of sulfonic acid groups (Figure 1). All the functionalized clays were characterized by Fourier transform infrared spectroscopy (FTIR-ATR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and Thermogravimetry (TG). The acidity of the functionalized clays was also determined by pHpzc. The catalyst activity was evaluated in the stearic acid esterification and the product formation was monitored by GC. The catalysts showed very good conversions (> 95 %) and high reusability.

Figure 1: Introduction of sulfonic groups into clay surface.

Acknowledgements: FCT and FEDER through grant no. PEst-C/EQB/LA0006/2011 and through Operation NORTE-07-0124-FEDER-000067 – NANOCHEMISTRY funded by FEDER and CCDRN. AFPeixoto thanks FCT post-doc grant (SFRH/BPD/72126/2010). [1] Corma, A.; Garcia, H. Adv. Synth. Catal. 2006, 348, 1391-1412. [2] Shirini, F.; Mamaghani, M.; Atghia, S. V. J. Nanostructure Chem. 2012, 3:2, 1-5. [3] Catrinescu, C.; Fernandes, C.; Castilho, P., Breen, C.; Carrott, M.M.L.R.; Cansado I.P.P. Appl. Catal. A.: Gen. 2013, 467, 38-46.


39

PFC7 - STUDIES ON THE OLIGO-/POLYMERISATION OF ETHYLENE EMPLOYING IMINOPYRROLYL NICKEL(II) COMPLEXES AS

ALUMINIUM-FREE CATALYSTS

Cláudia A. Figueira1, Joselaine S. Gomes1, Clara S. B. Gomes1, Pedro T. Gomes1, M. Amélia N. D. A. Lemos2, Francisco Lemos2

1Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa

2IBB / CERENA, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal. Email: [email protected]

Studies on the homo- or copolymerisation of α-olefins remain an important field in the search for new materials, new catalytic systems or in the use of more sustainable reaction media. Grubbs and co-workers [1] carried out a prominent work in the development of single-component catalysts for the homo- and copolymerisation of ethylene, using neutral nickel(II) complexes bearing phenoxyimine ligands. Several other authors such as Brookhart [2], Li [3] or Mecking [4], extended this research by developing new complexes with 2-anilinotropone or similar ligands. The iminopyrrolyl bidentate framework is isoelectronic with the previous ligands but until present it attracted little attention in this particular field. Driven by the lack of investigation and in the light of promising studies in our group comprising the oligomerisation of ethylene [5], we developed a new family of nickel(II) complexes of stereochemically crowded iminopyrrolyl ligands with the general structure shown in Figure 1. Several ethylene polymerisation tests were performed in the presence or absence of the phosphine scavenger [Ni(COD)2], at different pressures and temperatures. Kinetic studies in a low pressure ethylene rig were also carried out. Hyperbranched low molecular weight polyethylenes were obtained, which were characterised by 1H and 13C NMR spectroscopy and GPC/SEC chromatography.

Figure 1 Acknowledgements: The authors thank the Fundação para a Ciência e Tecnologia, Portugal, for financial support (Projects PTDC/EQU-EQU/110313/2009 and Pest-OE/QUI/UI0100/2013) and for fellowships to C.A.F. (SFRH/BD/47730/2008) and C.S.B.G (SFRH/BPD/64423/2009). [1] (a) Youkin, T. R.; Connor, E. F.; Henderson, J. I.; Friedrich, S. K.; Grubbs, R. H.; Bansleben, D. A. Science 2000, 287, 460; (b) Connor, E. F.; Youkin, T. R.; Henderson, J. I.; Waltman, A. W.; Grubbs, R. H. Chem. Commun. 2003, 2272. [2] Hicks, F. A.; Jenkins, J. C.; Brookhart M. Organometallics 2003, 22, 3533. [3] Song, D.-P.; Li, Y.-G.; Lu, R.; Hu, N.-H.; Li, Y.-S. Appl. Organomet. Chem. 2008, 22, 333. [4] (a) Zuideveld, M. A.; Wehrmann, P.; Röhr, C.; Mecking, S. Angew. Chem. Int. Ed. 2004, 43, 869; (b) Guironnet, D.; Friedberger, T.; Mecking, S. Dalton Trans. 2009, 8929. [5] Bellabarba, R. M.; Gomes, P. T.; Pascu, S. I. Dalton Trans. 2003, 4431.


40

PFC8 - CYCLAM-BASED Zr(IV) COMPLEXES FOR CYCLAM FUNCTIONALIZATION

Luis G. Alves, Filipe Madeira, Rui F. Munhá, Luis F. Veiros, Ana M. Martins

Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais 1, 1049-001 Lisboa, Portugal. [email protected]

Following our previous work on the chemistry of Zr(IV) complexes based on cyclam ligands [1], we present a comprehensive study on the reactions of heteroallenes with (Bn2Cyclam)ZrX2 (X = OiPr, OtBu, SPh, NHtBu) and the ortho-metallated species ((C6H4CH2)BnCyclam)Zr(NHtBu) (Scheme 1). The reactions may be modulated by the choice of ligands X and also depend on the type of heteroallene (RN=C=O, RN=C=S, RN=C=NR, S=C=S). The discussion of the reactivity and structures, using both experimental and computational data, attest the diversity of products obtained and the application of this methodology as a new procedure for the functionalization of cyclam rings.

Scheme 1

Acknowledgements: The authors thank FCT for funding (SFRH/BPD/86815/2012 and SFRH/BD/87679/2012). [1] (a) Alves, L. G. et al., Inorganic Chemistry 2012, 51, 10-12. (b) Alves, L. G. et al., Dalton Trans. 2012, 14288-14298. (c) Munhá, R. F. et al., Dalton Trans. 2009, 7494-7508. (d) Munhá, R. F. et al. Organometallics 2010, 29, 3753-3764.


41

PFC9 - MULTI-ANALYTICAL STUDY OF INDUCED FOXING STAINS ON MODERN PAPER

Cátia Relvas1, Margarida Nunes1, Francisca Figueira2, Joana Campelo2, António Candeias1-3, Ana Teresa Caldeira1,2, Teresa Ferreira1,2*

1HERCULES Laboratory, Évora University, Évora, Portugal

2José Figueiredo Laboratory, General Directorate for Cultural Heritage, Lisbon, Portugal 3Évora Chemistry Centre, Évora University, Évora, Portugal

*[email protected]

Foxing spots appear on the paper as stains of reddish-brown, brown or yellowish colour, generally of small dimensions, with sharp or irregular edges [1]. This phenomenon has been actively researched since the 1930s however the real cause of the deterioration is not well understood despite the numerous studies devoted to it. The cause of the formation of foxing is usually ascribed to heavy-metal-induced degradation of cellulose and sizing, fungal activity or both. Foxing may result from the oxidation of metal impurities incorporated in the paper during its manufacture. Biological foxing is caused by the presence of mould that reacts with the paper in a slow process and can be associated with iron salts present in the paper [2-3]. Another hypothesis that has developed on the foxing formation is cellulose oxidation. Oxidation occurs by a reaction between a cellulose molecule and oxygen that forms hydrogen peroxide radicals as a reactive intermediate. Metals or acids from various origins, e.g. fungal metabolites or cellulose degradation products, can accelerate the oxidation process [2]. In this work, two types of paper supports were used to study the influence of metal ions and microbiological activity as factors that promote the appearance of foxing stains. Test samples from a gravure printing paper and a watercolour paper were cut into (2x2) cm squares and were artificially aged with and without metallic ions. For the paper characterization and induced stains, non-destructive analytical techniques, were used. Conventional visual observation of the samples was done by light microscopy and colorimetric values were registered to evaluate colour differences. Morphological and chemical characterizations were carried out using variable pressure scanning electron microscopy coupled with energy dispersive X-ray spectrometry (VP-SEM/EDS) and attenuated total reflexion Fourier transform infrared spectroscopy (ATR-FT-IR). [1] Bicchieri, M.; Ronconi, S.; Romano, F.; Pappalardo, L.; Corsi, M.; Cristoforetti, G.; Legnaioli, S.; Palleschi, V.; Salvetti, A.; Tognoni, E. Spectrochim. Acta Part B 2002, 57, 1235-1249 [2] Manso, M.; Pessanha, S.; Figueira, F.; Valadas, S.; Guilherme, A.; Afonso, M.; Rocha, A.C.; Oliveira, M.J.; Ribeiro, I.; Carvalho, M.L. Anal. Bioanal. Chem. 2009, 395, 2029-2036 [3] Rakotonirainy, M.; Heude, E.; Lavédrine, B. J. Cult. Herit. 2007, 8, 126-133.

Posters

Posters

43

P1 - A DINUCLEAR COPPER(II) COMPLEX AS RECEPTOR FOR PHOSPHORYLATED SUBSTRATES

Lígia Mesquita1, Pedro Mateus1, Rita Delgado1

1 Instituto de Tecnologia Química e Biológica, Universidade Nova de Lisboa, Av. da República, 2780–157 Oeiras, Portugal

Phosphate anions and their derivatives are ubiquitous in biology and in the environment. In biological systems they play crucial roles in energy storage and signal transduction, whereas their uncontrolled spread in the environment contributes for the eutrophication of natural water sources.[1] Not surprisingly, significant efforts have been made over the years to develop artificial receptors to achieve the selective binding of phosphorylated molecules in order to provide new methods for the detection, extraction, and transport of biologically and environmentally important phosphates.[1] One of the most successful class of receptors for phosphorylated compounds in aqueous solution are dinuclear complexes of macrocyclic and macrobicyclic compounds. Theses complexes are able to form cascade species by the selective coordination of the guest between the metal centres with concomitant encapsulation within well defined molecular cavities.[2] In this work a new dinuclear copper(II) macrocyclic complex and its recognition properties towards phosphorylated substrates will be presented. Acknowledgements: The authors acknowledge FCT and POCI, with co-participation of the European Community funds FEDER, for the financial support under project PTDC/QEQ-SUP/2718/2012. The NMR spectrometers are part of The National NMR Facility, supported by Fundação para a Ciência e a Tecnologia (RECI/BBB-BQB/0230/2012). P. Mateus thanks FCT for the grant SFRH/BPD/79518/2011. [1] Hargrove, A. E.; Nieto, S.; Zhang, T.; Sessler, J. L.; Anslyn, E. V. Chem. Rev. 2011, 111, 6603–6782. [2] Mateus, P.; Lima, L.M.P.; Delgado, R. Polyhedron 2013, 52, 25–42.

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44

P2 - PREPARATION AND CHARACTERIZATION OF NOVEL PHOTOCHROMIC SPIROPYRAN-BASED HYBRID NANOMATERIALS

C. Freire,a P. Costa,a C. Sousa,a T. Pinto,a C. Pereira,a

O.S.G.P. Soares,b M.F.R. Pereira,b Y. Prostota,c C.M. Sousa,c P.J. Coelhoc

aDepartment of Chemistry and Biochemistry, Faculty of Sciences, University of Porto, 4169-007 Porto, Portugal

bLaboratory of Catalysis and Materials (LCM), Associated Laboratory LSRE/LCM, Department of Chemical Engineering, Faculty of Engineering, University of Porto,

4200-465 Porto, Portugal cDepartment of Chemistry and CQ-VR, University of Trás-os-Montes e Alto Douro,

5001-801 Vila Real, Portugal [email protected]

Smart hybrid nanomaterials are an important class of multifunctional, nanostructured and innovative scaffolds that has been attracting considerable attention due to the ability to combine, in a single material, the advantages of inorganic (high thermal and mechanical resistance) and organic (lightweight, flexibility, tunable functionality) compounds [1,2]. These dynamic materials have an important advantage over their static counterparts: they present specific functionalities that can be reversibly ‘‘turned on’’ and ‘‘off’’ in response to an external stimulus [1]. In particular, photochromic organic-inorganic materials are among the most studied smart systems owing to their versatile light-switchable features and potentialities for a variety of fields including optical memories, optical switches and photochromic inks [2]. Spiropyrans have emerged as one of the molecules-of-choice for the construction of novel smart devices [1]. Their incorporation onto silica nanomaterials constitutes a potential strategy to improve their robustness while taking advantage of the nanosized properties of the silica. The aim of this work was to prepare novel hybrid silica nanoparticles with photoswitchable properties through their functionalization with photochromic organic dyes. Silica nanoparticles with ~100 nm particle size were functionalized with a spiropyran dye by post-grafting; different ratios of spiropyran dye:nanosilica were tested. The parent and functionalized nanomaterials were characterized by Fourier transform infrared spectroscopy (FTIR), thermogravimetry (TG) and colorimetry. The new hybrid nanomaterials showed reversible photochromic properties, changing their color from light to dark pink when exposed to ultraviolet irradiation (λ=365 nm) for only 10 seconds, and fading back to their initial color after removal of the ultraviolet source. Finally, a relation between the spyropyran dye:nanosilica ratio and photochromic properties of the prepared material was established. Acknowledgments: This work was funded by Fundação para a Ciência e a Tecnologia (FCT) and FEDER through grant no. PEst-C/EQB/LA0006/2011 and through project ref. PTDC/CTM-POL/0813/2012 in the framework of Program COMPETE. The authors also acknowledge Operation NORTE-07-0124-FEDER-000067 – Nanochemistry. P. Costa, C. Sousa and T. Pinto thank FCT for their grants. [1] Klajn, R. Chem. Soc. Rev. 2014, 43, 148-184. [2] Pardo, R.; Zayat, M.; Levy, D. Chem. Soc. Rev. 2011, 40, 672–687.

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45

P3 - SILICA@CORROLE-AgNP SATELLITE NANOPARTICLES AS NEW HIBRID PROBES FOR IONS

Carla I. M. Santos1,2,3, Elisabete Oliveira2,3,4, Javier Fernandéz-Lodeiro2,3,

Joana F. Barata1,4, Sérgio M. Santos 4, M. Amparo F. Faustino1, José A. S. Cavaleiro1, M. Graça P. M. S. Neves1, Carlos Lodeiro2,3

1Department of Chemistry & QOPNA, University of Aveiro, 3810-193 Aveiro, Portugal

2BIOSCOPE Group, REQUIMTE/CQFB, Faculdade de Ciências e Tecnologia, University NOVA of Lisbon, 2829-516 Caparica, Portugal

3ProteoMass Scientific Society, Madam Park, Caparica Campus, 2829-516, Portugal 4Veterinary Science Department, (CECAV), University of Trás-os-Montes and Alto Douro,

5001-801 Vila Real, Portugal 5Chemistry Department and CICECO, University of Aveiro, Campus Universitário de

Santiago, 3810-193 Aveiro, Portugal. The design of new fluorescent chemosensors is an important topic due to its importance in fields such as biology and medicine,[1] where molecular probes are often useful tools for monitoring relevant analytes in vitro and in vivo. A fluorescent chemosensor is obtained by merging two fundamental moieties: the recognition site (receptor) and the signaling source (fluorophore). However, to provide an efficient detection, these species must have a high selectivity or specificity for the analyte and a stable luminescent signal.[2]

Corroles, tetrapyrrolic macrocycles that share close similarities with porphyrins, have useful properties to be considered as fluorophores in this type of applications. They show, in general, strong fluorescence emissions over 600 nm, and absorptions (> 400 nm) bands in the visible region of the electromagnetic spectra and high N–H acidity.[2]

As a part of our research project on the synthesis and applications of specific emissive ligands for nanoparticles design and chemosensors, we present here a new corrole derivative incorporating an imine group that will allow us to obtain silica nanoparticles, and explore their interaction with different metal ions. The new compounds were characterized by NMR-1H, NMR-13C, microanalyses, UV-vis and fluorescence emission spectroscopy. The interaction of the β-iminecorrole with Hg(II), Cu(II) and Ag(I) will be also discussed.[4] Acknowledgments: Authors are grateful to Scientific PROTEOMASS Association (Portugal) for financial support. Thanks are due to FCT-MEC, FEDER and COMPETE for funding the QOPNA unit (project PEst-C/QUI/UI0062/2011). C.S. and E.O thank also to FCT-MEC (Portugal) by their doctoral and Post-Doctoral grants, SFRH/BD/64155/2009 and SFRH/BPD/72557/2010, respectively. JFL thank Scientific PROTEOMASS Association (Spain). [1] Silva, de A. P.; Gunaratne, H. Q. N.; Gunnlaugsson, T.; Huxley, A. J. M.; Mccoy, C. P.; Rademacher, J.T.;. Rice, T. E; Chem. Rev., 1997, 97, 1515. [2] Lodeiro, C.; Capelo, J. L.; Mejuto, J.C.; Oliveira, E.; Santos, H.M.; Pedras, B.; Nunez, C.; Chem. Soc. Rev. 2010, 39, 2948 [3] (a) Bendix, J.; Dmochowski, I. J.; Gray, H. B.; Mahammed, A.; Simkhovich, L.; Gross, Z; Angew. Chem.Int. Ed., 2000, 39, 4049.(b) Aviv-Harel, I.; Gross, Z; Coord. Chem. Rev., 2011, 255, 717. (c) Santos, C. I. M.; Oliveira, E.; Barata, J. F. B.; Faustino, M. A. F.; Cavaleiro, J. A. S.; Neves, M. G. P. M.S; Lodeiro, C.; J. Mater. Chem., 2012, 22, 13811. [4] Santos, C. I. M.; Oliveira, E.; Fernandez-Lodeiro, J.; Barata, J. F. B.; Faustino, M. A. F.; Cavaleiro, J. A. S.; Neves, M. G. P. M.S; Lodeiro, C.; Inorg. Chem., 2013, 52, 8564-8572 .

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46

P4 - FROM SUCROSE TO ACTIVATED CARBON MICROSPHERES: SUPORTS FOR NANOSIZED METAL OXIDES PHOTOCATALYSTS

Ana S. Mestre1,2, Cristina Freire2, Ana P. Carvalho1

1 Departamento de Química e Bioquímica and CQB, Faculdade de Ciências da Universidade

de Lisboa, Ed. C8, Campo Grande, 1749-016 Lisboa (Portugal) 2 REQUIMTE, Departamento de Química e Bioquímica, Faculdade de Ciências,

Universidade do Porto, 4169-007 Porto (Portugal) [email protected]

Hydrothermal carbonization (HTC) is a cost effective and eco-friendly process to obtain spherical hydrophilic materials from carbon rich precursors (including renewable carbohydrate-rich biomass). Carbon materials obtained from HTC – hydrochars – have outstanding properties, related with their spherical morphology and high loading of oxygenated surface groups, which can be used for the synthesis of functional carbon-based materials [1]. However, hydrochars have as major drawback their low porosity and surface area and consequently the design of highly microporous spherical carbon materials is still a major challenge. Several routes have been developed to increase hydrochars porosity, with KOH activation being the usual chosen method [2,3], but this activation promotes the disruption of the spherical morphology of the resulting materials. In this context, the design of new activation routes using chemical/physical activation of hydrochars without the loss of the spherical morphology is an ongoing challenge. This work reports the preparation of a sucrose-based hydrochar by HTC and its activation by a novel method using K2CO3 or steam activation. The characterization of the activated carbons textural properties by N2 and CO2 adsorption isotherms at, respectively, -196 and 0 ºC, reveal that samples obtained are highly microporous (Vmicro attaining ~0.6 cm3g-1) and morphological analysis show that the spherical morphology was preserved (Figure 1). Moreover, carbons activated with K2CO3

combined the spherical morphology with very narrow micropore size distributions, which give them molecular sieves properties, and with an acidic surface chemistry (pHPZC 4-5) that opens new possibilities to the use of these eco-friendly materials in, for example, adsorption processes or for the synthesis of functional carbon-based materials. Spherical activated carbons will be used as supports for the preparation of composites with nanosized metal oxides with photocatalytic properties (i.e. TiO2, ZnO). Acknowledgements: This work was supported by FCT pluriannual programme of CQB and REQUIMTE (PEst-OE/QUI/UI0612/2013 and PEst-C/EQB/LA0006/2011, respectively) and by Operation NORTE-07-0124-FEDER-000067 - NANOCHEMISTRY. ASM thanks FCT for the Post-doc grant SFRH/BPD/86693/2012.

SSt800

1 m

1 m

SC800

1 m

1 m

SC900

1 m

1 m

Figure 1: SEM images of spherical carbons activated with steam (SSt800) and K2CO3 (SC800 and SC900).

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47

P5 - A SIMPLE COPPER SYSTEM FOR EFFECTIVE AEROBIC ALCOHOL OXIDATION

Margarida Espadinha,1 Helena Laronha,1 Vitor Rosa,1 Teresa Avilés1

1REQUIMTE, Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, 2829-516, Caparica, Portugal

[email protected]

Oxidations of alcohols to aldehydes or ketones are widely used transformations in synthetic organic chemistry, and extensive efforts have focused on the development of aerobic oxidation methods [1]. Combinations of homogeneous Cu salts and TEMPO have emerged as practical and efficient catalysts for the aerobic oxidation of alcohols [2]. Pursuing our research on practical and simple copper complexes based in BIAN ligands [3] and their use as catalysts in diverse reactions [4], we decided to test the potential of a series of Cu(I) and Cu(II) complexes as catalysts for the alcohol oxidation reaction. Herein we report, the study of several catalyst systems, which differ in the identity of the solvent, the identity of basic additives, the oxidation state of the Cu source and the ligand coordinated to the copper. These changes have a significant influence on reaction rates, yields, and substrate scope.

Figure 1: ORTEP view of [Cu(o,o’-iPr2C6H4-BIAN)(CH3CN)2]BF4 :

one of the copper complexes tested as catalyst in the aerobic alcohol oxidation reaction. [1] Bobbitt, J. M.; Brückner, C.; Merbouh, N. Organic Reactions 2009, 106-132. [2] Rahimi, A.; Azarpira, A.; Kim, H.; Ralph, J.; Stahl, S. S. J. Am. Chem. Soc. 2013, 135, 6415-6418. [3] Rosa, V.; Santos, C. I. M.; Welter, R.; Aullón, G.; Lodeiro, C.; Avilés, T. Inorg. Chem. 2010, 49, 8699-8708. [4] Li, L.; Lopes, P. S.; Rosa, V.; Figueira, C. A.; Lemos, M. A. N. D. A.; Duarte, M. T.; Avilés, T.; Gomes, P. T. Dalton Trans., 2012, 41, 5144-5154.

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48

P6 - IMMOBILIZATION OF BINOL BASED METAL COMPLEXES INTO INORGANIC SUPPORTS: THEIR CATALYTIC

EVALUATION AND REUTILIZATION

Mariette M. Pereira1, Carlos J. P. Monteiro1,2, Sónia A. C. Carabineiro2, José L. Figueiredo,2 Rui M. B. Carrilho1, César A. Henriques1, Mário J. F. Calvete1

1 Department of Chemistry, University of Coimbra, Coimbra, Portugal

2LCM – Laboratory of Catalysis and Materials – Associate Laboratory LSRE/ LCM, Faculty of Engineering, University of Porto, Porto, Portugal

[email protected]

The immobilization of chiral transition metal complexes into inorganic supports is an area with increased interest owing to the current demands to promote the metal and ligand reutilization.[1,2] BINOL is now considered one of the most relevant chiral backbones, due to the wide range of asymmetric reactions where it has been applied as ligand, either involving hard metal complexes, such as in titanium-catalysed alkylation reactions,[3] or soft metal complexes with their phosphorus derivatives, [4] such as in rhodium-catalysed hydroformylation. In this communication, we present a methodology for the functionalization of MWCNT, as well as modifications in BINOL to promote its immobilization on the carbon materials, Figure 1. The characterization, activity and selectivity of the corresponding immobilized titanium metal complexes in alkylation reactions of aldehydes will be presented. Furthermore, a new strategy to promote the immobilization of BINOL based phosphoramidite type ligands into MCM-41 will be described and their efficient application/reutilization in the rhodium catalyzed-hydroformylation of styrene will be also discussed.

CNH

HN

OHOH

OO

F

Figure 1: Covalent immobilization of BINOL in MWCNT.

Acknowledgements: The authors thank Fundação para a Ciência e Tecnologia (FCT) (PTDC/QUI-QUI/112913/2009) for financial support. C.J.P.M. also thanks FCT for Post-Doctoral grant SFRH/BPD/86525/2012, S.A.C.C. thanks CIÊNCIA 2007 program and R.M.B.C thanks QREN LUZACNE for Post-Doctoral grant. [1] Figueiredo, J. L.; Pereira, M. M.; Faria, J. (Eds.), Catalysis from Theory to Application. An Integrated Course, Coimbra University Press, Coimbra, 2008, p213. [2] Neves, A. C. B.; Calvete, M. J. F.; Pinho e Melo, T. M. V. D.; Pereira, M. M. Eur. J. Org. Chem. 2012, 32, 6309-6320. [3] Abreu, A. R.; Lourenço, M.; Peral, D.; Rosado, M. T. S.; Eusébio, M. E. S., Palacios, O.; Bayón, J. C.; Pereira, M. M. J. Mol. Catal. A: Chem. 2010, 325, 91-97. [4] Calvete, M. J.; Carrilho, R. M. B.; Abreu, A. R.; Pereira, M. M. Chem. Soc. Rev. 2013, 42, 6990-7027.

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49

P7 - N-HETEROCYCLIC CARBENE-COPPER (II) COMPLEXES AS POTENTIAL CATALYSTS FOR THE RING-OPENING

POLYMERIZATION OF CYCLIC ESTERS

Ricardo Lopes,1 Christophe Fliedel,1 Vitor Rosa,1 Teresa Avilés1


[email protected]

Biodegradable polyesters have received considerable interest in recent years due to their important biomedical and pharmaceutical applications and as an alternative to petrochemical-based plastics [1].The ring-opening polymerization (ROP) of cyclic esters (e.g. lactide, a renewal resource) was found to be a method of choice to access well-defined and narrowly disperse polyesters, but their production at low economical and environmental cost remains challenging. Recently, a copper (II) alkoxide complex showing activity as ROP initiator was described [2]. Based on that interesting report, we decide to coordinate our O- and S-NHC ligands to copper (II) alkoxydes in order to compare their catalytic activity with our previously published Zn catalysts [3]. Herein, we report the synthesis of (O-) and (S-NHC)CuCl(OAlk) complexes and the study of their catalytic activity in the ROP of epsilon-caprolactone.

Figure 1: Synthetic pathway of (O-) and (S-NHC)CuCl(OAlk) complexes. [1] Nair, L. S.; Laurencin, C. T. Prog. Polym. Sci. 2007, 32, 762. [2] Whitehorne, T. J. J.; Schaper, F. Chem. Commun. 2012, 48, 10334. [3] Accepted Manuscript: Fliedel, C.; Vila-Viçosa, D.; Calhorda, M. J.; Dagorne, S.; Avilés, T. ChemCatChem 2014.

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50

P8 - ACTIVATED CARBON/MFE2O4 COMPOSITES: PREPARATION, CHARACTERIZATION AND CATALYTIC ACTIVITY

Fernanda Dalto1, Ana S. Mestre1,2, Mariana Rocha1, Clara Pereira1, Ana P. Carvalho2, Cristina Freire1

1REQUIMTE, Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade

do Porto, 4169-007 Porto, Portugal 2Departamento de Química e Bioquímica and CQB, Faculdade de Ciências da Universidade de Lisboa, Ed. C8, Campo Grande, 1749-016 Lisboa, Portugal

[email protected] Spinel-type ferrite nanoparticles (MFe2O4, where M(II) is a d-block transition metal) are a family of magnetic nanomaterials with remarkable interest in several nanoscience and nanotechnology research fields such as catalysis, environmental remediation and biomedicine [1]. Activated carbons can be used as catalysts supports to disperse these oxides, allowing higher performance due to their high specific surface area and strong adsorption affinity towards pollutants. Moreover, activated carbons can be prepared from waste materials, as is the case of spent coffee grains (SCG) used in this study, lowering the production costs and minimizing the accumulation of residues. On the other hand, the MFe2O4 nanoparticles impart magnetic properties to the resulting activated carbon based catalyst, allowing its fast recycling by magnetic separation. In this study, we propose the synthesis and characterization of Co(II) and Mn(II) ferrite magnetic nanoparticles (MNPs) and their incorporation in an activated carbon matrix, in order to produce activated carbon/MFe2O4 composites for organic pollutants degradation. The CoFe2O4 and MnFe2O4 MNPs were prepared by coprecipitation using isopropanolamine (MIPA) as base [1] and impregnated in a matrix of activated carbon produced by steam activation of SCG (BET surface area of 694 m2 g-1) in a 1:1 ratio (denoted as CoFe2O4_C50 and MnFe2O4_C50). All the materials were characterized by FTIR, XRD, N2 adsorption-desorption isotherms at 77 K, TEM and SEM/EDS. The XRD diffractograms of CoFe2O4_C50 and MnFe2O4_C50 exhibited the characteristic diffraction peaks of the nanoferrites (spinel cubic structure, space symmetry group Fd3m) confirming their successful incorporation in the carbon matrix. The composites FTIR spectra of the composites exhibited the typical bands of the MNPs in the range of 590-570 cm-1. The N2 isotherms revealed an increase of the BET surface area of the composites relative to those of the pure oxides: CoFe2O4 (165 m2 g-1), CoFe2O4_C50 (423 m2 g-1), MnFe2O4 (79 m2 g-1), MnFe2O4_C50 (365 m2 g-1). The SEM and TEM images showed that the MNPs were distributed throughout the activated carbon surface. The MnFe2O4_C50 and CoFe2O4_C50 composites were active catalysts in the degradation of Congo Red dye using H2O2 as oxidant, with degradation efficiencies higher than 60%. Acknowledgements: This work was funded by FCT and FEDER through grant no. PEst- C/EQB/LA0006/2011. The authors acknowledge Operation NORTE-07-0124-FEDER-000067 – NANOCHEMISTRY. FD thanks CAPES/BRASIL for a doctoral grant. ASM thanks FCT for the Post-doc grant SFRH/BPD/86693/2012. [1] Pereira, C.; Pereira, A. M.; Fernandes, C.; Rocha, M.; Mendes, R.; Fernández-Garcia, M. P.; Guedes, A.; Tavares, P.B.; Grenèche, J. M.; Araújo, J. P.; Freire, C. Chem. Mater. 2012, 24, 1496-1504.

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51

P9 - CHIRAL DIAMINE BIS(PHENOLATE) VANADIUM COMPLEXES

Ana Coelho, Sónia Barroso, Ana M. Martins

Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa

Vanadium complexes have been long applied to asymmetric catalysis with excellent results. Our group has previously reported the synthesis of vanadium complexes supported by diamine bis(phenolate) ligands and their application to catalytic sulfoxidation reactions with promising results [1]. In an effort to achieve enantioselectivity in this process, the chiral ligand precursor H2L (H2L = (S)-6,6'-((1-ethylpyrrolidin-2-yl)methylazanediyl)bis(methylene)-bis(2,4-di-tert-butylphenol)) [2] was used to obtain the new chiral V(III) complex 1. The molecular structure of 1 reveals trigonal bipyramidal geometry around the metal. By oxidation in air, 1 gave a mixture of products including the oxovanadium(V) 2. The reaction of 1 with TEMPO in toluene afforded a 1:1 mixture of 2 and TEMPO-CH2C6H5. VOL(OiPr), 3, was obtained as a single product from direct reaction of VO(OiPr)3 with the ligand precursor. Preliminary studies of 2 for sulfoxidation catalysis gave quantitative yields in sulfoxide but, unfortunately, no enantioselectivity was yet obtained.

Acknowledgements: The authors thank the FCT for funding (SFRH/BPD/7394/2010, Pest-OE/QUI/UI0100/2013 and PEst-OE/QUI/UI0612/2011) [1] Barroso, S.; Adão, P.; Madeira, F.; Duarte, M. T.; Pessoa, J. C.; Martins, A. M. Inorganic Chemistry 2010, 49(16), 7452–7463. [2] Barroso, S.; Adão, P.; Duarte, M. T.; Meetsma, A.; Pessoa, J. C.; Bouwkamp, M. W.; Martins, A. M. European Journal of Inorganic Chemistry 2011, 27, 4277–4290.

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52

P10 - SYNTHESIS OF LUMINESCENT LEAD IODIDE NANOPARTICLES EMBEDDED IN ZEOLITE MATRIX AND

APPLICATION AS WATER SENSOR

Rúben R. Ferreira, César A.T. Laia

REQUIMTE, Departamento de Química, Faculdade de Ciências e Tecnologia,

Universidade Nova de Lisboa, 2829-516 Caparica, Portugal. [email protected]

We report, to the best of our knowledge, the first synthesis of a water sensor based on luminescent lead iodide nanoparticles embedded in a zeolite matrix. These nanoparticles were synthesized by ship-in-a-bottle method using the molecular sieve (zeolite) 4Å as matrix, controlling the size and preventing agglomeration. First, Pb2+ ions were introduced in the zeolite pore by ionic exchange with Na+. Then, I- ions were added to the solution drop-wise, forming the nanoparticles that become trapped in the zeolite pores. The as synthesized nanoparticles form luminescent clusters when embedded in the zeolite. These clusters show a high sensitivity to water, losing their luminescence at very low water contents. Our studies reveal a relation between the water content of a given solvent and the clusters luminescence, making them suitable to be use as a water sensor. After losing the luminescence the sensors can be recycle by drying under vacuum. Further studies will determinate how the temperature influences the luminescence and how to improve the sensors accuracy.

Figure 1: Samples of lead iodide clusters after 5min (top) and after 24h (bottom). Legend (from left to right): without solvent, in water, in acetonitrile/methanol 1:1, in toluene, without solvent (open to air).

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53

P11 - MAGNETIC IRON OXIDE NANOPARTICLES ANCHORED WITH Mo COMPLEX AS HIGHLY RECYCLABLE EPOXIDATION CATALYST

Cristina I. Fernandes1, Maria Deus Carvalho1, Liliana P. Ferreira2,3, Carla D. Nunes1, Pedro D. Vaz1

1CQB, Department of Chemistry and Biochemistry, Faculty of Sciences of University of

Lisbon, Campo Grande, Building C8, 1749-016 Lisbon, Portugal 2CFMC, Faculty of Sciences of University of Lisbon, Campo Grande, Building C8, 1749-

016 Lisbon, Portugal 3Department of Physics, Faculty of Science and Technology of University of Coimbra,

3004-516 Coimbra, Portugal [email protected]

Nanoparticle (NP) research is a very dynamic field that ranges across many areas of science, from physics to chemistry and medicine, among other fields. Size, shape, composition, crystallinity and structure are parameters of metal oxide NPs that tailor their intrinsic properties [1]. Heterogeneous catalysis offers as the main advantage the easy recovery of the catalyst from the reaction products (enhanced by other features, i.e., magnetism), making it the preferred approach in most industrial applications. The efficiency of such catalysts strongly depends on the capability to assemble an active and selective homogeneous catalyst for a given reaction (responsible for activity) with an appropriate support (preventing catalyst loss and facilitating recovery). Therefore, to this regard magnetic separation is a very important concept. Within the catalysis framework, olefin epoxidation is a major field of research in the preparation of relevant building blocks for organic synthesis [2]. Use of NPs in catalysis showed that the investment in this kind of systems is beneficial, since the high surface/volume ratio leads to high performance. In the present work the organometallic fragment [MoI2(CO)3] was coordinated to magnetic iron oxide nanoparticles of different sizes (average size of 11 and 30 nm) which have been previously coated with a silica shell and grafted with a pyridine derivative ligand. Olefin epoxidation of a variety of substrates promoted by these organometallic nano-hybrid materials using tert-butylhydroperoxide as oxidant, was performed with very good results. The catalytic studies show that the catalysts yield selectively the desired epoxides. In addition, the catalysts are found to work under a wide temperature range and over several catalytic cycles without notorious performance loss. . Acknowledgements: The authors are grateful to FCT for financial support (project PEst- OE/QUI/UI0612/2013 and project PEst-OE/QUI/UI0536/2011). Cristina I. Fernandes also thanks FCT for a grant (SFRH/BD/81029/2011). [1] Xu, R.; Wang, D.; Zhang, J.; Li, Y. Chem. Asian J., 2006, 1, 888-893. [2] Taguchi, A.; Schüth, F. Microporous Mesoporous. Mater., 2005, 77, 1-45.

Figure 1: Scheme of catalyst and TEM of the organometallic NPs

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54

P12 - EXPLORING THE CHEMISTRY OF BIS(KETOPYRROLYL) COBALT COMPLEXES FOR THE CONTROLLED/LIVING RADICAL POLYMERIZATION OF STYRENE AND METHYL METHACRYLATE

Tiago F. C. Cruz1, Clara S. B. Gomes1, José R. Ascenso1, Pedro T. Gomes1, João C. Bordado2, M. Amélia N. D. A. Lemos2

1Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, 2IBB / CERENA, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais 1,

Lisboa, Portugal. Email: [email protected]

1Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, 2IBB / CERENA, Instituto Superior Técnico, Universidade de Lisboa,

Av. Rovisco Pais 1, Lisboa, Portugal. Email: [email protected]

Controlled/Living radical polymerization and, in particular, Cobalt Mediated Radical Polymerization (CMRP) [1] provides a very capable way of producing well defined polymers and polymer architectures en route to diverse applications in material science and technology [2]. In this work, the first case of Bis(ketopyrrolyl) cobalt mediated radical polymerization of styrene and methyl methacrylate is presented. The initiation system composed by [Co{κ2N,O-NC4H3-C(H)=O}2(PMe3)2] (1) [3] and tert-butyl-α-bromoisobutyrate (2) controlled the radical polymerization of styrene (atactic polymers), by an Atom Transfer Radical Polymerization (ATRP) [4] mechanism, below 70 ºC and also of methyl methacrylate (syndiotactic-rich polymers), by a CMRP mechanism, below 50 ºC. The formation of the block-copolymer poly(styrene)-b-poly(methyl methacrylate) was also possible, as confirmed by GPC/SEC and NMR studies. On the other hand, the [Co{κ2N,O-NC4H3-C(H)=O}2(PMe3)2]Br (3) complex afforded, without the presence of 2, the formation of atactic poly(styrene) and syndiotactic-rich poly(methyl methacrylate) with some degree of molecular weight control in the first case, at 70 ºC.

Acknowledgements: We thank Fundação para a Ciência e a Tecnologia (Project PTDC/EQU-EQU/110313/2009 and Project PEst-OE/QUI/UI0100/2013) for the financial support.

[1] Debuigne, A.; Poli, R.; Jérôme, C.; Jérôme, R.; Detrembleur, C. Prog. Polym. Sci. 2009, 34, 211-239. [2] Braunecker, W. A.; Matyjaszewski, K. Prog. Polym. Sci. 2007, 32, 93-146. [3] Carabineiro, S. A.; Gomes, P. T.; Veiros, L. F.; Freire, C.; Pereira, L. C. J.; Henriques, R. T.; Warren, J. E.; Pascu, S. I. Dalton Trans. 2007, 32, 5460-5470. [4] Matyjaszewski, K. Macromolecules 2012. 45. 4015-4039.

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55

P13 – CHARGE TRANSFER SALTS OF A NEW ASYMMETRIC TTF DONNOR WITH CYANO COORDINATING GROUPS

S. Oliveira1, S. Rabaça1, I.C. Santos1, and M. Almeida1

1Center of Nuclear Science and Technology - C2TN, IST/CFMCUL, University of Lisbon,

Nuclear and Technological Campus, 2695-066 Bobadela, Portugal *e-mail: [email protected]

The chemical modification of the electron donor tetrathiafulvalene (TTF) has been extensively explored in search for new building blocks suitable for electroactive molecular materials namely organic conductors and superconductores. We focused our interest on TTF-derivatives, with cyano units which can be used to coordinate transition metals by N atoms and to form in the solid state segregated and partially oxidized structures. In this context we have synthesize the new donor CNB-EDT-TTF following a route adapted from a similar donor [1] and some of its charge transfer salts namely (CNB-EDT-TTF)2 [Au(mnt)2], (CNB-EDT-TTF)2.5 AuCl2 and (CNB-EDT-TTF)2 PF6.

In this communication we present the synthesis and characterization of the donor by cyclic voltammetry, optical properties and single crystal X-ray diffraction, as well as of these salts. The crystal structure of (CNB-EDT-TTF)2 [Au(mnt)2], presents the same crystal packing observed in the analogue with (BMDT-TTF)2 [Au(mnt)2] [2].

Figure 1- Molecular structure and packing of CT salt (CNB-EDT-TTF)2[Au(mnt)2]

Acknowledgements: Financial support from FCT- Fundação para a Ciência e Tecnologia under contract SFRH/BD/72722/2010. [1] Jia, C.; Liu, Shi-Xia.; Ambrus, C.; Labat, G.; Neels, A.; Decurtins, S.; Polyhedron, 2006, 25, 1613–1617. [2] Torrent, M. M.-; Alves, H.; Lopes, E. B.; Almeida, M.; Wurst, K.; Vidal-Gancedo, J.; Veciana, J.; and Rovira, C.; Journal of Solid State Chemistry, 2002, 168, 563–572.

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56

P14 - A NEW FAMILY OF IMINOPHENOLATES: SYNTHESIS, CHARACTERIZATION AND STUDIES OF THEIR REACTIVITY

TOWARDS TRANSITION METALS

Rosana Fernandes,1 Vitor Rosa,1 Teresa Avilés1


[email protected]

Ligand design and its in-depth characterization are often primordial in order to obtain successful catalysts. Based on our knowledge in the synthesis of bis-iminoacenaphtenequinone (BIAN) derivatives [1] and following the results of the reaction of these ligands with Zn(Et)2 [2], a new series of iminophenolates and amino-iminophenolates were developed. As already well established in literature, the BIAN ligand suffers a nucleophilic attack when in presence of nBuLi, originating an amino-imino type of ligand after hydrolysis. [3] Moved by that reaction and expanding its scope, we synthetized a series of mono-substituted BIAN’s and reacted them with organolithium and Grignard reagents. The obtained iminophenolates where fully characterized and their reactivity towards some transition metals was studied.

Figure 1: Synthetic pathway of iminophenolates.

Acknowledgements: V.R. thanks Fundação para Ciência e Tecnologia for the SFRH/BPD/ 44262/2008 fellowship. [1] Rosa, V.; Santos, C. I. M.; Welter, R.; Aullón, G.; Lodeiro, C.; Avilés, T. Inorg. Chem. 2010, 49, 8699-8708. [2] Romain, C; Rosa, V.; Fliedel, C.; Bier, F.; Hild, F.; Welter, R.; Dagorne S.; Avilés T. Dalton Trans. 2012, 41, 3377-3379. [3] Fedushkin, I. L.; Hummert, M.; Schumann, H. Eur. J. Inorg. Chem. 2006, 3266-3273.

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57

P15 - PREPARATION OF LANTHANUM-COPPER BIMETALLIC NANOPARTICLES

Ana C. Ferreira1,2*, T. Almeida Gasche1, João P. Leal1,2, Joaquim B. Branco1

1 C2TN, Campus Tecnológico e Nuclear- IST-UL, Estrada Nacional 10, ao km 139.7, 2695-066 Bobadela LRS, Portugal

2Departamento de Química Bioquímica - FCUL, Campo Grande, 1749-016 Lisboa, Portugal *e-mail: [email protected]

The synthesis of bimetallic nanoparticles has been the focus of many studies in the last few years. This kind of compounds has a lot of applications, giving them unusual magnetic and catalytic properties [1]. Some techniques were successfully applied to the synthesis of bimetallic nanoparticles containing d transition metals. The best results involve the application of modified polyol process [2-4]. However, the synthesis with f block elements presents different problems, related primarily to its redox potentials that are too negative. The challenge was to develop an efficient and reproducible methodology for synthesis in solution and at low temperature of bimetallic nanoparticles containing f block elements and d block transition elements. To face this challenge we have implemented different approaches to the direct synthesis of bimetallic La-Cu nanoparticles, namely via modified sol-gel methods. For example, in a typical procedure of solvothermal method, lanthanide nitrate and copper nitrate were dissolved in of ethylene glycol (EG) or tetraethylene glycol (TEG) in stoichiometric amount and then polyvinlypirrolidone (PVP) was added to the solution. Analysis by XRD, SEM and TEM were performed to characterize the obtained b imetallic nanoparticles. Figure 1 shows TEM (A) and SEM (B and C different solvents) images of some of the bimetallic La-Cu nanoparticles already prepared. The size of bimetallic nanoparticles obtained was around 7-30 nm.

(A) (B) (C)

Figure 1. TEM (A) and SEM (B and C) images for bimetallic La-Cu nanoparticles. Acknowledgements: Ana C. Ferreira thanks FCT for her PhD Grant (SFRH/BD/ 69942/2010).

[1] Schlapbach, L. ;Topics in Applied Physic: Hydrogen in Intermetallic Compounds II vol. 67, 1992, Springer-Verlang (cap. 2, 3). [2] Y. Vasquez et al., J. Am. Chem. Soc., 2008, 130, 11866–11867. [3]. R. Cable and R, Schaak, Chem. Mater., 2007, 19, 4098-4104. [4] C. N. Chinnasamy, et al., Appl. Phys. Lett., 2008, 93, 032505.

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58

P16 - WHITE OLED BASED ON A TEMPERATURE SENSITIVE LANTHANIDE β-DIKETONATE COMPLEX

Patrícia P. Lima1, Filipe A.A. Paz2, Carlos D.S. Brites1, Welber. G. Quirino3, Cristiano Legnani3, Marcos Costa e Silva4, Rute A.S. Ferreira1,

Severino A. Júnior5, Oscar L. Malta5, Marco Cremona4,6, Luís D. Carlos1

1Department of Physics and CICECO, University of Aveiro, 3810-193 Aveiro, Portugal

2Department of Chemistry and CICECO, University of Aveiro, 3810-193 Aveiro, Portugal 3LEO – Laboratório de Eletrônica Orgânica, Departamento de Física, Universidade Federal

de Juiz de Fora, Juiz de Fora, MG 36036-330, Brazil 4LADOR – Laboratório de Dispositivos Orgânicos, Divisão de Metrologia de Materiais,

Inmetro, Duque de Caxias, RJ 25250-020, Brazil 5Departamento de Química Fundamental, Universidade Federal de Pernambuco, Cidade

Universitária, Recife, PE 50740-560, Brazil 6Departamento de Física, Pontifícia Universidade Católica do Rio de Janeiro, PUC-Rio, Rio

de Janeiro, RJ 22453-970, Brazil

In this work a lanthanide β-diketonate complex, [Eu0.45Tb0.55(btfa)3(4,4’-bpy)(EtOH)] (btfa¯=4,4,4–trifluoro–1–phenyl–1,3–butanedionate; 4,4’-bpy=4,4’-dipyridyl; EtOH=ethanol), was synthesized and its structure was elucidated by single crystal X-ray diffraction [1]. The temperature dependence of the complex emission intensity between 11 and 298 K is illustrated by the Commission Internacionale l’Éclairage (CIE) (x,y) color coordinates change within the orange-red region, from (0.521, 0.443) to (0.658, 0.335). This lanthanide complex presents a thermometric response that can be calibrated using the ratio between the integrated areas of the 5D4→

7F5 (Tb3+) and 5D0→

7F2 (Eu3+) transitions [2]. The relative sensitivity was computed for this complex in the temperature range its operating range resulting in a maximum sensitivity of 4.0% K–1 at 225 K [1]. The existence of Tb3+-to-Eu3+ energy transfer [3] was observed at room temperature and as the complex presents a relatively high emission quantum yield (0.34±0.03) it was doped in a 4,4’-bis(carbazol-9-yl)biphenyl (CBP) organic matrix to be used as emitting layer to fabricate a white organic light-emitting diode (WOLED) [1]. Continuous electroluminescence emission was obtained varying the applied bias voltage showing a wide emission band from 400 to 700 nm. The white emission results from a combined action between the Eu3+ and Tb3+ peaks from the mixed Eu3+/Tb3+ complex and the other organic layers forming the device. The intensity ratio of the peaks is determined by the layer thickness and by the bias voltage applied to the OLED, allowing us to obtain a color tunable light source. Acknowledgements: FCT (SFRH/BPD/ 34365/2006 and SFRH/BPD/89003/2012), FEDER, Mais Centro – PORC (Pest-C/CTM/LA0011/2013 and CENTRO-07-ST24-FEDER-002032), CAPES, CNPq, FAPEMIG and inct-INAMI. [1] Lima, P. P.; Paz, F. A. A.; Brites, C. D. S.; Quirino, W. G.; Legnani, C.; Costa e Silva, M.; Ferreira, R. A. S.; Júnior, S. A.; Malta, O. L.; Cremona, M.; Carlos, L. D. Organic Electronics 2014, 15, 798-808. [2] Brites, C. D. S.; Lima, P. P.; Silva, N. J. O.; Millán, A.; Amaral, V. S.; Palacio, F.; Carlos, L. D. Adv. Mater. 2010, 22, 4499-4504. [3] Mohapatra, S.; Adhikari, S.; Riju, H.; Maji, T. K. Inorg. Chem. 2012, 51, 4891-4893.

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59

P17 – SYNTHESIS OF BIMETALLIC COMPOUNDS FOR PRODUCTION OF METHANOL

Cybelle O. Soares, Ana C.Ferreira, T. Almeida Gasche and Joaquim B. Branco

C2TN, Campus Tecnológico e Nuclear- IST-UL, Estrada Nacional 10, ao km 139.7, 2695-066 Bobadela LRS, Portugal

[email protected]

Given their harmful effect, there is growing concern about the abundant emission of greenhouse gases, namely CO2, CH4 and N2O [1]. An interesting alternative to mitigate its effects implies their use as reagents in different processes aiming the production of value-added chemicals such as hydrocarbons and alcohols [2-5]. Among those, the production of methanol became a major target addressing one of the major problems of this century: the depletion of fossil fuels and the development of sustainable alternatives. In this communication, we present preliminary catalytic studies for methanol synthesis over different bimetallic Cu – M (M= Zn, Ce and Th) catalysts dispersed in Al2O3. They were prepared by a co-precipitation technique. XRD and SEM-EDS measurements (Fig. 1) were performed for structure characterization.

Figure 1: SEM image for the Cu – Ce /Al2O3 catalyst. Acknowledgements: This work was supported by FCT, under contract number PTDC/AAG-TEC/3324/2012. [1] Blasing, T.J.; Carbon dioxide information analysis center 2013, Oak Ridge National Laboratory, US Department of Energy, Oak Ridge, TN, USA. [2] Shi, L.; Yang, G.; Tao, K.; Yoshiharu, Y.; Tan, Y.; Tsybaki, N. Accounts of Chemical Reseach 2013, 46, 1838-1847. [3] Bansode, A.; Urakawa, A. Journal of Catalysis 2014, 309, 66-70. [4] Ferreira, A.C.; Gonçalves, A.P.; Gasche, T.A.; Ferraria, A.M.; Rego, A.M.B.; Correia, M.R:; Bola, A.M.; Branco, J.B. Journal of Alloys and Compounds 2010, 497, 249-258. [5] Branco, J.B.; Ballivet-Tkatchenko. D.; Matos, A.C.; A. Journal of Molecular Catalysis A: Chemical 2009, 307, 37-42.

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60

P18 – OPTICAL OXYGEN SENSING MATERIALS BASED ON ROOM-TEMPERATURE LUMINESCENCE

QUENCHING OF IMMOBILIZED ERYTHROSIN B

Bernardo Monteiro1,*, Artur J. Moro2, João C. Lima2, Joaquim Marçalo1,*

1 Centro de Ciências e Tecnologias Nucleares (C2TN), Instituto Superior Técnico, Universidade de Lisboa, Estrada Nacional 10, 2695-066 Bobadela LRS, Portugal

2 REQUIMTE/CQFB, Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, 2829-516 Caparica, Portugal

*e-mail: [email protected], [email protected] Oxygen is by far one of the most important chemical species since it is essential for life. Measurements of its concentration are of extreme importance in many different research fields such as: medicine, chemistry, environmental and marine analysis, molecular biotechnology, bioprocess control, food packaging, and industrial production monitoring. In the majority of the cases, it would be ideal to monitor oxygen concentration which implies the use of oxygen sensors [1]. In this work we report the preliminary results of optical oxygen sensors based in room temperature luminescence changes of erythrosine B supported in anionic clays. The sensors were prepared by the immobilization of erythrosine B in two layered lanthanide hydroxide precursors, LDyH - Dy8(OH)20Cl4•6(H2O), and a Dy doped LYH:0.05Dy - Y7.6Dy0.4(OH)20Cl4•6(H2O). The influence of the different supports and different loading of Erythrosine B were studied as well as the relation between the fluorescence and phosphorescence emissions in the presence and absence of oxygen.

Figure 1: Emission spectra obtained for the LYH:0.04Dy-ErytB sensor with argon bubbling in the aqueous suspensions.

Acknowledgements: Thanks are due to Fundação para a Ciência e a Tecnologia (FCT) for the grants SFRH/BPD/47087/2008 (BM), and SFRH/BPD/69210 (AJM).

[1] Quaranta, M; Borisov, S.M.; Klimant, I.; Bioanal. Rev. 2012, 4,115–157.

530 555 580 605 630 655 680 705 730

I (a.u.)

Wavelength (nm)

100 min Argon

70 min Argon

50 min Argon

30 min Argon

15 min Argon

air

Fluorescence

Phosphorescence

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61

P19 - MILD AND SELECTIVE OXIDATION OF GRAPHENE

M. Araújo1, O.S.G.P. Soares2, M.F.R. Pereira2, A.J.S. Fernandes3, C. Freire1


Porto, Rua do Campo Alegre s/n, 4169-007 Porto, Portugal 2Laboratory of Catalysis and Materials (LCM), Associated Laboratory LSRE/LCM,

Department of Chemical Engineering, Faculty of Engeneering, University of Porto, Rua Dr. Roberto Frias s/n, 4200-465 Porto, Portugal

3Department of Physics, I3N (Institute for Nanostructures, Nanomodelling and Nanofabrication), University of Aveiro, Campus Universitário de Santiago, 3810-193

Aveiro, Portugal Corresponding author: [email protected]

Due to the outstanding properties of graphene [1], a great number of potential applications with this nanomaterial have been revealed in several areas, such as electronics, biotechnology or energy conversion systems [2]. In order to overcome its chemical inertness and to maximize its application, the functionalization of graphene without damaging its electronic structure is mandatory. Most of the studies involve graphene oxide (GO) or the material obtained upon its reduction (r-GO). GO is produced by several methods that involve drastic oxidative conditions, which introduce different functional groups that can be used to anchor other functional units [3]. However, the high degree of oxidation is also responsible for considerable disruption of the electronic delocalization of graphene, and therefore it affects severely its electronic-based properties [4]. Moreover, the post-reduction of graphene oxide – besides the addition of one more step in the process – has been pointed as ineffective in the complete removal of the introduced structural defects upon oxidation [5]. The aim of this work is to develop strategies for mild and selective oxidation of graphene for subsequent surface anchoring of chemical groups/building blocks, avoiding extensive structural damage. Commercial graphene and three oxidants were used – nitric acid, hydrogen peroxide and potassium permanganate/sulfuric acid – at different experimental conditions (oxidant concentration, temperature, reaction time and type of heating). The resulting oxidized graphenes were characterized by X-ray photoelectron spectroscopy, temperature programmed desorption, Fourier transform infrared spectroscopy and Raman spectroscopy.

Acknowledgements: This work was funded by FCT and FEDER through grants no. PEst-C/EQB/LA0006/2011 and PEst-C/EQB/LA0020/2013 and Operation NORTE-07-0124-FEDER-000067 – NANOCHEMISTRY and NORTE-01-0162-FEDER-000051 (SAIECT-IEC/2/2010) through FEDER and CCDRN. MA thanks FCT for her PhD grant (SFRH/BD/89156/2012) and support from Fundação Calouste Gulbenkian through Programa de Estímulo à Investigação 2013. O.S.G.P.S acknowledge FCT grant SFRH/BPD/80435/2011. [1] Geim, A.K.; Novoselov, K.S. Nature Materials 2007, 6, 183-191. [2] Georgakilas, V. et al. Chemical Reviews 2012, 112, 6156-6214. [3] Inagaki, M.et al. Journal of Materials Chemistry 2011, 21, 3280-3294. [4] Stankovich, S. et al. Carbon 2007, 45, 1558-1565. [5] Ciesielski, A et al. Chemical Society Reviews 2014, 43, 381-398.

Posters

62

P20 – REGIOSPECIFITY OF REACTIONS OF THE SECOND SUBSTITUENT INTRODUCTION IN MONOSUBSTITUTED

DERIVATIVES OF CLUSTER [B12H12]2– BORON ANION

A.I. Ogarkov1, A.S. Chernyavskii1, S.G. Sakharov1, 2, K.A. Solntsev1

1A. Baikov Institute of Metallurgy and Materials Science, Russian Academy of Sciences, Leninskii prosp. 49, 119991 Moscow, Russia

2N. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninskii prosp. 31, 119991 Moscow, Russia

[email protected]

Reactions of the following monosubstituted derivatives of dodecahydro-closo-dodecaborate (2–) anion were studied. Reaction of [B12H11Y]2–, Y = I, OH, OC(O)CH3 and SCN with acetic acid in the presence of oxygen and atmospheric moisture. The single-stage procedure of the hydroxy group introduction into monosubstituted [B12H12]

2– anion derivatives without the formation of acetoxo derivatives was developed. Reaction of [B12H11Y]2–, Y = I, OH, OC(O)CH3 and SCN with formic acid in an inert atmosphere (Fig. 1a).Reaction of [B12H11Y]2–, Y = I, OH, OC(O)CH3 and SCN with dimethyl sulfoxide in the presence of acetic anhydride in an inert atmosphere (Fig. 1b). Reaction of [B12H11Y]2–, Y = I, OH and OC(O)CH3 with (SCN)2 solution in dichloromethane in an inert atmosphere (Fig. 1c, 1d). a

b

c

d

Figure 1: Reactions of the second substituent introduction in monosubstituted derivatives of [B12H12]

2– anion

It was found for the reactions under consideration that substituents have the electron-seeking effect and decrease the reactivity of monosubstituted anions as compared to that of [B12H12]

2–. The reactions under consideration were shown to have the regioselective character. The I, OH, OC(O)CH3 and SCN substituents are meta-orientants with respect to the introduced OH, OC(O)H and S(CH3)2 groups and the OH, OC(O)CH3 substituents are meta-orientants with respect to the introduced SCN group. In the case of the reaction of thiocyanogenation of [B12H11I]

2– anion, the 1,12-[B12H10I(SCN)]2–para-isomer is formed. Data on the synthesis of disubstituted derivatives of cluster [B12H12]

2– boron anion and on the orientation effect of substituents can be used in developing BNCT preparations in the case of two biologically active substituents introduced into the boron skeleton of molecule.

Posters

63

P21 - PHOTOLUMINESCENT AND PHOTOCHROMIC INORGANIC MATERIALS

Andreia Ruivo1,2, César A.T. Laia2

1VICARTE, Vidro e Cerâmica para as Artes, Faculdade de Ciências e Tecnologia,

Universidade Nova de Lisboa, 2829-516 Monte da Caparica, Portugal. 2REQUIMTE, Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade

Nova de Lisboa, 2829-516 Monte da Caparica, Portugal. [email protected];

Photoinduced processes are in the core of many functional materials, namely photoluminescence and photochromism. Inorganic materials present several advantages, namely they usually are more durable than their organic counterparts, but many applications require the use of rare earths or other expensive elements which increase their cost greatly. We have developed glass materials avoiding the use of expensive raw materials with either photoluminescence or photochromism properties. Recently this work was extended to zeolites using chalcogen clusters (sulfur, selenium, and tellurium). In this communication we will review the work carried out in both type of materials, emphasizing the common mechanisms involving photoinduced electron-transfer reactions, e.g., in AgCl (photochromic) or PbBr2 (photoluminescent) clusters. These roles are extended sulfur clusters encapsulated in zeolite materials.

Acknowledgements: This work has been supported by the European project NMP4-SL-2012-310651 under FP7-NMP-2012-SMALL-6 and by Fundação para a Ciência e a Tecnologia through grants PEst-C/EQB/LA0006/2011 and PEst-C/CTM/LA0011/2011. The authors would like to thank the Fundação para a Ciência e Tecnologia (FCT) for financial support REF: POCI 2010 under contract PTDC/EAT/67354/2006. A. Ruivo would like to thank a grant by FCT (SFRH/BD/46659/2008).

Posters

64

P22 - FLUORESCENT Eu(III) DOPED NANOPARTICLES AS IMAGING BIOPROBES IN LIVING CELLS

Inês J. Marques, Carla D. Nunes

CQB, Departamento de Química e Bioquímica, FCUL, Campo Grande, Ed. C8, 1749-016 Lisboa, Portugal

[email protected]

Nanomaterials exhibit special properties because of a high surface/volume ratio. At nanoscale, their optical, electronic, magnetic, and catalytic properties change and all these properties mostly depend upon their size and shape, showing potential applications in many areas, as biomedicine/biotechnology, magnetic sensors, magnetic fluids, and catalysis, among others. NPs in which magnetic and optical properties coexist have been widely explored in biomedical applications, ranging from in vivo imaging to therapy [1]. In this study iron (Fe-NP) and silica (SNP) nanoparticles were synthesized [2,3] and subsequently functionalized to prepare, magneto-fluorescent (Fe-NP), and fluorescent (SNP) probes. The Fe-NP core is inactive, but contains an important property, magnetism, allowing the particles to be directed to where it is needed, for applications such as contrast agents in imaging. The Fe-NP and SNP (without magnetism) act as fluorescent probes by means of an anchored Europium (Eu) complex (Fig. 1) which is used as fluorescence promoter, holding condensed aromatic ring ligands – phenanthroline – that enhance fluorescence. All materials have been characterized by FTIR, SEM/TEM, X-Ray and elemental analysis. To evaluate the biocompatibility of these materials for their potential biomedical applications, as contrast agents, 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assays were performed on HeLa cell line to evaluate the cytotoxicity of our samples. We pretend to approach a new method with a potential application in imaging using a solution less toxic and more economically viable, compared to existing ones. Acknowledgements: The authors thank FCT, POCI and FEDER (PEst-OE/QUI/UI0612/2013) for financial support.

[1] Jung, J.; Kim, M.; Cho, J.; Lee, S.; Yang, I.; Cho, J.; Kim, S.; Lee C.; Park, J. Biomaterials 2012, 33, 5865. [2] Sun X.; Liu F.; Sun L.; Wang Q.; Ding Y. J. Inorg. Organomet. Polym. 2012, 22, 311. [3] Lim J.; Ha S.; Lee J. Bull. Korean Chem. Soc. 2012, 33, 1067

Figure 1: Ligand that allow the

functionalization of Fe-NP and SNP.

Posters

65

P23 - NEW FUNCTIONALIZED NANOPARTICLES AS INORGANIC HYBRID CHEMOSENSORS

Carlos Lodeiro1,2, Adrián Fernandez-Lodeiro1,2 , Maria Benavides1, Cristina Núñez1,2,3, Elisabete Oliveira1,2, Hugo M. Santos1,2, Carla I Santos1,2, Javier Fernandéz-Lodeiro1,2,4 Nuno Moura,1,5 Mario E. Diniz1 José Luis Capelo1,2

1BIOSCOPE Group, REQUIMTE, Chemistry Department, Faculty of Science and Technology, University NOVA of Lisbon 2829-516, Monte da Caparica, Portugal. Email:

[email protected] (www.bioscopegroup.org) 2ProteoMass Scientific Society, Madan Parque. Rúa dos Inventores. 2825-182. Caparica.

Portugal 3Ecology Research Group, Department of Geographical and Life Sciences, Canterbury Christ

Church University, CT1 1QU, Canterbury, United Kingdom 4 Instituto de Química, Universidade de São Paulo, Av. Prof. Lineu Prestes, 748, CxP.

26077, 05508-000 São Paulo, Brazil 5Chemistry Department and QOPNA, University of Aveiro, Campus Universitário Santiago,

3810-193 Aveiro, Portugal.

In the present communication will be presented several examples recently published by the BIOSCOPE Group in the application of functionalized emissive and colorimetric nanoparticles for analytical, environmental and bio-medical/proteomics applications. [1]

Figure 1: Example of AgNPs fuctionalized with a fluorescein derivative for toxic metal ion recognition.

Acknowledgements: Authors thank Scientific Association ProteoMass (Portugal) for financial support. C.N. thanks Xunta de Galicia for the I2C program postdoctoral contract. E. O. and H. M. S. acknowledge, the post-doctoral grants from FCT (Portugal) SFRH/BPD/72557/2010 and SFRH/BPD/73997/2010, respectively. [1] (a) C. Lodeiro, et al Chem. Soc. Rev. 2010, 39, 2948-2976.; (b) E. Oliveira et al, Inorg. Chem 2011, 8797-8807; (c) R. Lopez-Cortes et al, Talanta 2012, 100, 239-245; (d) C. Santos et al, Inorg. Chem., 2013, 52, 8564-8572; (e) J. Fdez Lodeiro et al, J. Nano. Res., 2013, 15, 1828-1838; (f) A. Fdez Lodeiro et al., ChemistryOpen, 2013, 2, 200-207.(f) E. Oliveira et al., Frontiers in Chemistry, 2013, 1, 29, 1-11.; (g) C. Nuñez et al., J. Inorg. Biochem., 2014 in press; (h) J. Fdez Lodeiro et al, J. Nano. Res., 2014, in press.

Posters

66

P24 – AMMONIUM-FUNCTIONALISED SILICA NANOPARTICLES AS NOVEL SUPPORTS FOR PHOTOLUMINESCENT

LANTHANOPOLYOXOMETALATES

Tânia V. Pinto1, Sandra M. A. Cruz2, Clara Pereira1, Rute A. S. Ferreira3, Luis D. Carlos3, Helena I. S. Nogueira2, Cristina Freire1


Porto, 4169-007 Porto, Portugal 2Department of Chemistry, CICECO, University of Aveiro, 3810-193 Aveiro, Portugal

3Departmentof Physics, CICECO, University of Aveiro, 3810-193 Aveiro, Portugal [email protected]

In the last decades, photoluminescent materials which have the capacity to emit light in response to several external stimuli have attracted much attention due to their potential application as fluorescent sensors, in biological microscopy and in optoelectronics [1]. Polyoxometalates (POMs) are a unique class of anionic metal-oxide clusters with remarkable structural, electronic and magnetic properties. POMs containing rare earth metals have been the focus of intensive studies owing to their structure, with formation of a large variety of complexes between LnIII cations and POM units, and their characteristic luminescent properties [2]. The immobilization of POMs onto solid supports, such as silica nanoparticles (SNPs) - large surface area to volume ratio, biocompatibility, tunable surface properties and high chemical and mechanical stabilities - allows not only to overcome the poor processability of pure POMs, but also make possible technological applications of these compounds [3]. In this work, the europium complex of lacunary Keggin type polyoxotungstate, K11[Eu(PW11O39)2]·5H2O [Eu(PW11)2] was immobilized onto ammonium-functionalized SNPs (f-SiO2). The f-SiO2 were prepared by two methods: a) sol-gel co-condensation between tetraethoxysilane (TEOS) and dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride (C18) and b) post-derivatization with polyethylenimine (PEI). The resulting materials were characterized by Fourier transform infrared spectroscopy with attenuated total reflectance (FTIR-ATR), Raman spectroscopy and scanning electron microscopy with X-ray microanalysis (SEM-EDS). Photoluminescence studies were performed on the novel photoluminescent silica nanoparticles and compared with the free Eu(PW11)2. Acknowledgements: This work has been supported by Fundação para a Ciência e a Tecnologia (FCT) and FEDER through grants no. PEst-C/EQB/LA0006/2011 and Pest-C/CTM/LA0011/2011 and through project ref. PTDC/CTM-POL/0813/2012 in the framework of Program COMPETE. The authors also acknowledge Operation NORTE-07-0124-FEDER-000067-Nanochemistry and to COST Action CM-1203 PoCheMoN. TP thanks FCT for her grant SFRH/BD/89076/2012 and SMAC for grant SFRH/BD/68598/2010. [1] Carlos, L. D.; Ferreira, R. A. S.; Bermudez, V. Z.; Ribeiro, S. J. L. Adv Mater 2009, 21, 509–534. [2] Pinto, R. J. B.; Granadeiro, C. M.; Freire, C. S. R.; Silvestre, A. J. D.; Neto, C. P.; Ferreira, R. A. S.; Carlos, L. D.; Cavaleiro, A. M. V.; Trindade, T.; Nogueira, H. I. S.; Eur J Inorg Chem 2013, 1890-1896. [3] Vivero-Escoto J. L.; Huang, Y.-T. Int J Mol Sci 2011, 12, 3888–3927.

Posters

67

P25 - RHODAMINE APPENDED BIPYRIDINE: AN EXAMPLE OF CONTROLLED METAL JUMPING?

Cristina Núñez1,2,3, Sérgio M. Santos4, Elisabete Oliveira1,5,

Adrián Fernandez Lodeiro1,5, Hugo M. Santos1,5, Carla I Santos1,5, Javier Fernandéz-Lodeiro1,5, Carlos Lodeiro1,5, José Luis Capelo1,5

1BIOSCOPE Group, REQUIMTE, Chemistry Department, Faculty of Science and Technology, University NOVA of Lisbon 2829-516, Monte da Caparica, Portugal. Email:

[email protected] 2Inorganic Chemistry Department, Faculty of Chemistry, University of Santiago de

Compostela, 15782 Santiago de Compostela, Spain 3Ecology Research Group, Department of Geographical and Life Sciences, Canterbury Christ

Church University, CT1 1QU, Canterbury, United Kingdom 4Department of Chemistry and CICECO,University of Aveiro

Campus de Santiago, 3810-193 Aveiro, Portugal 5ProteoMass Scientific Society. Madan Parque. Rua dos Inventores. 2825-182. Caparica.

Portugal

The development of artificial receptors for sensing and recognition of environmentally and biologically important ionic species is currently of great interest [1,2]. Having in mind this idea, we report here a novel colorimetric and fluorescent receptor 1 derived from Rhodamine B appended with one bipyridine unit (see Figure 1). The sensing ability of molecular probe 1 towards Cu2+, Zn2+, Cd2+, Hg2+ and Hg+ was evaluated in solution by absorption and fluorescence spectroscopy. The behavior observed towards different metal ions could be related with their internal jumping ability.

Figure 1: Spectrophotometric and spectrofluorimetric titrations of compound 1 in dichloromethane in the presence of increasing amounts of Cu(BF4)2 (A and B) and Hg(ClO4) 2 (C and D) in acetonitrile at 298 K. The inset shows the absorption at 319, 346 and ca. 562 nm and the normalized fluorescence

intensity at ca. 580 nm ([1] = 5.00 x 10-6 M, λexc=520 nm) (left). Schematic representation of the internal jumping effect (right)

Acknowledgements: Authors thank Scientific Association Proteomass (Portugal) for financial support. C.N. thanks Xunta de Galicia for the I2C program postdoctoral contract. [1] C. Lodeiro, et al Chem. Soc. Rev. 2010, 39, 2948-2976.; [2] Amendola, V.; et al. Coord. Chem. Rev. 2006, 250, 273-299.

Posters

68

P26 - IRON OXIDE NANOSTRUCTURES FOR MAGNETIC HYPERTHERMIA

S. G. Mendo1, A. F. Alves1, M. H. Mendonça1, L. P. Ferreira2,3, M. M. Cruz3, M. Godinho3, M. D. Carvalho1

1 CQB / Dep. Química e Bioquímica, Faculdade de Ciências, Universidade de Lisboa, Campo

Grande, 1749-016 Lisboa, Portugal. ([email protected]) 2 Dep. Física, Faculdade de Ciências e Tecnologia, Universidade de Coimbra, 3004-516

Coimbra, Portugal 3 CFMC / Dep. Física, Faculdade de Ciências, Universidade de Lisboa, Campo Grande,

1749-016 Lisboa, Portugal

Magnetic hyperthermia has been used in cancer treatment both as a way to destroy carcinogenic cells and also to increase the efficiency of chemo- or radiotherapy. Magnetite nanoparticles are considered one of the best candidates for this type of treatment/therapy due to the good biocompatibility and suitable magnetic properties, which are dependent on size and chemical composition [1, 2]. In order to tailor the magnetic properties, iron oxide nanostructures combining different magnetic phases have been synthesized by varying several experimental conditions. This work describes the synthesis and the structural, morphological and magnetic characterization of nanostructures composed by magnetite nanoparticles (Fe3-xO4) of different mean sizes decorated with hematite, using XRD, TEM, SQUID magnetometry and Mössbauer spectroscopy. To evaluate their potential interest for magnetic hyperthermia, induction heating studies under the influence of alternating magnetic fields were also performed to determine the heating efficiency of the samples.

Figure 1: Magnetite decorated with hematite in the presence of a permanent magnet (left) and TEM image of the nanostructures (right).

Acknowledgements: This work was carried out with the support of Portuguese FCT foundation through project PTDC/CTM-BIO/2102/2012.

[1] M. D. Carvalho, F. Henriques, L. P. Ferreira, M. Godinho, M. M. Cruz, J. Solid State Chem. 2013, 201, 144-152.

[2] M. B. López, A. Teijeiro, J. Rivas, Rep. Pract. Oncol. Radiother. 2013, 18, 397-400.

Posters

69

P27 - THE EFFECTIVE CHARGE DENSITY OF URANYL, UO2

2+, IN THE GAS PHASE – EXPERIMENTAL AND COMPUTATIONAL STUDIES

Ana F. Lucena1, José M. Carretas1, Maria C. Michelini2,

Philip X Rutkowski3, John K. Gibson3, Joaquim Marçalo1

1 Centro de Ciências e Tecnologias Nucleares, Instituto Superior Técnico, Universidade de Lisboa, 2696-066 Bobadela LRS, Portugal

2 Dipartamento di Chimica, Università della Calabria, Arcavacata di Rende, Italy 3 Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA

([email protected]) In this work, we used electrospray ionization quadrupole ion trap mass spectrometry (ESI-QIT/MS) to probe the effective charge density of uranyl, UO2

2+, in the gas-phase. Ethanol solutions of uranyl, divalent alkaline-earth (A = Ca, Sr, Ba) and trivalent lanthanide (Ln = La, Ce, Pr, Eu, Tb, Ho, Tm, Lu) nitrates readily yielded, in the negative ion mode, species of the type [(UO2)x(NO3)2x+1]-, [Ax(NO3)2x+1]- and [Lnx(NO3)3x+1]-, where x=1,2,… . With solutions of two metals in equimolar amounts, we observed the formation of the mixed species [A(UO2)(NO3)5]-, [Ln(UO2)(NO3)6]- and [ALn(NO3)6]-. Collision induced dissociation (CID) experiments in the QIT of the [A(UO2)(NO3)5]- species showed only the formation of the [UO2(NO3)3]- ion (Fig. 1A). CID of [Ln(UO2)(NO3)6]- showed a preferential formation of the [UO2(NO3)3]- ion for the Ln with larger ionic radii (Fig. 1B) and a preferential formation of the [Ln(NO3)4]- ions for the smaller Ln. CID of [ALn(NO3)6]- yielded the [Ln(NO3)4]- ions exclusively (Fig. 1C).

Figure 1: ESI-QIT/MS(-) CID spectra of: A. [CaUO2(NO3)5]-; B. [PrUO2(NO3)6]-; C. [CaPr(NO3)6]-. Computational studies (DFT) of the energetics of fragmentation of selected mixed species were in agreement with the experimental observations. The overall results suggest that, in the gas phase, the effective charge density of the uranyl ion is closer to that of a trivalent metal ion than to that of a divalent metal ion. This ordering is similar to that derived from the complexation stability with different ligands in solution studies [1]. Acknowledgments: The ESI-QIT/MS is part of RNEM-Rede Nacional de Espectrometria de Massa, supported by Fundação para a Ciência e a Tecnologia (FCT). Additional support from FCT (PhD grant SFRH/BD/70475/2010 to A.F.L.) is also acknowledged. [1] Choppin, G.R.; Rao, L. Radiochim. Acta 1984, 37, 143-146.

A B C

Posters

70

P28 - NEW COPPER(II) COMPLEXES WITH THE DNA BASES CYTOSINE AND GUANINE:

SYNTHESIS, CHARACTERIZATION AND CRYSTAL STRUCTURES

Teresa Santos1,2, Paula Brandão2, Bárbara Ferreira2, Darleila Costa1, João Calixto1, Vitor Félix1,2,3

1Department of Chemistry, University of Aveiro, 3810-193, Aveiro, Portugal; 2CICECO,

University of Aveiro, 3810-193, Aveiro, Portugal; 3Department of Health Sciences University of Aveiro, 3810-193, Aveiro, Portugal

[email protected]

Complexes of almost all transition metal elements nowadays are getting more and more importance due to the type of role they are involved either in biochemical, pharmacological or medicinal chemistry. Their different stereo-electronic properties, which depend on the metal centre, on their oxidation state and on the type of the coordinated ligands afford them a wide and versatile spectrum of applications. Among transition metal coordination compounds those with copper, mono, bi or multi-centred, have reached today a prominent place in the research for new metal drugs [1]. In this work we present our results on the synthesis and characterization of new copper(II) complexes coordinated with the DNA bases cytosine and guanine (Figure 1.a and 1.b). The DNA-bases have been used as models for the interaction of coordination metal drugs with DNA by covalence or by intercalation [2]. The new copper(II) complexes have been synthesized using a standard procedure, that is, the synthesis have been accomplished in aqueous or ethanol solution under reflux for 3-4 hours. The obtained solids have been characterized by FTIR, UV-VIS (solution and diffuse reflectance) and by single crystal X-ray analysis, and their structures have been determined.

a b

Figure 1: Cu(II)/Cytosine (a) and Cu(II)/Guanine (b) complexes

Acknowledgements: Thanks are due to CICECO and to the Dep. of Chemistry (University of Aveiro).

[1] Anbu, S.; Kandaswamy M.; Kamalraj, S.; Muthumarry, J.; Varghese, B., Dalton Trans., 2011, 40(8), 7310. [2] Mastropietro T.F., Armentano D, Grisolia E, Zanchini C, Lloret F, Julve M, De Munno G, Dalton Trans., 2008, 28(4), 514.

Posters

71

P29 - MAGNETITE NANOPARTICLES: PARTICLE SIZE CONTROL FOR HYPERTHERMIA

A. F. Alves1, S. G. Mendo1, L. P. Ferreira2,3, M. H. Mendonça1, M. M. Cruz3, M. Godinho3, M. D. Carvalho1

1CQB / Dep. Química e Bioquímica, Faculdade de Ciências, Universidade de Lisboa, Campo

Grande, 1749-016 Lisboa, Portugal. ([email protected]) 2Dep. Física, Faculdade de Ciências e Tecnologia, Universidade de Coimbra, 3004-516

Coimbra, Portugal 3CFMC / Dep. Física, Faculdade de Ciências, Universidade de Lisboa, Campo Grande,

1749-016 Lisboa, Portugal Synthesis of magnetite nanoparticles for treatment of cancer cells by hyperthermia is a trendy topic nowadays. For this application the particle size, the morphology and the magnetic properties of these particles are very important since they dictate the energy loss under an alternate magnetic field. Thus, an important issue is to synthesize monodisperse particles, since large size distributions behave differently under the influence of the magnetic field [1]. The main focus of this work is to obtain magnetite nanoparticles with narrow size distribution. Therefore, different methods of synthesis, such as the well-known coprecipitation and reflux methods, were used with the addition of surfactants in order to control the shape and size of the resulting nanoparticles. A new and environmental friendly synthesis method in gelatin medium was also explored. The magnetite nanoparticles were characterized by XRD, SQUID magnetometry and 57Fe Mössbauer spectroscopy. Induction heating measurements (figure 1) were performed afterwards and the results will be presented in correlation with the size, morphology and magnetic properties of the nanoparticles.

Figure 1: Assembly for heating measurements.

Acknowledgements: The work was carried out with the support of Portuguese FCT foundation through project PTDC/CTM-BIO72102/2012. [1] Li, Z.; Kawashita, M.; Araki, N.; Mitsumori, M.; Hiraoka, M.; M. Mater. Sci. Eng. C 2010, 30, 990996.

Posters

72

P30 - HIERARCHICAL MCM-22 ZEOLITE THROUGH ALKALINE TREATMENTS USING MICROWAVE ASSISTED HEATING

Susana Costa1,4, Isabel M. Fonseca1, Ana P. Carvalho2,3, Angela Martins3,4

1DQ, REQUIMTE CQFB, FCT, UNL, Quinta da Torre, 2829-516 Caparica, Portugal

2DQB, FCUL, Campo Grande, C8, 1749-016 Lisboa, Portugal 3CQB, FCUL, Campo Grande, C8, 1749-016 Lisboa, Portugal

4ADEQ, ISEL, Rua Conselheiro Emídio Navarro, 1959-007 Lisboa, Portugal [email protected]

Zeolites are versatile materials used in adsorption, separation processes and heterogeneous catalysis. To improve the accessibility and molecular transport in these purely microporous materials several strategies have been attempted, being the alkaline treatment with NaOH – desilication - one of the most popular. MCM-22 (MWW structure) is a synthetic zeolite comprising three independent pore systems, two internal, with supercages accessed through narrow windows and a third one located at the external surface. In our previous study, mesoporosity was generated on this zeolite using a conventional heat source [1]. This work deals with the use of microwave radiation as a heating source, aiming to create mesoporosity with short exposure times. This procedure was already explored by us for mordenite (MOR) [2] and now some preliminary results are presented for MCM-22. The synthesis of MCM-22 zeolite (Si/Al=14) was made as described elsewhere [3]. For the alkaline treatments a suspension with a volume ratio NaOH/zeolite = 90 was prepared. The treatments were carried out using [NaOH] = 0.03 or 0.05 M during 5 or 10 min in a CEM Discover MW reactor with power adjustments to maintain the temperature at 50 ºC. The suspension was then quenched, the solid recovered by centrifugation, dried, submitted to ion exchange with NH4NO3 and calcined in air flow at 500 ºC for 4 h. The materials were characterized by powder XRD revealing that the crystalinitty is maintained. Table 1 shows the preliminary results of textural characterization by N2 adsorption proving the development of mesoporosity upon the treatments. Acidity characterization by pyridine adsorption followed by FTIR spectroscopy and catalytic model reaction of m-xylene transformation are currently being studied.

Table 1: N2 adsorption results for MCM22 and 5 min irradiated samples.

Sample Vmicro

(cm3 g‐1)

Vmeso

(cm3 g‐1)

Aext

(m2 g‐1)

MCM22 0.14 0.15 89

MCM22/0.03 0.13 0.18 92

MCM22/0.05 0.11 0.18 94

Acknowledgements: This work was supported by FCT pluriannual programme of CQB (PEst-OE/QUI/UI0612/2013).

[1] Machado, V. et al., Appl. Catal. A: Gen. 2012, 445-446, 329-338. [2] Paixão, V. et al., Appl. Catal. A: Gen., 2011, 402, 50-68. [3] Güray, J. et al., Micropor. Mesopor. Mater., 1999, 31 241-251.

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73

P31 - AN IRIDIUM(III) COMPLEX WITH LISSAMINE RHODAMINE-B DERIVATIVE: A FLUORESCENT MOLECULAR LOGIC GATE USING MERCURY, CYSTEINE AND GREEN QUANTUM DOTS AS INPUTS

Elisabete Oliveira1,2, David J. Peitinho1, Carla I. M.Santos1,2,

Hugo M. Santos1,2, Adrián Fernandéz-Lodeiro1,2, Cristina Núñez1,2,3, Javier Fernandéz-Lodeiro1,2,4 José Luis Capelo1,2, Carlos Lodeiro1,2

[email protected] (www.bioscopegroup.org)

1BIOSCOPE Research Group, REQUIMTE, Chemistry Department, Faculty of Science and Technology, Caparica Campus, NOVA University of Lisbon, 2829-516, Caparica, Portugal. 2ProteoMass Scientific Society. Madan Parque. Rua dos Inventores. 2825-182. Caparica.

Portugal 3Ecology Research Group, Department of Geographical and Life Sciences, Canterbury Christ

Church University, CT1 1QU, Canterbury, United Kingdom. 4Instituto de Química, Universidade de São Paulo, Av. Prof. Lineu Prestes, 748, CxP. 26077,

05508-000 São Paulo, Brazil

Actually, the design of fluorescent supramolecular systems with emissive properties that can be modulated by external inputs has been target of several studies. These systems could be applied in elementary electronic devices greatly increasing the development of miniaturized device components [1]. Iridium complexes due to their intense phosphorescence at room temperature, likewise the highly fluorescence of quantum dots (QDs) made them the most promising dyes in organic light-emitting diodes (OLEDs). Following our interest in new fluorescent materials [2], herein we present a compound derivative from lissamine rhodamine B (1) and their iridium (III) complex at room temperature in aqueous solution. The 1@iridium complex was also studied in presence of mercury (II) metal ions and the amino acid L-cysteine (see figure 1). In addition, it was performed the interaction of green fluorescent QDs with compound 1.

Figure 1: (Left) Image of compound 1, the complex 1@Ir(III), 1@Ir(III)@Hg(II) and of

1@Ir(III)@Hg(II)@cysteine in aqueous solution under a UV-Lamp, exc=365 nm. (Right) The logic circuit equivalent to the molecular switches.

Acknowledgements: E. Oliveira and H. M. Santos acknowledge, the post-doctoral grants from

FCT/MEC (Portugal) SFRH/BPD/72557/2010 and SFRH/BPD/73997/2010, respectively. PROTEOMASS Scientific Society (Portugal) and PROTEOMASS Scientific Society (Spain) are also

acknowledged for funding. [1] Balzani, V.; Credi, A.; Raymo, F. M.; Stoddart, J. F. Angew. Chem., Int. Ed. 2000, 39, 3348-3391. [2] Oliveira, E.; Santos, C.; Poeta, P.; Capelo, J. L., Lodeiro, C. Analyst, 2013, 138, 3642-3645.

1 1Ir3+ 1Ir3+ +Hg2+ +Cys

Posters

74

P32 – CAMPHOR CARBOXAMIDES: CARRIERS OF AMINO ACIDS TO THE Cu(II) SITE

M. Fernanda N.N. Carvalho, Alexandra P.S. Roseiro, Ana Knittel, Adelino M. Galvão and João Costa Pessoa

Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais 1049-001 Lisboa, Portugal, E:mail: [email protected].

There is a renewed interest in the study of the properties of copper complexes derived from amino acids, due to recent achievements concerning their properties as antibacterial, anticancer or multi drug resistance reversing agents [1]. Camphor lithium carboxamides (OC10H15CONHCH(R)CO2Li) (R= H, 1, R=CH2Ph, 2) react with CuCl2, under inert atmosphere, affording the amino acid complexes [Cu(NH2CHRCOO)2] (R=H, I; R=CH2Ph, II) by cleavage of the carboxamide CN bond and release of the lithium camphor carboxylate (3). Exposure of the reaction mixture to air enables formation of camphorquinone (4) from lithium camphor carboxylate (3, [2]) (Scheme 1) and amino acid degradation within a process that involves CO2, NH3 and aldehyde formation (Strecker-type process) [3] due to the high oxidative character of the system.

Scheme 1

In the processes Cu(II)Cu(I) reduction was corroborated through isolation of [CuCl(phen)2] formed by addition of phenantroline to the reaction mixture. Acknowledgements: Financial support by FCT-Fundação para a Ciência e Tecnologia (Projecto Estratégico – PEst-OE/QUI/UI0100/2013) and the NMR and MS (IST-Node) Networks for facilities. [1] (a) Thalamuthu,S., Annaraj, B., Neelakantan, M.A. Spectrochem. Acta (A): Mol. & Biomol. Spectroscopy, 2014, 118, 120-129. (b) Ganguly, A., Chakraborty, P., Banergee, K., Choudhuri, S.K. Eur. J. Pharm. Scie. 2014, 51, 96-109. [2] Ferreira A.S.D., Schulz, J., Galvão, A. M., Roseiro, A.P.S., Štěpnička, P., Veiros, L.F., Carvalho, M.F.N.N. KOM, 2014, (http://dx.doi.org/10.1016/j.jorganchem.2013.11.039). [3] Rizzi, G.P. Food Rev. Int. 2008, 24, 416-435.

Posters

75

P33 - THE ANION ROLE ON PROMOTING ROOM TEMPERATURE THERMAL SPIN CROSSOVER IN Fe(III) COMPLEXES

Ana I. Vicente,1 Sara Realista,1 Liliana P. Ferreira,2,3 Maria de Deus Carvalho,1

Ana I. Melato,1 Paula Brandão,4 Maria José Calhorda,1 Paulo N. Martinho1

1 Departamento de Química e Bioquímica, CQB, Faculdade de Ciências, Universidade de Lisboa, Campo Grande, 1749-016 Lisboa, Portugal.

2 CFMC, Faculdade de Ciências, Universidade de Lisboa, Campo Grande, 1749-016 Lisboa, Portugal

3 Departamento de Física, Faculdade de Ciências e Tecnologia, Universidade de Coimbra, 3004-516 Coimbra, Portugal

4 Departamento de Química, CICECO, Universidade de Aveiro, 3810-193, Aveiro, Portugal Spin crossover (SCO) complexes have long been considered as promising candidates for the next generation of data storage devices [1,2]. SCO candidate compounds can be found among a limited group of 3d4–3d7 transition metal ions, the most common being Fe(II), Fe(III) and Co(II). Fe(III), with its advantageous redox stability, is a good candidate for fabrication of SCO materials, an area towards which research has been moving [3]. Despite this, the search for new examples and the study of SCO properties should not be disregarded. In order to analyse the effect of unit cell contents on the magnetic behaviour of a SCO centre, we prepared a series of Fe(III) complexes. Five salts of a mononuclear Fe(III) complex [FeL2]Y, L = 5-Br-salEen and Y = NO3

-, BF4-, PF6

-, ClO4- and BPh4

- were synthesised and investigated by different experimental techniques and DFT calculations. SQUID magnetometry and 57Fe Mössbauer spectroscopy demonstrate that all complexes display thermal SCO with transition temperatures around RT, ranging from incomplete and gradual to complete. The ClO4

- complex shows an interesting SCO with a 70 K hysteresis window and the BPh4

- complex displays magnetic field dependent SCO.

Figure 1: Magnetic profiles of both ClO4

- and BPh4- Fe(III) complexes.

Acknowledgements: We thank Fundação para a Ciência e Tecnologia for financial support (PEst-OE/QUI/UI0612/2013, PEst-OE/QUI/UI0536/2011, PEst-OE/FIS/UI0261/2011 and PTDC/QUI-QUI/101022/2008) and fellowships to AM (SFRH/BPD/69526/2010), PNM (SFRH/BPD/73345/2010). [1] Kahn, O.; Launay J. P. Chemtronics 1988, 3, 140-144. [2] Kahn, O.; Krober, J.; Jay, C. Adv. Mater. 1992, 4, 718-728. [3] Halcrow, M. A. Spin-Crossover Materials: Properties and Applications; John Wiley & Sons Ltd, 2013.

Posters

76

P34 - BINUCLEAR ZINC COMPLEXES FOR GREEN CO2 CAPTURE AND REDUCTION

Sara Realista, Paulo Nuno Martinho, Ana Isabel Melato, Maria José Calhorda

Departamento de Química e Bioquímica, CQB, Faculdade de Ciências, Universidade de Lisboa, Campo Grande, 1749-016 Lisboa, Portugal, [email protected]

Hydrocarbon fuels are currently the most important source of energy because of their ready availability, stability, and high energy density. Unfortunately, combustion of this source of energy carries a significant issue to the environment and environmental pollution, for which carbon dioxide emissions are responsible [1]. Recent reports of reaction of pressurised CO2 with epoxides to form polycarbonates [2] or cyclic carbonates [3] have attracted both academic and industrial interest, but the recycling of CO2 to produce high value products via low-cost catalysts has not been much exploited. Among others, zinc(II) complexes with salen derived ligands have shown to have good catalytic activity for CO2 conversion to either cyclic or acyclic carbonates [4]. In addition, the development of modified electrodes with conducting polymers containing metal centres along the polymer backbone has been a very active area of research [5]. Salphen-type polymers are attractive, because extra synthetic steps to attach electropolymerisable groups can be avoided as Schiff base complexes can be directly electropolymerised. Here we present the synthesis of new binuclear zinc(II) complexes (figure 1) which can be electropolymerised on an inert substrate by potentiostatic and/or potentiodynamic modes. The so-formed films are characterized by cyclic voltammetry, atomic force microscopy and spectroscopic techniques. The electrocatalytic potential of these modified electrodes for CO2 recycling is investigated.

Figure 1: Binuclear zinc(II) complexes.

Acknowledgements: We thank Fundação Calouste Gulbenkian for financial support - Programa Estímulo à Investigação 2013.

[1] Whipple D. T., Kenis P. J. A., The journal of Physical Chemistry Letters, 2010, 1, 3451-3458 [2] Coates G. W., Moore D. R., Angew. Chem. Int. Ed., 2004, 43, 6618-6639. [3] Meléndez J., North M., Pasquale R., Eur. J. Inor. Chem., 2007, 21, 3323-3326. [4] Shen Y., Duan W., Shi M., J. Org. Chem., 2003, 68, 1559–1562. [5] Aubert P. H., Aubert P., Roche M., Capedevielle P., Maumy M., Ricart G., Chem. Mater., 2001, 13, 2223-2230

Posters

77

P35 – SYNTHETIC PATHWAYS FOR NOVEL Y(III) COMPLEXES SUPPORTED BY DIANIONIC CYCLAM LIGANDS

Filipe Madeira, Luís G. Alves, Ana M. Martins

Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal Email: [email protected]

Several studies on the reactivity of Zr(IV) cyclam-based complexes have been described by our group [1]. Here we present the preparation of new yttrium(III) complexes bearing a trans-disubstituted cyclam fragment. The compound (Bn2Cyclam)Y(N(SiMe3)2) (1) (Bn = CH2Ph) was prepared through the reaction of Y[N(SiMe3)2]3 with H2Bn2Cyclam, with elimination of HN(SiMe3)2 (Figure 1). Attempts to generate a cationic complex from 1 with [HNMe3][BPh4] led to the formation of the peculiar species [(HBn2Cyclam)Y(N(SiMe3)2)][BPh4] (2). Aiming at the synthesis of Y(III) alkyl compounds, reactions of Y(CH2SiMe3)3(THF)2 with H2R2Cyclam (R = PhCH2,

3,5-tBuPhCH2) were performed. These reactions generated the orthometallated complexes ((C6H4CH2)BnCyclam)Y(THF) (3) and Li[Y(3,5-tBuC6H3CH)2Cyclam](THF) (4), respectively, via SiMe4 elimination and C-H activation, but in low yields. The zwitterionic complex 4 was obtained in high yield by reacting the Li[Y(CH2SiMe3)4(THF)2] precursor with H2(

3,5-tBuBn)2Cyclam. All products were analysed by NMR spectroscopy and single crystal X-ray structures were obtained.

Figure 1: Synthetic pathways to obtain 1-4 yttrium(III) complexes Acknowledgements: Funding from FCT, Portugal, is acknowledged (SFRH/BD/87679/2012 and SFRH/BPD/86815/2012) [1] Martins, A. M, Munhá, R. F., Alves, L. G., Bharathi, S., A new family of zirconium complexes anchored by dianionic cyclam-based ligands: syntheses, structures, and catalytic applications. In Advances in Organometallic Chemistry and Catalysis (The Silver/Gold Jubilee ICOMC Celebratory Book), Pombeiro, A. J. L., John Wiley & Sons, Hoboken, USA, 2014, 315-323, and all the references cited in it.

Posters

78

P36 - SYNTHESIS AND CHARACTERIZATION OF MONONUCLEAR IMINOPYRROLYL BORON COMPLEXES WITH LUMINESCENT

PROPERTIES

D. Suresh1, Patrícia S. Lopes1, Cláudia A. Figueira1, Clara S. B. Gomes1, Pedro T. Gomes1, Bruno Ferreira1, Roberto E. Di Paolo1, António L. Maçanita1,

M. Teresa Duarte1, Ana Charas2, Jorge Morgado2, Maria José Calhorda3

1Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa 2Instituto de Telecomunicações, Instituto Superior Técnico, Universidade de Lisboa

3Centro de Química e Bioquímica, Faculdade de Ciências, Universidade de Lisboa, Portugal. E-mail: [email protected]

In recent years, there has been an increasing interest on coordination and organometallic compounds exhibiting photoluminescent properties due to their potential applications in electroluminescent displays. Fluorescent tri- and tetracoordinate boron complexes have attracted attention because of their potential applications in functional materials and in sensors [1]. Variations in the chromophore moiety of the molecules revealed an influence in the HOMO-LUMO energies and thereby the color of emission. The 2-arylformiminopyrrole ligand precursors are one of such synthons where the electronic and steric nature can be easily fine-tuned. A family of Ph2B(Iminopyrr-Ar) complexes were synthesized in good to average yields by the reaction of the corresponding ligand precursors and BPh3 [2]. The complexes with electron-withdrawing aryl substituents show intense (F= 0.71; e.g. Ar= 4-CN-C6H4) blue fluorescent emission while those bearing electron-donating aryl substituents are blue-green emitters with relatively lower quantum yields (F=0.13; e.g. Ar= 4-OMe-C6H4). The presence of bulkier substituents in 2,6-positions of the aryl groups restricts the rotation of this moiety inducing a shift in the emission to the violet region and a significant decrease in the quantum yield(F= 0.005; e.g. Ar= 2,6-Me2-C6H3).

NH

NAr

N

N ArB

BPh3

Toluene, ref lux16-20 h

1 Ar= C6H52 2,6-Me2-C6H33 2,6-iPr2-C6H34 4-OMe-C6H4

5 Ar=3,4-Me2-C6H36 4-F-C6H47 4-NO2-C6H48 4-CN-C6H4

9 Ar= 3,4,5-F3C6H2

10 C6F5

Acknowledgements: We thank the Fundação para a Ciência e Tecnologia for financial support (Project PTDC/QUI/65474/2006) and for fellowships SFRH/BPD/47853/2008 (DS), SFRH/BD/47730/2008 (CAF), SFRH/BPD/64423/2009 (CSBG) and SFRH/BD/88639/2012 (PSL).

[1] a) Hudson, Z. M.; et al. Acc. Chem. Res. 2009, 42, 1584. b) Liu, Q.-D.; et al. Adv. Funct.Mater. 2005, 15, 14. c) Sole, S.; et al. Chem. Commun. 2004, 1284. [2] a) Suresh, D.; et al. Dalton Trans. 2012, 41, 8502. b) Suresh, D.; et al. Chemistry A European Journal 2014, in press, DOI:10.1002/chem.201303607.

Posters

79

P37 – HYBRID MESOPOROUS SILICA GRAFTED WITH PHOTOISOMERIZABLE 2-HYDROXYCHALCONES

Sandra Gago, Isabel M. Fonseca, A. Jorge Parola

REQUIMTE, Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, 2829-516 Caparica, Portugal. e-mail: [email protected]

Hybrid photochromic mesoporous materials based on MCM-41 and SBA-15 were synthesized by covalent attachment of 3'-butoxy-7-hydroxyflavylium (Fl-OH) and 3'-butoxy-7-metoxyflavylium (Fl-OCH3) hydrogensulfates to yield MCM-41-Fl-OH and SBA-15-Fl-OCH3 (Scheme 1). The materials were characterized by powder X-ray diffraction, N2 adsorption, solid-state 13C CPMAS NMR spectroscopy, and thermogravimetric and elemental analyses, which confirm the successful covalent bonding of the flavylium moieties with loadings of 16.90±0.05 and 11.78±0.04% (w/w) for MCM-41-Fl-OH and SBA-15-OCH3, respectively. Flavylium compounds originate in solution a multiequilibria reaction network than can be actuated by pH and light, defining pH-coupled photochromic systems. The new hybrids show pH-dependent reflectance spectra resembling those observed in solution and photochromism upon irradiation [1].

Figure 1: Synthetic strategy leading to the hybrid materials

MCM-41-Fl-OH and SBA-15-Fl-OCH3

Acknowledgements: This work was supported by European project NMP4-SL-2012-310651 under FP7-NMP-2012-SMALL-6 and by Fundação para a Ciência e Tecnologia through the National Portuguese NMR Network, grant PEst-C/EQB/LA0006/2011 and projects PTDC/QUI-QUI/104129/2008 and PTDC/QUI-QUI/119932/2010. [1] Gago, S.; Fonseca, I. M.; Parola, A. J. Microporous Mesoporous Mater. 2013, 180, 40-47.

Si

OEt

EtO

EtO Cl

O

HOreflux, toluene

+ +

O

O+

R

OH

O

O

O

R KI, K2CO3

R= OH, OCH3

HSO4-

H2SO4 /CH3COOH (2:8, v/v), RT

MCM-41 or SBA-15

R= OH: MCM-41-Fl-OHR= OCH3: SBA-15-Fl-OCH3

SiO

OH

SiO

OH

SiO

O

SiO

OSi

EtO

Cl

DMF, 100 ˚C 2 days

MCM-41-Cl or SBA-15-Cl

SiO

O

SiO

OSi

EtO

MCM-41-AcPh or SBA-15-AcPh

SiO

O

SiO

OSi

EtO

Posters

80

P38 - 67Ga ESTRADIOL BASED COMPLEX FOR BREAST CANCER ER+ IMAGING: SYNTHESIS AND PRECLINICAL EVALUATION

Susana Cunha1, Célia Fernandes1, Fernanda Marques1, M. Cristina Oliveira1, Isabel Santos1, Lurdes Gano1

1C2TN, Campus Tecnológico e Nuclear-IST, Estrada Nacional 10 (km 139,7), 2695-066

Bobadela LRS, Portugal

Cancer is recognized as a major leading cause of death worldwide. The oestrogen receptor (ER) is an important tumour biomarker for molecular imaging and radionuclide therapy due to its overexpression in many malignant cells (breast, ovarian, endometrial) when compared to normal cells [1]. Moreover, ER status can predict the tumor prognosis or response to hormonal therapy as such cancers are often hormonally regulated. Therefore, the search for novel ligands to specifically target ER-positive (ER+) tumours continues to be a very demanding task and may improve the diagnosis and monitoring of individual therapeutic responsiveness [2, 3].

Recently we have described the preclinical studies obtained with two 67Ga/111In-16α-DOTA-estradiol based complexes to specifically target ER+ cancer cells [4].

Herein we describe the synthesis and preclinical evaluation of a new 67Ga complex 16α-NODAGA-estradiol derivative (L) to access its feasibility for functional imaging of ER+ tumors.

Figure 1: Structure of 67GaL

Acknowledgements: Susana Cunha acknowledges Fundação para a Ciência e Tecnologia (FCT) for PhD grant (SFRH/BD43432/2008). This work was supported by project PTDC/QUI-QUI/111891/2009 and EXCL/QEQ-MED/0233/2012.

[1] Bai, Z., Gust, R., Arch. Pharm. Chem., Life Sci, 2009, 342, 133. [2] Kumar, R., Eur J Nucl Med Mol Imaging, 2007, 34, 346 [3] Weigel, M. T., Dowsett,. M., Endocrine-Related Cancer, 2010, 17, R245 [4] Cunha, S., Fernandes, C., Oliveira, Gano, L., Santos, I., The Quart. J. Nucl. Med. Mol. Imaging, 2012, 56 Supl 1, 40.

Posters

81

P39 - THE CURIOUS CASE OF 3D METAL/SULFOXIDE BINDING

Bernardo de Pina Cardoso1, Maria José Calhorda1, João M. S. Cardoso2, Beatriz Royo2

1Departamento de Química e Bioquímica, CQB, Faculdade de Ciências da Universidade de

Lisboa, Campo Grande, Ed. C8, 1749-016 Lisboa, Portugal, [email protected] 2Instituto de Tecnologia Química e Biológica, ITQB, Av. da República EAN, 2780-157 Oeiras,

Portugal

3d metals are known to bind sulfoxides predominantly by the O atom, in contrast with 4d and 5d transition metals, which prefer the S atom (Re, Ru, Os, Rh, Ir, Pd, Pt),[1] as expected from the larger soft acid character of the latter. However, a limited number of examples of S-bonded sulfoxide compounds are known for 3d transition metals. The discovery of a new S-bonded Fe(II)-DMSO complex Figure 1), which acts as catalyst in sulfoxide reduction,[2] led us to explore the nature of sulfoxide binding in Cr(0), Co(I), Fe(I) and Fe(II) complexes.[3] All of these examples showed S-bond DMSO in the reported X-ray structures. DFT calculations were performed for the parent Fe(II) complex, containing as coligands a pentamethylcyclopentadienyl with a pending NHC arm and a carbonyl (NHC = N-heterocyclic carbene) and for the other metal centers. It was found that the calculated energies were always lower for the observed S-M bonding mode, except in the case of the complex [Fe(II)pc(DMSO)2] (pc = phthalocyanine), where O-bonding was favored, by a tiny energy difference (< 1 kcal mol-1). In the complexes of the form [ML4(DMSO)2], coordination by both sulfur moieties is favored over a mixed S and O or only O bonding.

Figure 1: X-ray structure of a Fe(II)-S bonded sulfoxide complex (left) and the calculated structures for

the S-bonded isomer (center) and O-bonded isomer (right) with relative energies (kcal.mol-1).

Acknowledgements: We thank Fundação para a Ciência e Tecnologia, Portugal, for financial support (Projects PEst-OE/QUI/UI0612/2013).

[1] Calligaris, M. Coord. Chem. Rev. 2004, 248, 351–375. [2] Cardoso, J. M. S.; Royo, B. Chem. Commun. 2012, 48, 4944–4946. [3] Allen, F. H. Acta Crystallogr. Sect. B Struct. Sci. 2002, 58, 380–388.

Posters

82

P40 - EFFECTS OF THE METHYLATION OF 1,10-PHENANTHROLINE IN THE INTERCALATION BETWEEN GUANINE-CYTOSINE AND

ADENINE-THYMINE TETRAMERS. A THEORETICAL STUDY

Adrià Gil1, Vicenç Branchadell2, Maria José Calhorda1

1Departamento de Química e Bioquímica, CQB, Faculdade de Ciências, Universidade de

Lisboa, Campo Grande 1749-016 Lisboa, Portugal 2Departament de Química, Universitat Autònoma de Barcelona, 08193 Bellaterra, Barcelona,

Spain The in vitro cytotoxicity of [Pt(en)(phen)]2+ complexes (en = ethylendiamine and phen = 1,10-phenanthroline) and mehylated-phen derivatives was observed against the L1210 mouse Leukemia cell lines.[1] It was concluded that the position and number of the substituting methyl groups and the resulting geometry of the bound complex in the base pair pocket affect cytotoxicity. NMR studies showed that [Pt(en)(phen)]Cl2 intercalated in the hexamer d(GTCGAC)2 from the minor groove at the C3-G4 site.[2] By means of DFT methods that take into account dispersion forces [3,4] and “sandwich” models used before [5,6] we tried to rationalize how methylation of phen affects the intercalation between guanine-cytosine (G-C) tetramers and to give some insight on the influence on cytotoxicity. Our results show that the most favored intercalation from the minor groove corresponds to the 5,6-Me2phen ligand in agreement with maximum cytotoxicity observed before.[1] We extended our study to intercalation taking place from the major groove and to adenine-thymine (A-T) tetramers. Interactions are analyzed in terms of energy decomposition analysis, polarizability, dipole moments, molecular electrostatic potential maps (MEPs, see Figure 1), electronic density, analysis of the frontier orbitals and charge transfer.

Figure 1: Two views for the MEPs corresponding to the intercalation of phen from the minor groove

between G-C/C-G base paris. Acknowledgements: Thanks are due to the Fundação para a Ciência e a Tecnologia (FCT) for the grants SFRH/BPD/89722/2012 and Pest-OE/QUI/UI0612/2013). [1] Brodie, C. R.; Collins, J. G.; Aldrich-Wright, J. R. Dalton Trans. 2004, 2004, 1145-1152. [2] Collins, J. G.; Rixon, R. M.; Aldrich-Wright, J. R. Inorg. Chem. 2000, 39, 4377-4378. [3] Zaho, Y.; Truhlar, D. G. Acc. Chem. Res. 2008, 41, 157-167. [4] Zaho, Y.; Truhlar, D. G. Theor. Chem. Acc. 2008, 120, 215-241. [5] Biancardi, A.; Biver, T.; Marini, A.; Mennucci, B.; Secco, F. Phys. Chem. Chem. Phys. 2011, 13, 12595-12602. [6] Gil, A.; Branchadell, V.; Calhorda, M. J. submitted.

Posters

83

P41 - SOLID-STATE SENSITIZED SOLAR CELLS BASED ON CH3NH3PbI3 PEROVSKITE/MWCNTs NANOCOMPOSITES

B. Jarrais and C. Freire

REQUIMTE, Department of Chemistry and Biochemistry, Faculty of Science, University of Porto, Rua do Campo Alegre, s/n, 4169-007 Porto, Portugal. [email protected]

The abundant supply and environmental friendliness of solar energy make the efficient and cost-effective conversion of solar radiation into electricity a compelling scientific goal. Since their discovery in 1991, by Grätzel and his co-workers, dye-sensitized solar cells (DSSCs) became a key alternative to conventional photovoltaic cells. [1] Moreover, attempts have been going on over many years to find an alternative to the liquid electrolytes with an improved solid state analogue of DSSCs. The efficiency increase in the solid state sensitized solar cells (SSSCs) from about 5% to over 15% have been reported within two years, mainly due to the efforts in the perovskites based mesoporous solar cells developments. Organometal halide perovskites were first used as sensitizers for DSSCs in 2009 by Kojima et al. [2], but it was only in 2013 that a solid state device using a lead iodide perovskite and a poly-triarylamine as the hole conductor, reached a remarkable efficiency of 12%. [3] In this work, new SSSCs were fabricated through the incorporation of MWCNTs in the perovskite layer, as it can act both as light harvester and hole conductor. The photoelectrodes were characterized by UV-Vis, SEM-EDX and XRD and the assembled solid-state sensitized solid cells were characterized by their I-V curve as well as a standard DSSC using the N719 dye.

Figure 1. Crystal structure of CH3NH3PbI3 perovskite. Acknowledgements: This work was funded by FCT and FEDER through grant no. PEst-C/EQB/LA0006/2011 and Operation NORTE-07-0124-FEDER-000067 – NANOCHEMISTRY. B.J. thanks FCT for the grant ref. SFRH/BD/90015/2012. [1] O’Reagen, B.; Grätzel, M. Nature, 1991, 353, 737-740. [2] Kojima, A.; Teshima, K.; Shirai, Y.; Miyasaka T. J. Am. Chem. Soc., 2009, 131, 6050-6051. [3] Heo, J. H.; Im, S. H.; Noh, J. H.; Mandal, T. N.; Lim, C.; Chang, J. A.; Lee, Y. H.; Kim, H.; Sarkar, A.; Nazeeruddin, Md. K.; Grätzel, M.; Seok, S. I. Nat. Photonics, 2013, 7, 486–491.

Posters

84

P42 - SYNTHESIS OF LANTHANIDES COMPLEXES WITH LUMINESCENT AND THERAPEUTIC PROPERTIES

Mário Felício1, Pedro D. Vaz1, Mariela Nolasco2

1 Centro de Química e Bioquímica da Faculdade de Ciências da Universisdade de Lisboa,

Campo Grande, 1749-016, Lisboa – Portugal 2 CICECO, Department of Chemistry, University of Aveiro, Campus de Santiago, 3810-193,

Aveiro – Portugal [email protected]

In the last years, lanthanides (Ln) have been studied extensively because of their unique lumiscent/fluorescent properties, such as a long Stokes shift, exceptionally decay times and long excitable wavelength [1, 2]. The complexation of these metals, especially europium (Eu), terbium (Tb) and gadolinium (Gd), have a large number of applications in medicine, like drug scanning, biosensor and imaging, and in technology, like tunable lasers and amplifiers for optical telecommunication. With these discoveries, the synthesis of the lanthanides complexes that target cancer cells has been gaining a major interest. In merge with this, an organic compound (8-hydroxyquinoline) was identified to target cancer cells specifically, by recruiting copper from the cell, reducing their proliferation and leading to apoptosis [3]. The objective of the current work is to synthetize Eu/Tb complexes that can recruit copper specifically from cancer cells, having a therapeutic action and working like imaging probe. The complexes (16 in the total, 8 without and 8 with copper), besides the metal, have a molecule of 2,2-bypyridine, that promote the antenna effect for the Ln, and have one ligand that can target and recruit copper in tumours cells, (four different ligands were tested). The complexes by several techniques: UV/Vis, Raman and infrared spectroscopy, elemental analysis, mass spectrometry and fluorescent essays. Proliferation and cytotoxic effects of the complexes were studied in HeLa cells, concluding that the complexes without copper don’t have a cytotoxic effect and, by contrast, the complexes with copper reduce the proliferation and induce the apoptosis. Acknowledgements: Authors are grateful to FCT for financing support, (Projects PEst-OE/QUI/UI0612/2011 and PTDC/CTM-NAN/112168/2009). MRF acknowledges a research fellowship (BI/UI89/6092/2012), within project PTDC/CTM-NAN/112168/2009. [1] Lima, P.; Nolasco, M. M.; Paz, F. A. A.; Ferreira, R. A. S.; Longo, R. L.; Malta, O. L.; Carlos, L. D. Chem. Mater. 2013, 25, 586. [2] Pandya, S.; Yu, J.; Parker, D. Dalton Trans. 2006, 2757. [3] Daniel, K. G.; Gupta, P.; Harbach, R. P.; Guida, C. W.; Dou, Q.P. Biochem. Pharmacol. 2004, 67, 1139.

Posters

85

P43 - MOLYBDENUM(II) COMPLEXES BEARING PYCAPH LIGANDS AND THEIR ACTIVITY AS HOMOGENOUS AND HETEROGENOUS

CATALYSTS

João Tiago Marreiros1, Maria Vasconcellos-Dias1, Maria José Calhorda1

1Departamento de Química e Bioquímica CQB, Faculdade de Ciências da Universidade de Lisboa, 1749-016 Lisboa, Portugal.

Mo(II) complexes [MoBr(η3-C3H5)(CO)2(L’)] can be obtained from the reaction between [MoBr(η3-C3H5)(CO)2(NCMe)2] and bidentate –diimine ligands, such as N-(n-propyl)-2-pyridylphenylmethanimine (C5H4NCR=N(CH2)2CH3, R=Ph), and some of them have been immobilized in MCM-41], affording some examples of heterogeneous catalysts more active than their homogeneous counterparts in olefin epoxidation [1, 2]. Following such alluring ability we studied the immobilization of the complex [MoBr(η3-C3H5)(CO)2(L)], where L is C5H4NCR=N(CH2)2CH3, R=Ph (pycaPh, a in Fig. 1). For this purpose, we synthesized a ligand with the anchor group –Si(OEt3) (pycaPhSi, b in Fig. 1), and adopted an immobilization methodology previously tested [3], in which the functionalized ligand reacted with SiOH groups of an MCM-41 support matrix. The supported ligand reacted then with [MoBr(η3-C3H5)(CO)2(NCMe)2] yielding a new MCM type material containing Mo(II), [MoBr(η3-C3H5)(CO)2(L)]-MCM (b).

The ligands and complexes were characterized by IR and NMR spectroscopy, and elemental analysis, and the materials by N2 adsorption, X-ray powder diffraction, DRIFT, solid state NMR spectroscopy, and Elemental analysis. The catalytic properties of the complex and material were tested in the oxidation of S-(-)-limonene , geraniol, 1-octene, cis-hexen-1-ol, trans-hexen-1-ol, cis-cyclooctene, styrene, in the presence of t-butylhydroperoxide. For instance, the homogeneous catalyst converted 100% of cis-cyclooctene selectively in the epoxide, while the conversion of styrene was only 40% with 35.5% selectivity for the epoxide. [1] Vasconcellos-Dias, M., Nunes, C. D., Vaz, P. D., Ferreira, P., & Calhorda, M. J., European Journal of Inorganic Chemistry, 2007, 18, 2917–2925. [2] Vasconcellos-Dias, M., Nunes, C., Vaz, P., Ferreira, P., Brandao, P., Felix, V., & Calhorda, M.J. Journal of Catalysis, 2008, 256, 301–311. [3] Gimenez, J., Nunes, C. D., Vaz, P. D., Valente, A. a., Ferreira, P., & Calhorda, M. J. Journal of Molecular Catalysis A: Chemical, 2006, 256, 90–98.

Figure 1 - Representation of pycaPh (a) and pycaPhSi (b) ligands and the complex

Posters

86

P44 - MOLYBDENUM COMPLEXES WITH PYRIDINE DERIVATIVES AS CATALYSTS IN OXIDATION REACTIONS

Marta S. Saraiva1, Maria José Calhorda1

1Centro de Química e Bioquímica, DQB, FCUL, Campo Grande, 1749-016 Lisboa, Portugal.

[email protected]

Molybdenum(II) complexes [MoBr(3-C3H5)(CO)2(L)] (L=L1, C1; L=L2, C2) were synthesized from the reaction of the precursor [MoBr(3-C3H5)(CO)2(CH3CN)2] and the bidentate ligands 2,9-di-tert-butyl-2,2’-bipyridyl (L1), 1,10-phenanthroline (L2) by the substitution of the acetonitrile ligands. A second family of complexes [Mo(3-C3H5)(CO)2(L)(L’)] was obtained through the reaction of the complexes C1 and C2 with TlPF6

- in the presence of pyridines (L’). The cationic complexes were characterized by FTIR, 1H and 13C NMR and elemental analysis.

Figure 1: Complexes [MoBr(3-C3H5)(CO)2(L)] and [Mo(3-C3H5)(CO)2(L)(L’)] (L = 2,9-ditertbutyl-2,2’-

bipyridyl (L1), 1,10-phenanthroline (L2); L' = pyridine derivatives; R = CH3, CHO ).

All the complexes were tested as homogeneous catalysts in the oxidation of olefins and alcohols, such as cis-cyclooctene, styrene, geraniol, cis-3-hex-1-ol, trans-2-hex-1-ol and R(+)-limonene, using tert-butyl-hydroperoxide as the oxidant. These studies were carried out in order to determine the influence of the pyridine ligands on the complexes catalytic activity. Acknowledgements: We thank Fundação para a Ciência e Tecnologia for financial support (PEst-OE/QUI/UI0612/2013). MSS thanks FCT for Grant SFRH / BPD / 88082 / 2012.

[1] Saraiva, M.S.; Quintal, S.; Portugal, F. C. M.; Lopes, T. A.; Félix, V.; Nogueira, J. M. F.; Meireles, M.; Drew, M. G. B.; Calhorda, M. J., J. Organomet. Chem. 2008, 693, 3411-3418.

Posters

87

P45 - RUTHENIUM(II) COMPLEXES BEARING CARBOHYDRATE AND NUCLEOSIDE DERIVATIVE LIGANDS

Pedro R. Florindo and Ana Cristina Fernandes

Centro de Química Estrutural,Instituto Superior Técnico, Universidade de Lisboa Av. Rovisco Pais, 1, 1049-001 Lisboa, Portugal

Email: [email protected]

Cisplatin and its derivatives are still used as chemotherapeutic drugs in the treatment of about 70% of cancer cases worldwide, despite problems such as toxicity and drug resistance.Among the metal complexes studied as alternative anticancer metallodrugs, ruthenium compounds show remarkable features, such as low general toxicity, the ability to mimic iron and stronger affinity for cancer tissues over normal tissues [1]. As part of our on-going effort to produce a library ruthenium(II) complexes bearing bioactive ligands [2], we here report the synthesis and characterization of five new cyclopentadienyl-ruthenium(II) complexes of general formula [(η5-C5H5)Ru(PPh3)(L)][PF6] (Fig. 1), where L is a N,N-bidentate ligand bearing a carbohydrate or nucleoside derivative. Our approach intends to take advantage of the improved sugar consumption from cancer cells and of nucleoside transporters, glycoproteins that mediate nucleoside uptake through cell membranes, thus aiming for ruthenium organometallic drugs with improved cytotoxic properties.

O N

HO

NH

O

O

X

O N

HO

NH

O

OO OMe

OHHOOH

O OMe

HOOH

OH

NN

N

N

R

Ru

[PF6]

PPh3

PPh3

Cl RuPPh3

RN

NNN

TlPF6

R =

X= CH3, I Figure 1: Ruthenium complexes bearing biocompatible ligands.

Acknowledgements: The authors thank FCT for financial support (PTDC/QUI-QUI/110532/2009, PEst-OE/QUI/QUI0100/2013) and the NMR Network (IST-Node) for facilities. [1] G. Süss-Fink,Dalton Trans.2010, 39, 1673-1688. [2] Florindo, P.; Marques, I.J.; Nunes, C.D.;Fernandes, A.C.; J. Organomet. Chem. 2013, http://dx.doi.org/10.1016/j.jorganchem.2013.09.004

Posters

88

P46 – SYNTHESIS AND CHARACTERIZATION OF NOVEL ZINC(II) AND COPPER(II)

COMPLEXES WITH CARBOHYDRATE DERIVATIVES

Tiago A. Fernandes1, Pedro R. Florindo,1 Ana C. Fernandes1

1 Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa Av. Rovisco Pais, 1, 1049-001 Lisboa, Portugal E-mail: [email protected]

The development of new biologically active organometallic or coordination complexes is a challenge for inorganic chemists. Amongst the non-platinum active compounds there is a great interest in the synthesis of metal-based drugs containing essential elements such as copper and zinc. Copper plays a key role in biological processes and its complexes are known to exhibit antitumor activity. Besides this, it has also been demonstrated that copper accumulates in tumors due to selective permeability of cancer cell membranes to copper compounds. Zinc is the most abundant trace intracellular element and plays an important role in both genetic stability and function. Appending a carbohydrate in an coordination compound has the ability to reduce toxicity, improve solubility and molecular targeting to a wide variety of metal-based drugs. In continuation of our work to prepare carbohydrate–metal complexes,[1,2] in this communication we describe the synthesis of novel zinc(II) and copper(II) complexes containing carbohydrates from the reaction between zinc or copper halides (chloride or bromide) with a ciano or tetrazole carbohydrate derivative.[3]

Figure 1: Arial 10, centered, line spacing 1.0.

Acknowledgements: Financial support by FCT-Fundação para a Ciência e Tecnologia (PTDC/QUI-QUI/110532/2009, PEst-OE/QUI/QUI0100/2013) and the NMR and MS (IST-Node) Networks for facilities. [1] Ana C. Fernandes, Carlos C. Romão, Beatriz Royo, Journal of Organometallic Chemistry 2003, 682, 14-19. [2] Pedro Florindo, Inês J. Marques, Carla D. Nunes, Ana C. Fernandes, Journal of Organometallic Chemistry 2013 (accepted), DOI:10.1016/j.jorganchem.2013.09.004 [3] Fahmi Himo, Zachary P. Demko, Louis Noodleman and K. Barry Sharpless; J. Am. Chem. Soc. 2003, 125, 9983-9987.

Scheme 1

RN3 , ZnCl2

CH2 Cl2 , isopropanol, 100ºC

Posters

89

P47 - STRAIGHTFORWARD APPROACH TO NOVEL CHIRAL ACYCLIC DIAMINOCARBENE SPECIES VIA THE ADDITION OF

AMINES TO METAL-BOUND ISOCYANIDES

T. B. Anisimova1, M. F. C. Guedes da Silva1, A. J. L. Pombeiro1, V. Yu. Kukushkin2, K. V. Luzyanin1,2

1 Instituto Superior Técnico, University of Lisbon, Av. Rovisco Pais, Lisbon, 1049-001, Portugal

2 Department of Chemistry, St. Petersburg State University, Universitetskiy Prospect, 26, Saint-Petersburg, 198504, Russian Federation

e-mail: [email protected] In pursuit of our studies, we explored an approach to acyclic diaminocarbenes (ADCs) – acyclic analogues of N-heterocyclic carbenes – based on the nucleophilic addition of chiral amines to metal-bound isocyanides [1]. Thus, we found that the integration between isocyanides in cis-[PdCl2(CNR1)2] (R1 = Xyl, Cy) and corresponding enantiopure amines H2N*CHR2R3 furnishes novel chiral aminocarbene complexes cis-[PdCl2(CNR1)(C(NH*CHR2R3)NHR1)] [R1 = Xyl, Cy] in good (76–95%) isolated yields (12 examples).

All compounds were fully characterized by elemental analyzes (C, H, N), ESI-MS, IR, 1D (1H and 13C{1H}) and 2D (1H,1H-COSY, 1H,13C-HMQC/1H,13C-HSQC, 1H,13C-HMBC) NMR spectroscopic techniques, and by X-Ray diffraction for three complexes. It was found that absolute configuration of the chiral center is retained in the course of the metal-mediated coupling [2]. This work has been partially supported by the Fundação para a Ciência e a Tecnologia (FCT), Portugal (through the research projects PTDC/QUI-QUI/109846/2009, PEst-OE/QUI/UI0100/2013 and Ph.D. Grant for TBA SFRH/BD/81459/2011) and by the Russian Fund for Basic Research (grants 13-03-12411-ofim and 14-03-01005). References [1] a) Luzyanin, K. V.; Tskhovrebov, A. G.; Carias, M. C.; Guedes da Silva, F. M. C.; Pombeiro, A. J. L.; Kukushkin, V. Yu. 2009, 28, 6559; b) Boyarskiy, V. P.; Luzyanin, K. V.; Kukushkin, V. Yu. Coord. Chem. Rev. 2012, 256, 2029. [2] Anisimova, T. B.; Guedes da Silva, F. M. C.; Pombeiro, A. J. L.; Kukushkin, V. Y.; Luzyanin, K. V. unpublished results.

Posters

90

P48 - SYNTHESIS AND CHARACTERIZATION OF BIOCOMPATIBLE MAGNETIC IONIC LIQUIDS

Andreia Forte1, Fernando Pina1, Luís C. Branco 1

1 REQUIMTE, Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade

Nova de Lisboa, 2829-516 Caparica, Portugal ; email: [email protected]

Ionic Liquids (ILs) are novel organic salts with low melting point (<100ºC) and exceptional physicochemical properties such as low vapour pressure (feature that allows them to include in Green Chemistry), high thermal and chemical stability, high ionic conductivity, wide electrochemical window, among others.[1] The discovery of magnetic ILs (MILs) was only recently reported which are primarily based on high-spin d5 Fe(III) in the form of tetrachloro- or tetrabromoferrate (III) anions combined with various counter cations [2]. Most of the cations of the MILs have been limited to the traditional alkylimidazolium, tetraalkylammonium and tetraalkylphosphoniums. Depending on the cation structure and their alkyl chain length can be possible to change different physical properties such as viscosity, density, conductivity and magnetic susceptibility. Recent magnetic and luminescent ILs have been reported with other paramagnetic ions including ruthenium and europium[3-5]. Potential applications of MILs have been described mainly for separations processes as well as chiral extraction and enrichment of chiral compounds. Herein, some MILs based on Fe(III), Mn(II), Gd(III) and Tb(III) complexes as anions combined with biocompatible choline derivatives cations have been presented (Figure 1). Also, novel azamacrocycle ligands have been prepared for the complexation with specific paramagnetic and/or luminescent metals in order to develop another class of MILs or molten salts.

Figure 1: Structure of synthesized biocompatible magnetic ionic liquids

All prepared compounds were completely characterized by 1H, 13C NMR, FTIR, UV-Vis spectroscopy, magnetic susceptibility and solubility profiles.

Acknowledgements: The authors would like to thanks to FCT-MCTES (PTDC/CTM-NAN/120658/2010 project) and Solchemar.

[1] Kokorin, A.; Ionic Liquids: Applications and Perspectives, InTech, 2011. [2] Takagi, Y.; A, Kusunoki, F. Y.; Yoshida, A. Y.; Tanaka, B. C. H.; Saito, B. G.; Katagiri, B. C. K.; Oshiki, D.; and Oshiki, T., Aust. J. Chem. 2012, 65, 1557. [3] .Branco, A.; Branco, L. C.; Pina, F. Chem. Commun. 2011, 2300. [4] Gago, S.; Cabrita, L.; Lima, J. C.; Branco, L. C.; Pina, F. Dalton Trans. 2013, 42, 6213. [5] Pereira, C. C. L.; Dias, S.; Coutinho, I.; Leal, J. P.; Branco, L. C.; Laia, C. A. T. Inorg. Chem. 2013, 52, 3755.

N

R 2

R 1 R 1

O H

M X n

R 2 = C 2 H 5 , C 4 H 9 , C 5 H 1 1 O 2 , C 3 H 7 O R 1 = C H 3 , C 2 H 5

M ( P a r a m a g n e t i c M e t a l ) = F e , M n , G d , T b

Posters

91

P49 – SYNTHESIS, STRUCTURAL ANALYSIS AND ANTIMICROBIAL ACTIVITY OF NEW SILVER BIOMOFS DRIVEN BY

1,3,5-TRIAZA-PHOSPHAADAMANTANE-7-SULFIDE (PTA=S)

Sabina W. Jaros 1, Piotr Smoleński 2, M. Fátima C. Guedes da Silva 1,3, Magdalena Florek 4, Jarosław Król 4,

Zdzisław Staroniewicz 4, Alexander M. Kirillov1 and Armando J. L. Pombeiro1

1Centro de Química Estrutural, Complexo I, Instituto Superior Técnico, Universidade de Lisboa,

Portugal. 2Faculty of Chemistry, University of Wrocław, Poland

3Universidade Lusófona de Humanidades e Tecnologias, ULHT Lisbon, Portugal 4Department of Veterinary Microbiology, Wroclaw University of Environmental and Life

Sciences, Wroclaw, Poland. Email: [email protected], [email protected], [email protected]

The research on metal-organic frameworks (MOFs) or coordination polymers (CPs) is nowadays a hot topic that spreads along diverse areas of chemical science, with an emphasis on crystal engineering, coordination and materials chemistry. The design of bioactive framework materials through the search for new types of biorelevant organic linkers or spacers capable to bind bioactive metal nodes has emerged in recent years as an attractive research direction [1]. In particular, the water-soluble aminophosphine 1,3,5-triaza,7-phospaadamantane (PTA) and its various cagelike derivatives represent an interesting class of ligands in aqueous organometalic chemistry owing to the promising applications of their metal complexes as antimicrobial and antitumor agents. The interest in probing 1,3,5-triaza-7-phosphaadamantane-7-sulfide (PTA=S) as a multiple N,S-building block is governed by the fact that this cagelike compound with up to four potential coordination sites was barely applied in coordination chemistry [2] Hence, we report the self-assembly generation, structures, topological analysis and antimicrobial activity of two distinct 3D silver-organic frameworks, [Ag(µ3-PTA=S)]n(NO3)n·nH2O (1) and [Ag4(µ4-PTA=S)(µ5-PTA=S)(µ2-SO4)2(H2O)2]n·2nH2O (2), which reveal unprecedented N2S-coordination modes of PTA=S and represent the first MOFs derived from this cagelike building block. Apart from representing the first MOFs derived from PTA=S, the compounds 1 and 2 display antibacterial and antifungal activities studied in vitro against E. coli, P. aeruginosa, S. aureus, and C. albicans. [2]

Acknowledgements: This work was supported by the Foundation for Science and Technology (FCT) (projects PTDC/QUI-QUI/121526/2010 and PEst-OE/QUI/UI0100/2011), Portugal.

[1] Horcajada, P.; Gref, R.; Baati, T.; Allan, P. K.; Maurin, G.; Couvreur, P.; Férey, G.; Morris, R. E.; Serre, C. Chem. Rev. 2012, 112, 1232. [2] Jaros, S. W.; Smoleński,P.; Guedes da Silva, M. F. C.; Florek, M.; Król, J.; Staroniewicz, Z.; Pombeiro, A. J. M.; Kirillov. A. M. CrystEngComm. 2013, 13, 8060.

Posters

92

P50 – PHYSICOCHEMICAL CHARACTERIZATION OF 20TH CENTURY PHOTOGRAPHY NEGATIVES

Cátia Coelho1, Cátia Relvas1, Sónia Costa1,

Ana T. Caldeira1,2, Teresa Ferreira1,2*

1HERCULES - Cultural Heritage Studies and Safeguard Centre

2Évora Chemistry Centre, Universidade de Évora, 7000-676 Évora, Portugal *[email protected]

Photographic documents represent an important component of the historic and cultural heritage, because they have ethnographic, social and artistic values. Photographic negative supports are composed of at least three components: a rigid support (plastic or paper), an image-forming material (black and white images are formed by metallic silver particles) and a binder that in 20th century documents is mainly based on gelatin. Gelatin silver based positive prints and negative films were the dominant photographic process nearly from the period of their introduction in the 1880s until the 1960s. The gelatin silver or black-and-white print and films represented, in fact, a primary form of visual documentation in the 20th century [1]. Nevertheless, understanding the chemical and physical properties of each type of negative, as well as the kind of processing they may have undergone, is the first step towards preservation [2]. In this work 4 photographic negatives of a private collection were studied. Non-destructive characterization of photographs is an important tool for studying, cataloging and preserving them [3]. Photography and detailed macro-photography were done under standard light, UV/Vis fluorescence light and raking light. Morphological aspects were also evaluated by optical microscopy and variable pressure scanning electron microscopy with energy dispersive X-ray spectrometry (VP-SEM/EDS). For information about composition, besides from EDS, X-ray fluorescence (XRF) spectroscopy and Fourier transform infrared (FT-IR) spectroscopy in attenuated total reflexion and specular reflectance modes were used. Acknowledgements: The authors wish to acknowledge Francisco Almeida for the photographic negatives collection. References [1] Sclocchi, M.; Damiano, E.; Maté, D.; Colaizzi, P.; Pinzari, F. Intern. Biodeter. Biodegrad. 2013, 84, 367 – 371. [2] Valverde, M F. Photographic negatives. Nature and evolution processes, 2nd ed., George Eastman House and Image Permanence Institute, Rochester, USA. 2005. [3] Neiva, A.; Marcondes, M.; Pinto, H.; Almeida, P. Radiat. Phys. Chem. 2014, 95, 378 – 380.

Posters

93

P51 - PORPHYRIN-CHALCONE TYPE DERIVATIVES AS NEW RED-FLUORESCENT MATERIALS FOR METAL ION PROBES

Nuno M. M. Moura,1,2,3 Cristina Núñez,2,3,4* M. Amparo F. Faustino,1 José A. S. Cavaleiro,1 M. Graça P. M. S. Neves,1 José Luis Capelo,2,3 Carlos Lodeiro2,3*

1Chemistry Department and QOPNA, University of Aveiro, Campus Universitário Santiago,

3810-193 Aveiro, Portugal. 2BIOSCOPE Group, REQUIMTE-CQFB, Chemistry Department, Faculty of Science and

Technology, University NOVA of Lisbon, 2829-516 Monte de Caparica, Portugal. 3ProteoMass Scientific Society. Madan Parque. Rua dos Inventores. 2825-182. Caparica.

Portugal. 4Ecology Research Group, Department of Geographical and Life Sciences, Canterbury Christ

Church University, CT1 1QU Canterbury, United Kingdom.

The biological importance of porphyrins and their role in the development of catalysts, new electronic materials, drugs and sensors are responsible for the considerable work involving this type of derivatives [1]. In particular, these compounds are considered attractive candidates to be used as fluorescent and colorimetric chemosensors due to their remarkable photophysical properties, such as large Stokes shifts and relatively long excitation (>400 nm) and emission (>600 nm) wavelengths [2]. The relevance of zinc, a widespread metal ion with significant functions on biological and environmental fields [3] and the toxicity of heavy metallic ions like mercury, cadmium or lead for living organisms, [4] makes the design of synthetic receptors for these metal ions an important issue to be considered. In this communication, we present the sensorial ability of a new series of porphyrins containing an unsaturated unit in one of the β-pyrrolic positions towards the soft metal ions Zn2+, Cu2+, Hg2+, Cd2+ and Ag+. [5]

Figure 1: Porphyrin-chalcone type derivative titration with Zn2+.

Acknowledgements: Authors are grateful to the Universidade de Aveiro, Fundação para a Ciência e a Tecnologia (FCT), European Union, QREN, FEDER and COMPETE for funding the QOPNA research unit (project PEst-C/QUI/UI0062/2013). We acknowledge the Portuguese National NMR Network (RNRMN), supported by funds from FCT, Scientific PROTEOMASS Association (Portugal) and REQUIMTE (PESt-C/EQB/La0006/2013) for general. N. M. M. M. thanks FCT/MEC for her Post-Doctoral grant SFRH/BPD/84216/2012. C. N. thanks the Xunta de Galicia (Spain) for her postdoctoral contract (I2C program).

[1] Handbook of Porphyrin Science, Kadish, K. M.; Smith, K. M.; Guilard, R. (Eds.) Vols. 10-12, World Scientific Publishing Co: Singapore, 2010. [2] Li, C.-Y.; Zhang, X.-B.; Dong, Y.-Y.; Ma, Q.-J.; Han, Z.-X.; Zhao, Y.; Shen, G.-L.; Yu, R.-Q. Anal. Chim. Acta 2008, 616, 214. [3] Partha, R.; Dhara, K.; Manassero, M.; Ratha, J.; Banerjee, P. Inorg. Chem. 2007, 46, 6405. [4] Yang, Y.; Jiang, J.; Shen, G.; Yu, R. Anal. Chim. Acta 2009, 636, 83. [5] N. Moura et al, Submitted 2014.

Posters

94

P52 - OPTIMIZATION OF MICROWAVE-ASSISTED RHODIUM CATALYSED HYDROFORMYLATION

REACTION WITH EXPERIMENTAL DESIGN

Marta Pineiro,1 Liliana Damas,1 Ana R. Almeida,1 Lucas D. Dias,2 Carlos J. P. Monteiro,1 Mário J. F. Calvete,1

Mariette M. Pereira,1 Alberto A. C. C. Pais,1 Gilberto Aquino2

1Universidade de Coimbra, Departamento de Química,3004-535 Coimbra, Portugal

2Universidade Estadual de Góias, Faculdade de Farmácia, Anapolis, Brasil ([email protected])

Rhodium catalysed hydroformylation of alkenes is one of the most powerful methods to transform, in just one step, a carbon-carbon double bond into an aldehyde with an extra carbon atom.[1] This is a reaction with 100% atom economy but the demand for development of greener processes involving lower energy consumption and lower pressures is still a great challenge. There are in the literature just few examples of the use of microwave irradiation in hydroformylation reactions. [2] In this communication we present a 22 factorial design for the optimization of the reaction conditions of microwave-assisted rhodium catalysed hydroformylation of styrene, using temperature and time as factors, at relatively low pressure (10 bar) (Figure 1). The experiments were carried out on a 10 mL vial of a Discover microwave pressure oven connected with a gas addition system to a cylinder of CO and H2, using Rh/triphenylphosphine as catalyst. The effect of time of irradiation, temperature and solvent will be discussed.

HYDROFORMYLATION

Rh/PPh3

35 % of conversion89 % of regioselectivity

CHO

10 bar65 ºC

MW

Figure 1: Styrene hydroformylation under microwave conditions.

Acknowledgements: The authors are thankful to CEM corporation and FCT for financial support (FCT/QREN/FEDER/COMPETE, PTDC/QUI-QUI/112913/2009). A. R. Almeida and C. J. P. Monteiro also thank to FCT for PhD grant SFRH/BD/73190/2010 and post-doc grant SFRH/BPD/86525/2012, respectively. The Coimbra Chemistry Centre is supported by the Fundação para a Ciência e a Tecnologia (FCT), Portuguese Agency for Scientific Research, through the project PEst-OE/QUI/UI0313/2014.

[1] a) Almeida, A. R.; Peixoto, A. F.; Calvete, M. J. F.; Gois, P. M. P.; Pereira M. M. Curr. Org. Synth. 2011, 8, 764-77. b) Neves, A. C. B; Calvete, M. J. F.; Pinho e Melo, T. M. V. D.; Pereira, M. M. Eur. J. Org. Chem. 2011, 6309-6320. [2] Elena, P.; Mann, A; Schoenfelder, A.; Rota, A.; Taddei, M. Org. Lett., 2006, 8, 3725-3727.

Posters

95

P53 - REDUCTION OF CARBONYL COMPOUNDS CATALYZED BY OXO-RHENIUM COMPLEXES

J. R. Bernardo1, P. R. Florindo1, M. Wolff2, B. Machura,2 and A. C. Fernandes1

1 Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal

2 Department of Crystallography, Institute of Chemistry, University of Silesia, 9th Szkolna St., 40-006 Katowice, Poland Email: [email protected]

The synthesis of alcohols by reduction of carbonyl compounds is one of the most important reactions in organic synthesis. Among the large variety of reagents reported, high valent oxo-rhenium complexes have emerged, in the last years, as an efficient class of catalysts for the reduction of carbonyl compounds.1

In continuation of our studies about the use of oxo-complexes in organic reductions,1

in this communication we describe the catalytic activity of several oxo-rhenium complexes containing heterocyclic ligands,2-5 as catalysts for the reduction of aldehydes and ketones, using phenylsilane as reducing agent.

Figure 1: Reduction of carbonyl compounds catalyzed by oxo-rhenium complexes.

Acknowledgements: This research was supported by FCT through projects PTDC/QUI-QUI/110080/2009 and PEst-OE/QUI/UI0100/2013. J. R. Bernardo (SFRH/BD/90659/2012) and P. R. Florindo thank FCT for grants. [1] Sousa, S. C. A.; Cabrita, I.; Fernandes, A. C. Chem. Soc. Rev. 2012, 41, 5641. [2] Machura, B.; Wolff, M.; Kruszynski, R.; Kusz, J. Polyhedron, 2009, 28, 1211. [3] Machura, B.; Kruszynski, R.; Kusz, J. Polyhedron, 2008, 27, 1679. [4] Machura, B.; Kruszynski, R.; Kusz, J. Polyhedron, 2007, 26, 3455. [5] Machura, B.; Wolff, M.; Benoist, E.; Schachner, J. A.; Mösch-Zanetti, N. C. Dalton Trans., 2013, 42, 8827.

Posters

96

P54 – SOLID RESIDUES PRODUCED FROM PINE GASIFICATION AS PERCURSORS OF

ACTIVATED CARBONS FOR CATALYST SUPPORTS

Margarida Galhetas1,2, Ana S. Mestre1, Helena Lopes2, Ana P. Carvalho1

1Departamento de Química e Bioquímica and CQB, Faculdade de Ciências da Universidade

de Lisboa, 1749-016 Lisboa, Portugal. 2LNEG, Estrada do Paço do Lumiar, 22, 1649-032 Lisboa, Portugal.

[email protected]

Gasification, an alternative process to combustion, has as main objective the production of syngas that may be used in turbines for energy generation. During the process there is also the production of solid residues that are collected in distinct areas of the reactor: char (removed from the bed), and fly ash (removed from the cyclone). These solid residues present high levels of carbon content (> 70 %) which allowed our group to recently envisage their use as, for instance, precursors of materials to be used in adsorption or catalytic processes. In this line, the aim of the present work was to study the influence of several experimental parameters like, type of residue (char and fly ash), temperature and activating agent amount, in order to establish the experimental conditions that lead to the higher porosity development. The activated carbons were prepared by chemical activation (with K2CO3) of char and fly ashes from pine gasification, at different temperatures (800 and 900 ºC) and residue:K2CO3 weight ratios (1:1 and 1:3). The influence of the temperature and K2CO3 amount was evaluated and the results revealed that, for both type of residues, the use of higher temperature and K2CO3 amount lead to higher porosity development, and that the temperature seemed to be the parameter that mostly affected the porosity development. Materials with ABET attaining 1100 m2g-1 with preparation yields of between 25 and 56% were obtained. The ash content of the materials reached values > 50 % (w/w), being composed by TiO2 and Fe2O3, as it was demonstrated by the X-ray diffraction patterns. The characteristics of the materials allow us to consider their use as support of catalytic active species (e.g. TiO2 or ZnO). Thus, in a future study the solids will be used for the preparation of composites with nanosized metal oxides with photocatalytic properties. Acknowledgements: Margarida Galhetas and Ana S. Mestre thank FCT for Ph.D. grant (SFRH/BD/69909/2010) and a Post-Doc grant (SFRH/BPD/86693/2012), respectively. FCT is also acknowledged for the pluriannual funding of CQB (Project PEst-OE/QUI/UI0612/2013).

[1] Galhetas, M., Mestre, A.S., Pinto, M.L., Gulyurtlu, I., Lopes, H., Carvalho A.P., Chemical Engineering Journal 2014, 240, 344-351.

Posters

97

P55 - ORGANIC-INORGANIC HYBRID MATERIALS FOR NANOTHERMOMETRY

Carlos D. S. Brites1, Patricia P. Lima1, Nuno J. O. Silva1, Angel Millan2, Vitor S. Amaral1, Fernando Palacio2, Luís D. Carlos1

1Departamento de Física & CiCECO, Universidade de Aveiro,

Campus Santiago 3810-193 Aveiro, Portugal 2Departamiento de Física de la Matéria Condensada & ICMA, Universidad de Zaragoza,

Pedro Cerbuna 50009, Zaragoza, Spain [email protected]

Non-invasive precise thermometers working at the nanoscale with high spatial resolution, where the conventional methods are ineffective, have emerged over the last years as a very active field of research. This has been strongly stimulated by the numerous challenging requests arising from nanotechnology and biomedicine [1]. In this communication we present luminescent ratiometric nanothermometers based on a magnetic core coated with an organosilica shell co-doped with Eu3+ and Tb3+ chelates. The design of the hybrid host and chelate ligands permits the working of the nanothermometers in a nanofluid at 293–320 K with an emission quantum yield of 0.38, a maximum relative sensitivity of 1.5%·K-1 at 293 K and a spatio-temporal resolution (constrained by the experimental setup) of 64 μm/150ms, and 0.4 K temperature uncertainty [2]. Using the same ligands, a molecular thermometer involving a di-ureasil organic-inorganic hybrid thin film co-doped with Eu3+ and Tb3+ tris-(β-diketonate) chelates is used to obtain the temperature map of a FR4 printed wiring board (Figure 1) with spatio-temporal resolutions of 0.42 μm/4.8 ms and 0.2 K temperature uncertainty [3].

Figure 1: Pseudo-color temperature maps reconstructed from the emission of organic-inorganic hybrid nanothermometer along the directions A and B indicated the inset. The shadowed areas correspond to

the position of the copper tracks. Acknowledgements: CDS Brites thanks FCT for a grant (SFRH/BPD/89003/2012). [1] Brites, C. D. S.; Lima, P. P.; Silva, N. J. O; Millan, A.; Amaral, V. S.; Palacio, F.; Carlos, L. D. Nanoscale 2012, 4, 4779-4829. [2] Brites, C. D. S.; Lima, P. P.; Silva, N. J. O; Millan, A.; Amaral, V. S.; Palacio, F.; Carlos, L. D. Nanoscale 2013, 5, 7572-7580. [3] Brites, C. D. S.; Lima, P. P.; Silva, N. J. O; Millan, A.; Amaral, V. S.; Palacio, F.; Carlos, L. D. Frontiers in Chemistry 2013, 9, 1-6.

Posters

98

P56 – СOMPOSITE MATERIALS CONTAINING Pt@Fe2O3 NANOPARTICLES

Marina Biriukova, Gleb Yurkov

1A.A.Baikov Institute of Metallurgy and Materials Science of the Ruaasian Academy of

Science, Leninsky 49, Moscow 119991, Russia. E-mail: [email protected] 2All-Russian Institute of aviation materials, Radio str. 17, Moscow 105005, Russia

Noble metal nanoparticles draw special attention because of their unique optical, electrical, magnetic, physico-chemical and chemical propeties. Creation of nanoparticulate noble metal alloys, such as FePt, are of particular interest as they can be used in magnetic information storage systems. Bimetallic nanoparticles are known to have dufferent structures, ranging from solid solutions to more complex «cluster-in-cluster» systems, layered structures and «core-shell» nanoparticles. Bimetallic nanoparticles are of special interest lately due to their possible use in biosensors, electronics, optoelectronics, catalysis, etc. The presense of a (usually, oxide) shell on the surface of nanoparticles increases their stability in extreme conditions, alters their optical and catalytical properties. Encapsulation of metallic nanoparticles by a thin shell is often used for attachment of functional groups to nanoparticles or control of their electrical charge distribution, which is important for creation of nanostructures; oxide or polymeric shells are normally used for this purposes. Noble metal nanoparticles are usually prepared using chemical methods because most noble metal ions can be readily reduced, while these metals are difficult to evaporate (which reduces the interest in application of physical methods for preparation of their nanoparticles). Specific methods for preparation of platinum nanoparticles and their properties are described alsewhere. Herein we describe a material consisting of Pt@Fe2O3 nanoparticles immobilised in low density polyethylene (LDPE) prepared using the method described elsewhere. The structure of the nanoparticles was determined using a number of physico-chemical methods, and a study of their biocidal properties was also performed. A composite material prepared by thermal decomposition of chroloplatinic acid with further addition of the nanoparticles to a low density polyethylene solution-melt in hydrocarbon oil contains core-shell Pt@Fe2O3 nanoparticles with the average diameter of 4.2 nm and narrow unimodal size distribution. All the samples studied exhibit antibacterial activity against both Gram-positiove and Gram-negative strains.

The work was financially supported by the RFBR grants №14-08-31435 and the RAS Presidium program P-8.

Posters

99

P57 - NiII, CuII AND ZnII COMPLEXES WITH A STERICALLY HINDERED SCORPIONATE LIGAND (TpmsPh) AND CATALYTIC APPLICATION IN THE

DIASTEROSELECTIVE NITROALDOL (HENRY) REACTION

Bruno G.M. Rocha,1 Tatiana C.O. Mac Leod,1 M. Fátima C. Guedes da Silva,1,2 Konstantin V. Luzyanin,1 Luísa M.D.R.S. Martins,1,3 Armando J.L. Pombeiro1

1Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049–001 Lisboa, Portugal. E-mail: [email protected]

2Universidade Lusófona de Humanidades e Tecnologias, ULHT Lisbon, Campo Grande 376, 1749-024 Lisboa, Portugal.

3Chemical Engineering Department, ISEL, R. Conselheiro Emídio Navarro, 1959-007 Lisboa, Portugal.

This work aims to contribute to the development of the C-scorpionate coordination chemistry by synthesizing new late transition metal (Ni, Cu or Zn) complexes with the sterically hindered and water soluble tris(3-phenylpyrazol-1-yl)methanesulfonate (TpmsPh) ligand (Scheme 1). The use of this ligand favours the synthesis of half-sandwich complexes preferably to the full sandwich ones. Moreover, the bulky scorpionate (TpmsPh)– adapts its coordination mode to the electronic and steric preferences of the NiII, CuII or ZnII centre showing different coordination modes (Scheme 1). The ZnII and CuII complexes, are effective catalyst precursors for the diastereoselective nitroaldol reaction, leading to β-nitroalkanols in high yield (up to 99%), with predominance of the anti diastereoisomer. The combination of CuII or ZnII with the TpmsPh ligand provides a Lewis acid metal centre (capable to promote the nitroethane deprotonation and the electrophilicity of benzaldehyde) and a Brönsted base (able to assist the proton loss from nitroethane) that is favorable for that reaction.

Scheme1 .TpmsPh coordination modes in the synthetized complexes

Acknowledgements: This work has been partially supported by the Fundação para a Ciência e a Tecnologia (FCT), Portugal, and its PPCDT program (FEDER funded) through the research projects PTDC/QUI-QUI/102150/2008, PTDC/QUI-QUI/109846/2009, PTDC/QUI-QUI/119561/2010, PTDC/EQU/EQU-122025-2010 and Pest-OE/QUI/UI0100/2013. BGMR is also grateful to CATSUS PhD program (PD/00248/2012). [1] Naïli, H.; Hajlaoui, F.; Mhiri, T.; Mac Leod, T.C.O.; Kopylovich, M.N.; Mahmudov, K.T.; Pombeiro, A.J.L.; Dalton Transactions, 2013, 42(2), 399-406.

Posters

100

P58 – CHARGE TRANSFER SALTS BASED ON α–DT-TTF

R.A.L. Silva1, A.I.S. Neves2, E.B. Lopes1, I.C. Santos1, M.L. Afonso3, J.T. Coutinho1, L.C.J. Pereira1, C. Rovira4, M. Almeida1, D. Belo1

1Center of Nuclear Science and Technology - C2TN, IST/CFMCUL, University of Lisbon,

Nuclear and Technological Campus, P-2695-066 Bobadela LRS, Portugal. Email: [email protected]

2INESC – MN, 1000-029 Lisboa, Portugal 3Instituto de Telecomunicações, Polo de Lisboa, Av. Rovisco Pais,

P-1049-001 Lisboa, Portugal 4Institut de Ciència des Materials de Barcelona (CSIC), Campus UAB, E-08193 Bellaterra,

Spain

The recent report of an efficient synthesis of the donor α-DT-TTF (alpha-dithiophene-tetrathiafulvalene) [1] allowed the preparation of a large series of charge transfer salts based on this donor which had previously remained almost entirely unexplored. In this communication we report the synthesis and characterization of several charge transfer salts of this donor with a variety of anions and their properties are compared with those of the corresponding salts with other thiophenic TTF donors. (α-DT-TTF)2[Au(mnt)2] and (α-DT-TTF)2[Au(i-mnt)2] share the same donor ladder structure of the DT-TTF and ETT-TTF analogues. In spite of the disorder in the position of the thiophenic ring these compounds present properties of a spin-ladder system with a room temperature conductivity, RT, of ~2 S/cm and ~7.6x10-2 S/cm, respectively [2]. With (α-DT-TTF)2[Co(mnt)2], which shows a RT~7 S/cm, the crystal packing is similar to the previous examples but the anions are dimerised. With other [M(mnt)2] anions (M= Pt, Ni) there is a redox reaction between the donor and the acceptors, resulting in the full oxidation of the donor. With Ni two stoichiometries (α-DT-TTF)2

2+[Ni(mnt)2]2- and (α-

DT-TTF)+[Ni(mnt)2], both with segregated donor stacks could be obtained. With Pt the salt obtained is (α-DT-TTF)2

2+[Pt(mnt)2]2-.

Two different crystal structures and stoichiometries were identified in salts of this donor with the PF6 anion; (α-DT-TTF)(PF6)0.6 and (α-DT-TTF)2(PF6), with electrical conductivities measured in single crystal, in the range RT~ 9-50 S/cm. Both structures display semiconducting behavior and properties comparable to those of the non-aromatic BET-TTF analogous salts [1]. Similar compounds are obtained with BF4

– and ClO4– anions.

Acknowledgements: Work supported by FCT PTDC/QEQ-SUP/1413/2012 and grant SFRH/BD/86131/2012. [1] Silva, R. A. L.; Neves, A. I.; Afonso, M. L., Santos, I. C.; Lopes, E. B.; Del Pozo, F.; Pfattner, R.; Torrent, M. M.-; Rovira, C.; Almeida, M.; Belo, D.; Eur. J. Inorg. Chem. 2013, 13, 2440-2446. [2] Silva, R. A. L.; Neves, A. I.; Lopes, E. B.; Santos, I. C.; Coutinho, J. T.; Pereira, L. C. J.; Rovira, C.; Almeida, M.; Belo, D.; Inorg. Chem. 2013, 52, 5300-5306.

Posters

101

P59 - INTERCALATION OF A MOLYBDENUM 3-ALLYL DICARBONYL COMPLEX IN A LAYERED DOUBLE HYDROXIDE AND

CATALYTIC PERFORMANCE IN OLEFIN EPOXIDATION

Ana C. Gomes,1 Sofia M. Bruno,1 Carla A. Gamelas,2,3 Anabela A. Valente,1

Marta Abrantes,4 Isabel S. Gonçalves,1 Carlos C. Romão2 and Martyn Pillinger1

1Department of Chemistry, CICECO, University of Aveiro, Campus Universitário de Santiago,

3810-193 Aveiro. [email protected]; 2Instituto de Tecnologia Química e Biológica, Universidade Nova de Lisboa, EAN, 2780-157

Oeiras 3Escola Superior de Tecnologia, Instituto Politécnico de Setúbal, 2910-761 Setúbal

4Centro de Quıímica Estrutural, Instituto Superior Técnico, Av. Rovisco Pais, 1, 1049-001 Lisboa

Interest in molybdenum allyl dicarbonyl complexes stems mainly from their use as starting materials or as (pre)catalysts for various organic transformations. In recent work we showed that the complexes [Mo(η3-C3H5)Cl(CO)2(L)] (L=2,2′-bipyridine, 4,4′- di-tert-butyl-2,2′-bipyridine) are convenient precursors to oxomolybdenum(VI) compounds that selectively catalyze the epoxidation of olefins 1. The immobilisation of the metal carbonyls on a suitable support could bring numerous benefits, such as easier catalyst recycling and product separation. In the present work, the complex [Mo(η3-C3H5)Cl(CO)2(2,2′-bipyridine-5,5′- dicarboxylate)] has been successfully incorporated into a Zn–Al layered double hydroxide (LDH) by a one-pot coprecipitation route from aqueous solution and the resulting hybrid nanocomposite Zn,Al-bpdcMo was characterized by various techniques 2. The material Zn,Al-bpdcMo was used as a precatalyst in the selective liquid phase epoxidation of cis-cyclooctene with tert-butylhydroperoxide as oxidant. Figure: Schematic representation of the interlayer arrangement of guest anions in the material Zn,Al-

bpdcMo (on the left); SEM image of Zn,Al-bpdcMo (on the right) Acknowledgements: Fundação para a Ciência e a Tecnologia (FCT, project PTDC/QEQ- SUP/1906/2012), QREN, Fundo Europeu de Desenvolvimento Regional (FEDER), COMPETE, the European Union, and the Associate Laboratory CICECO (PEst-C/CTM/LA0011/2013). [1] Gamelas, C. A.; Gomes, A. C.; Bruno, S. M.; Paz, F. A. A.; Valente, A. A.; Pillinger, M.; Romão, C. C.; Gonçalves, I. S. Dalton Trans. 2012, 41, 3474. [2] Gomes, A. C.; Bruno, S. M.; Gamelas, C. A.; Valente, A. A.; Abrantes, M.; Gonçalves, I. S.; Romão, C. C.; Pillinger, M. Dalton Trans. 2013, 42, 8231.

Posters

102

P60 – SYNTHESIS AND REACTIVITY OF A BIS(PHENOLATE) CYCLAM SAMARIUM (II) COMPLEX: REDUCTION CHEMISTRY

Leonor Maria1,2,*, Marina P. Soares1,2,

Vânia Sousa1, Isabel C. Santos1,2, Joaquim Marçalo1,*

1Centro de Ciências e Tecnologias Nucleares, Instituto Superior Técnico, Universidade de Lisboa, 2695-066 Bobadela LRS, Portugal 2Centro de Química Estrutural, Instituto Superior Técnico,

Universidade de Lisboa, 1049-001 Lisboa, Portugal *e-mail: [email protected], [email protected]

Over the past few decades, there has been a growing interest in the search for alternative ligand sets which are able to satisfy the coordination requirements of the large lanthanide cations. In this context, we have recently demonstrated that a new bulky ligand derived from a tetraazamacrocycle, bis(phenolate) cyclam, is adequate for the stabilization of solvent-free yttrium(III) and lanthanide(III) complexes of general formula [Ln{ArtBu2O)2Me2cyclam}Cl] (Ln= Y, La, Sm, Yb).1 As we are interested in redox events associated with small molecule or unsaturated substrates activation, we expect that the dianionic hexadentate ligand [(ArtBu2O)2Me2cyclam]2- (Figure 1-a) will allow to stabilize divalent lanthanide metals. In fact, the new divalent samarium complex [Sm{(ArtBu2O)2Me2cyclam}] has been synthesized by salt metathesis reaction between SmI2(THF)2 and the potassium salt of the ligand. The Sm(II) complex was characterized by elemental analysis, X-ray diffraction analysis and 1H NMR. The XRD analysis revealed the formation of a mononuclear Sm(II) complex (Figure 1-b), with the macrocyclic bis(phenolate) acting as a hexadentate chelator. Here we report the synthesis, structural analysis and solution behavior of this new Sm(II) complex.

(a) (b) Figure 1: The reductive chemistry of the bis(phenolate) cyclam Sm(II) complex is currently in progress

and the results will be also reported. Acknowledgements: The authors are grateful to Fundação para a Ciência e a Tecnologia for funding (projects PTDC/QUI-QUI/109846/2009 and RECI/QEQ-QIN/0189/2012, and “Ciência 2008” Programme). [1] Maria, L.; Santos, I. C.; Alves, L. G.; Marçalo, J.; Martins, A. M. J. Organomet. Chem. 2013, 728, 57-67.

Posters

103

P61 - MOLECULAR STRUCTURE OF HEMOZOIN-LIKE CRYSTALS AND THEIR INTERACTION WITH CHLOROQUINE

Carlos Caro1, Ana Góis2, Carolina Tempera2, Vânia André3, Peter Eaton4, Peter Burke5, M. Teresa Duarte3, Miguel Prudêncio2, Thomas Hänscheid2,

Ricardo Franco1

1 REQUIMTE, Departamento de Química, FCT/UNL, 2829-516 Caparica, Portugal

2 Instituto de Medicina Molecular, Fac. Medicina Univ. Lisboa, 1649-028 Lisboa, Portugal 3 CQE, IST/UL, 1049-001 Lisboa, Portugal

4 REQUIMTE, Departamento de Química e Bioquímica, FC/UP, 4169-007 Porto, Portugal 5 STERIS Corporation, St. Louis, Missouri, USA

Hemozoin-like crystals (HLC) are a heme-containing compound of biological origin that has recently become useful in the screening of new antimalarial drugs[1]. HLC constitute an alternative to β-hematin, a synthetic form of hemozoin that is harder to synthesize. Antimalarials of interest include those that interact with the natural hemozoin crystals, such as chloroquine, although the nature of such interaction at the molecular level is still a matter of debate. Here, we present a complete structural characterization of HLC and compare it with β-hematin, and also with natural hemozoin. Scanning Electron Microscopy of HLC revealed flower-like dendritic structures (Fig. 1), whereas synthetic and natural hemozoin presented crystalline structures similar to what has been previously reported. These results were confirmed by X-Ray Diffraction, with HLC revealing to be less crystalline than their hemozoin counterparts. The Raman Effect provides information about molecular vibrational states. Here, Raman spectroscopy using a 633 nm laser allowed confirmation not only of the presence of heme in HLC, but also of its poorly structured organization (Fig. 1). Spectra in the presence of chloroquine presented shifts in important heme-specific vibrational lines, suggesting a direct molecular interaction between the two molecules.

Fig. 1: SEM micrograph of HLC; and Raman spectra of different heme-containing species

Acknowledgements: FCT-MEC Grant PEst-C/EQB/LA0006/2011 and 2013; RECI/QEQ- QIN70189/2012, COMPETE and EXPL/CTM-NAN/0754/2013 (to R.F.), SFRH/BPD/78854/2011 (to V.A.). STERIS Corporation. Junta de Andalucía P07-FQM-02595 (to C.C.). [1] Thomas, V. et al. PLOSone 2012, 7, e41006.

Posters

104

P62 – MEASUREMENT OF AUROPHILIC INTERACTIONS IN WATER

Laura Rodríguez a, Elisabet Aguiló a, Raquel Gavara b, João Carlos Limab

a Departament de Química Inorgànica, Universitat de Barcelona, Barcelona, Spain.

b REQUIMTE, Departamento de Química, CQFB, Universidade Nova de Lisboa, Monte de Caparica, Portugal.

e-mail: [email protected]

Gold(I) complexes with small ligands oligomerize to give dimers, trimers, tetramers , chain polymers, or layers with short Au···Au contacts.

In the specific case of water soluble complexes we have recently shown the formation of hydrogels.1,2 Both absorption and emission of Au(I) complexes are modulated by the presence of aurophilic (Au···Au) interaction.1-4 We present spectroscopic and photophysical evidences for the presence of Au···Au contacts in the hydrogel: the appearance of new absorption bands assigned to (*Au···Au-*) and the increase in non-radiative and radiative rate constants of the low lying triplet emissive sate attributed to the short (Au···Au) average distances in the oligomers.4 An Isodesmic model of aggregation was used to estimate the equilibrium constant and the free energy for a single step aggregation (dimerization) which measures the magnitude of the intermolecular attractive interaction. The use of a cyclic polyanion to perturb the supramolecular aggregation is also shown.

… ~3 Å

Posters

105

P63 - NOVEL COLORIMETRIC MACROCYCLIC MOLECULAR PROBES WITH LOGIC GATES FUNCTIONS

Adrián Fernández-Lodeiro1,2, Cristina Núñez1,3,4, Carlos Lodeiro1,2, José Luis Capelo1,2, Verónica García3,

Rodrigo Lamelas3, Alejandro Macías3, Rufina Bastida3, Emilia Bértolo4

1REQUIMTE, Chemistry Department, Faculty of Science and Technology, University NOVA

of Lisbon 2829-516, Monte da Caparica, Portugal. Email: [email protected] 2ProteoMass Scientific Society. Madan Parque. Rua dos Inventores. 2825-182. Caparica.

Portugal 3Inorganic Chemistry Department, Faculty of Chemistry, University of Santiago de

Compostela, 15782 Santiago de Compostela, Spain 4Ecology Research Group, Department of Geographical and Life Sciences, Canterbury Christ

Church University, CT1 1QU, Canterbury, United Kingdom. Continuing our efforts improving the colorimetric properties of different substituted receptors [1,2], we present the synthesis of two novel colorimetric anion sensors that comprise two urea (sensor 1) and thiourea (sensor 2) groups (anion binding site) coupled with a nitrophenyl group (chromogenic unit) (see Figure 1). It was found that these systems can recognize different anions (OH-, F-, CN- CH3COO- and H2PO4

-) resulting in a red shift of electronic transition and correspondingly color-switching of 1 and 2. In addition, based on above sensing mechanism with systems 1 and 2, IFNOT logic operations can be achieved using OH- and Cu2+ ion as inputs, and/or F- and Hg2+, respectively, making 1 and 2, promising candidate for further applications in molecular logic devices.

Figure 1: Schematic representation of compounds 1 and 2. Changes in UV-vis spectra for compound

1* with the addition of Cu2+ in DMSO (1* = deprotonated molecular probe 1 after titration with F [1*]=1.00x10-5M): executive procedure of an IFNOT logic gate. Colorimetric effect in systems 2 after

the interaction with different metal ions in DMSO solution (t=48h). Acknowledgements: Authors thank Scientific Association Proteomass (Portugal) for financial support to AFL. C.N. thanks Xunta de Galicia for the I2C program postdoctoral contract. We are grateful to the Xunta de Galicia (Spain) for the Project PGIDI10PXIB209028PR and IN845B-2010/057 for financial support. [1] Aldrey, A.; Núñez, C.; García, V.; Bastida, R.; Lodeiro, C.; Macías, A. Tetrahedron 2010, 66, 9223-9230. [2] Oliveira, E.; Batista, R. M. F.; Costa, S. P. G.; Raposo, M. M. M.; Lodeiro, C.; Photochem. Photobiol. Sci. 2014 (in press) Cover Picture of March Issue.

Posters

106

P64 - SUPRAMOLECULAR SYSTEMS CONNECTING FLAVYLIUM MOITIES WITH METAL COMPLEXES

Ana M. Diniz, A. Jorge Parola, Fernando Pina

Departamento de Química, REQUIMTE, Faculdade de Ciências e Tecnologia Universidade Nova de Lisboa, Portugal.

E-mail: [email protected]

Information processing at the molecular level requires systems capable of

switching between several states under control of specific inputs. Examples of such multistate/multiresponsive systems have been developed on the basis of the pH and light dependent network of chemical reactions occurring in flavylium (2-phenyl-1-benzopyrylium) compounds, analogs of naturally occurring anthocyanin dyes.[1,2] Extension of these systems to include redox responsive moieties has been developed by coupling viologen units to flavylium salts.[3]

In Nature, anthocyanins are stabilised in the vacuoles through an array of supramolecular interactions including -stacking of the aromatic moieties and complex formation with several metal ions. On the other hand, polypyridine Ru(II) complexes have long been employed as building blocks in supramolecular systems where they play the role of electron transfer components, luminescent moieties or redox relays when cyclic processes are involved. The building of supramolecular dyads and triads involving flavylium cations and polypyridine Ru(II) complexes opens the possibility of (i) extending the pH and light stimuli to electric inputs and, (ii) study energy and electron transfer processes.

In this work, the synthesis of a symmetrical supramolecular triad constituted by two 7-hydroxyflavylium moieties covalently linked to a Ru(bpy)2 (phen)2+ is presented, Fig. 1. The thermodynamic equilibria and the kinetics of the chemical reaction network as well as the photochemical reactivity of the chalcones will be reported. References: [1] Pina, F.; Parola, A. J.; Gomes, R.; Maestri, M.; Balzani, V., Multistate/Multifunctional Molecular-Level Systems: Photochromic Flavylium Compounds. In Molecular Switches, 2nd ed., Feringa, B. L.; Browne, W. R., Eds., Wiley-VCH: Weinheim, 2011, Vol. 1, Ch. 6, pp. 181-226, ISBN 978-3-527-31365-5. [2] Pina, F.; Melo, M. J.; Laia, C. A. T.; Parola, A. J.; Lima, J. C., Chemistry and Applications of Flavylium Compounds: a Handful of Colours, Chem. Soc. Rev. 2012, 41(2), 869-908. [3] Diniz, A. M.; Pinheiro, C.; Petrov, V.; Parola, A. J.; Pina, F., Synthesis and Characterization of a Symmetric Bis-7-hydroxyflavylium Containing a Methyl Viologen Bridge, Chem. Eur. J., 2011, 17, 6359-6368. Acknowledgements: A. M. Diniz wishes to thank FCT for a PhD grant (SFRH/BD/48226/2008). This work has been supported by Fundação para a Ciência e a Tecnologia through grants PTDC/QUI-QUI/119932/2010.

Posters

107

P65 - THE REACTIVITY OF [RUCL2(CO)3L] COMPLEXES IN AQUEOUS MEDIA AND WITH PROTEINS

João D. Seixas1, Abhik Mukhopadhyay2, Ana Catarina Coelho,3, Marino F. A. Santos2, Patrícia M. Reis3, Gonçalo J. L. Bernardes1, Luis F. Veiros4, Ana M.

Gonçalves1, Maria João Romão2, Teresa Santos-Silva2 and Carlos C. Romão1,3

1Alfama Lda, IBET, Av. República, EAN, 2780-157, Oeiras, Portugal

2 Requimte, FCT-,Universidade Nova de Lisboa, 2829-516 Caparica, Portugal 3ITQB-António Xavier, UNL, Av. República, EAN, 2780-157, Oeiras, Portugal

4Centro de Química Estrutural, Técnico Lisboa, Av. Rovisco Pais, 1049 Lisboa, Portugal Email of author for contact: [email protected]

The use of transition metal carbonyl complexes in the therapeutic delivery of CO for the treatment of a variety of disease indications is well established [1]. The complexes CORM-2 and CORM-3 (Figure 1) have been the most widely used but their chemistry and mode of action remains largely unexplained [2]. Based on the

expectation that the reactivity of the title complexes can be modulated by the nature of the ancillary ligand L we studied a series of new complexes bearing C, N, O, S and P ligands (Figure 1). When dissolved in aqueous buffers, none of the complexes releases CO to the headspace of their solutions. Their chemistry is controlled by the water-gas shift reaction with initial formation of a Ru-C(O)OH bond which decays to

release CO2 and Ru-H species. These mechanistic features were confirmed with HPLC, LC-MS, 1HNMR and GC. The more stable complex is the thioether 4 and the least stable ones are the isocyanide derivatives 9-11. Crystals of HEWL (lysozyme) soaked with 3, 7 and 8 showed i.a. Ru(CO)x(H2O)5-x and Ru(CO)(COOH)(H2O)3 fragments mainly coordinated to the His15 but also to other binding sites. No Ru(CO)3 fragment was detected, in agreement with this mode of decomposition. DFT calculations suggest an exceedingly small activation barrier for the nucleophilic addition of HO- to CO. Acknowledgements: Alfama Lda and Project PTDC/QUI-BIQ/117799/2010 for funding. [1] Romão, C. C.; Blättler, W. A.; Seixas, J. D.; Bernardes, G. J. L. Chem Soc Rev 2012, 41, 3571–3583. [2] Santos-Silva, T., Mukhopadhyay, A., Seixas, J. D.; Bernardes, G. J. L.; Romão C. C.; Romão, M.J. J Am Chem Soc 2011,133, 1192–1195.

Figure 1: [RuCl2(CO)3L] complexes studied.

Posters

108

P66 - SYNTHESIS AND CHARACTERIZATION OF NEW LUMINESCENT GLASSES FOR ARTISTIC APPLICATIONS

A. Ruivo1,2, C. A. T. Laia1, A. Pires de Matos2, F. Pina1

1REQUIMTE, Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, Campus de Caparica, 2829-516 Caparica, Portugal

2VICARTE, Vidro e Cerâmica para as Artes, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, Campus de Caparica, 2829-516 Caparica, Portugal

e-mail: [email protected] Luminescent glasses can be used not only in technological applications, but also in art works [1]. In this project innovative luminescent glasses were produced through two different strategies: using lanthanide oxides and using other elements such as lead halides and copper. Single lanthanide oxides and a mixture of the same oxides (Tb4O7, Eu2O3 and CeO2) were used to dope soda-lime silicate glasses giving rise to a large range of luminescence colours. Chromaticity studies were applied, which can allow the estimation of the luminescent colour produced for a given composition and/or understand the impact of excited-state processes in the final luminescence colour. An aluminoborosilicate glass was also produced and doped with lead and halides, originating glasses with blue luminescence. Using different techniques, crystalline nanoparticles were identified and attributed to lead halide nanoparticles. The same glass composition was doped with copper, which gave rise to a yellow luminescence due to formation of Cu+. These materials can be used by artists to improve or to complement their artworks. Some of the produced glasses were already used in artworks and a few examples will be presented.

[1] T. Almeida, A. Ruivo, A. Pires de Matos, R. Oliveira and A. Antunes, J. Cultural Heritage, 2008, 9, e138-e142.

Acknowledgements: This work has been supported by the European project NMP4-SL-2012-310651 under FP7-NMP-2012-SMALL-6 and by Fundação para a Ciência e a Tecnologia through grants PEst-C/EQB/LA0006/2013 and PEst-C/CTM/LA0011/2011. The authors would like to thank the Fundação para a Ciência e Tecnologia (FCT) for financial support under contract PTDC/EAT/67354/2006 and PTDC/EAT-AVP/118520/2010. A. Ruivo would like to thank a grant by FCT (SFRH/BD/46659/2008). .

Autor Index

109

Author Index

Abrantes, M. ........................................ 101 Adão, P. ................................................ 36 Afonso, M. L. ....................................... 100 Aguiló, E. ...................................... 10, 104 Albrecht, M. ........................................... 23 Almeida, A. R. ....................................... 94 Almeida, M. ............................... 5, 55, 100 Almeida, M. G. ...................................... 33 Almeida, R. ........................................... 33 Alves, A. F. ..................................... 68, 71 Alves, L. G. ..................................... 40, 77 Amaral, V. S. ......................................... 97 Andrade, M. A. ...................................... 35 Andrade, S. ........................................... 33 André, P. ............................................... 34 André, V. ............................................. 103 Ania, C. O. ............................................ 35 Anisimova, T. B. .................................... 89 Aquino, G. ............................................. 94 Araújo, J. P. .......................................... 19 Araújo, M. ............................................. 61 Ascenso, J. R. ...................................... 54 Avecilla, F. ............................................ 36 Avilés, T. ............................. 25, 47, 49, 56 Baleizão, C. .......................................... 22 Balula, S. S. .................................... 17, 18 Barata J. F. ........................................... 45 Barroso, S. ................................ 26, 36, 51 Bastida, R. .......................................... 105 Bebiano, S. S. ....................................... 28 Belo, D. ............................................... 100 Belo, J. H. ............................................. 19 Benavides, M. ....................................... 65 Bernardes, G. J. L. .............................. 107 Bernardo, J. R. ...................................... 95 Bértolo, E. ........................................... 105 Besson, S. ............................................ 33 Biriukova, M. ......................................... 98 Bordado, J. C. ...................................... 54 Borges, M. .............................................. 6 Branchadell, V. ..................................... 82 Branco, J. B. ................................... 57, 59 Branco, L. C. ................................... 27, 90 Brandão, P. ..................................... 70, 75 Brites, C. D. S. ................................ 58, 97 Bruno, S. M. ........................................ 101 Burke, P. ............................................. 103 Burrows, H. D. ...................................... 28 Caldeira, A. T. ................................. 41, 92

Calhorda, M. J. . 25, 26, 75, 76, 78, 81, 82, 85, 86 Calixto, J. ............................................. 70 Calvete, M. J. F. ........................ 28, 48, 94 Campelo, J. .......................................... 41 Campo, J. ............................................. 21 Candeias, A. ........................................ 41 Capelo, J. L. ................ 65, 67, 73, 93, 105 Carabineiro, S. A. C. ............................ 48 Cardoso, B. P. ...................................... 81 Cardoso, J. ........................................... 20 Cardoso, J. M. S. ............................12, 81 Carepo, M.S.P. ...................................... 8 Carlos, L. D. ........................ 34, 58, 66, 97 Caro, C. ............................................. 103 Carretas, J. M. ..................................... 69 Carrilho, R. M. B. ............................37, 48 Carvalho, A. P. .............. 35, 46, 50, 72, 96 Carvalho, M. D. ................... 53, 68, 71, 75 Carvalho, M. F. N. N. ........................... 74 Castro, B. ............................................. 17 Cavaleiro, J. A. S. ...........................45, 93 Charas, A. ............................................ 78 Chernyavskii, A. S. ............................... 62 Codolà, Z. ............................................ 12 Coelho, A. ............................................ 51 Coelho, A. C. ...................................... 107 Coelho, C. ............................................ 92 Coelho, P.J. ......................................... 44 Correia, I. ............................................. 31 Correia, M. R. ....................................... 16 Costa, D. .............................................. 70 Costa, G. N. ......................................... 37 Costa, J. A. L. ...................................... 20 Costa, P. .............................................. 44 Costa, S. .........................................72, 92 Costas, M. ............................................ 12 Coutinho, J.T. ..................................... 100 Cremona, M. ........................................ 58 Cruz, M. M. .....................................68, 71 Cruz, S. M. A. ....................................... 66 Cruz, T. F. C. ....................................... 54 Cunha, S. ............................................. 80 Cunha-Silva, L. .................................... 18 Dagorne, S. .....................................11, 25 Dalto, F. ............................................... 50 Damas, L. ............................................. 94 Delgado, R. .....................................29, 43 Di Paolo, R. E. ..................................... 78

Participants List

110

Dias, D. ................................................. 15 Dias, L. D. ............................................. 94 Dias, M. V. ............................................ 85 Diniz, A. M. ......................................... 106 Diniz, M. E. ........................................... 65 Duarte, M. T. ........................... 24, 78, 103 Eaton, P. ............................................. 103 Einsle, O. ................................................ 4 Espadinha, M. ....................................... 47 Faria, R. B. ............................................ 20 Farinha, J. P.S. ..................................... 22 Fateixa, S. ............................................. 16 Faustino, F. ........................................... 93 Faustino, M. A. F. ................................. 45 Felício, M. ............................................. 84 Félix, V. ................................................. 70 Fernandes, A. ....................................... 28 Fernandes, A. C. ....................... 87, 88, 95 Fernandes, A.J.S. ................................. 61 Fernandes, C. ....................................... 80 Fernandes, C. I. .................................... 53 Fernandes, R. ....................................... 56 Fernandes, T. A. ................................... 88 Ferreira, A. C. ................................. 57, 59 Ferreira, B. ...................................... 70, 78 Ferreira, L. P. ..................... 53, 68, 71, 75 Ferreira, R. A. S. ....................... 34, 58, 66 Ferreira, R. R. ....................................... 52 Ferreira, T. ...................................... 41, 92 Figueira, C. A. ................................. 39, 78 Figueira, F. ............................................ 41 Figueiredo, J. L. .................................... 48 Fliedel, C. ........................................ 25, 49 Florek, M. .............................................. 91 Florindo, P. R. ........................... 87, 88, 95 Fonseca, I. M. ................................. 72, 79 Forte, A. .......................................... 27, 90 Franco, R. ........................................... 103 Freire, C. ..... 14, 38, 44, 46, 50, 61, 66, 83 Freitas, V. ............................................. 34 Gago, S. .......................................... 27, 79 Galhetas, M. ......................................... 96 Galvão, A. M. ........................................ 74 Gama, S. ............................................... 30 Gamelas, C. A. ................................... 101 Gano, L. ................................................ 80 Garcia, M. H. ......................................... 20 García, V. ............................................ 105 Garribba, E. .......................................... 31 Gasche, T. A. .................................. 57, 59 Gavara, R. .................................... 10, 104 Geraldes, C. F. G. C. ...................... 14, 15

Gibson, J. K. ........................................ 69 Gil, A. ................................................... 82 Godinho, M. ....................................68, 71 Góis, A. .............................................. 103 Gomes, A. C. ..................................... 101 Gomes, C. S. B. .................. 24, 39, 54, 78 Gomes, I. T. ......................................... 19 Gomes, J. S. ........................................ 39 Gomes, P. T. ....................... 24, 39, 54, 78 Gonçalves, A. M. ................................ 107 Gonçalves, I. S. .................................. 101 Granadeiro, C. M. ................................ 18 Guardingo, M. ........................................ 6 Hadimani, R. L. .................................... 19 Hänscheid, T. ..................................... 103 Henriques, C. A. ................................... 48 Henriques, R.T. .................................... 20 Herold, B. J. ......................................... 20 Heyduk, A. F. ......................................... 9 Hild, F. ................................................. 11 Jardim, M. G. ....................................... 21 Jaros, S. W. ......................................... 91 Jarrais, B. ............................................. 83 Jiles, D.C. ............................................. 19 Julião, D. .............................................. 17 Júnior, S. A. ......................................... 58 Justino, G. ............................................ 31 Kirillov, A. M. ........................................ 91 Knittel, A............................................... 74 Knuw, K.................................................. 6 Król, J. .................................................. 91 Kukushkin, V. Y. ................................... 89 Laia, C. A. T. ..................... 27, 52, 63, 108 Lamelas, R. ........................................ 105 Lapa, N. ............................................... 35 Laronha, H. .......................................... 47 Laurents, D. ......................................... 15 Leal, J. P. ............................................. 57 Legnani, C. ........................................... 58 Lemos, F. ............................................. 39 Lemos, M. A. N. D. A. .....................39, 54 Lima, J. C. ............................... 10, 60, 104 Lima, P. P. ................................ 34, 58, 97 Lloret-Fillol, J. ....................................... 12 Lodeiro, A. F. .................... 65, 67, 73, 105 Lodeiro, C. ............ 45, 65, 67, 73, 93, 105 Lodeiro, J. F. ....................... 45, 65, 67, 73 Lograsso, T.A. ...................................... 19 Lopes, A. M. L. ..................................... 19 Lopes, E.B. ........................................ 100 Lopes, H............................................... 96 Lopes, P. S. ......................................... 78

Autor Index

111

Lopes, R. .............................................. 49 Lucena, A. F. ........................................ 69 Luzyanin, K. V. ................................ 89, 99 Mac Leod, T. C. O. ............................... 99 Maçanita, A. L. ...................................... 78 Machado, A. .......................................... 20 Machura, B. .......................................... 95 Macías, A. ........................................... 105 Madeira, F. ................................ 26, 40, 77 Magalhães, M.C. ................................... 20 Malta, O. L. ........................................... 58 Marçalo, J. ........................ 20, 60, 69, 102 Maria, L. .............................................. 102 Marques, F. ........................................... 80 Marques, I. J. ........................................ 64 Marreiros, J. T. ...................................... 85 Martinho, P. N. ................................ 75, 76 Martins, A. ............................................. 72 Martins, A. F. ........................................ 15 Martins, A. M. ...................... 26, 40, 51, 77 Martins, L. M. D. R. S............................ 99 Mateus, P. ....................................... 29, 43 Melato, A. I. ..................................... 75, 76 Mendes, B. ............................................ 35 Mendes, F. ............................................ 30 Mendo, S. G. ................................... 68, 71 Mendonça, M. H. ............................ 68, 71 Mesquita, J. C. ...................................... 21 Mesquita, L. .......................................... 43 Mestre, A. S. ....................... 35, 46, 50, 96 Michelini, M. C. ..................................... 69 Millan, A. ............................................... 97 Monteiro, B. .......................................... 60 Monteiro, C. J. P. ............................ 48, 94 Morfin, J-F ............................................. 15 Morgado, J. ........................................... 78 Moro, A. J. ...................................... 10, 60 Moura, I. ............................................ 8, 33 Moura, J. J. G. .................................. 8, 33 Moura, N. M. M. .............................. 65, 93 Mukhopadhyay, A. .............................. 107 Munhá, R. F. ..................................... 9, 40 Nador, F. ................................................. 6 Neves, A.I.S. ....................................... 100 Neves, M. G. P. M. S. ..................... 45, 93 Nogueira, H. I. S. .................................. 66 Nolasco, M. ..................................... 34, 84 Novais, J. P. .......................................... 38 Novio, F. ................................................. 6 Nunes, C. D. ................................... 53, 64 Nunes, M. ............................................. 41 Núñez, C. .................... 65, 67, 73, 93, 105

Ogarkov, A. I. ....................................... 62 Oliveira, E. .......................... 45, 65, 67, 73 Oliveira, M. C. ...................................... 80 Oliveira, M. C. M. A. ............................. 36 Oliveira, S. ........................................... 55 Pais, A. A. C. C. ................................... 94 Palacio, F. ............................................ 97 Palma, E. ............................................. 30 Parola, A. J. .................................. 79, 106 Pauleta, S. R. ......................................... 8 Paulo, A. .............................................. 30 Paz, F. A. A. ......................................... 58 Pedroso, H. A. ...................................... 33 Peitinho, D. J. ....................................... 73 Peixoto, A. F. ....................................... 38 Pellegrino, O. ....................................... 20 Pereira, A. M. ..................................14, 19 Pereira, C. ........................... 14, 44, 50, 66 Pereira, L.C.J. .................................... 100 Pereira, M. M. ..................... 28, 37, 48, 94 Pereira, M.F.R. ................................44, 61 Pessoa, J. C. ............................. 31, 36, 74 Petronilho, A. ....................................... 23 Pillinger, M. ........................................ 101 Pina, F. ........................... 27, 90, 106, 108 Pineiro, M. ............................................ 94 Pinto, T. V. ......................................44, 66 Pires de Matos, A. .............................. 108 Pires, A. L. ........................................... 19 Pombeiro, A. J. L. ..................... 89, 91, 99 Prostota, Y. .......................................... 44 Prudêncio, M. ..................................... 103 Quirino, W. G. ...................................... 58 Rabaça, S. ........................................... 55 Realista, S. ......................................75, 76 Reis, P. M. ......................................... 107 Relvas, C. .......................................41, 92 Ribeiro, M. F. ....................................... 28 Ribeiro, S. ............................................ 18 Ribeiro, T. ............................................ 22 Ribeiro-Claro, P. .................................. 34 Rissanen, K. ......................................... 21 Rocha, B. G. M. ................................... 99 Rocha, M. ........................................14, 50 Rodrigues, A.S. .................................... 22 Rodrigues, I. ......................................... 30 Rodrigues, J. ........................................ 21 Rodríguez, L. ................................ 10, 104 Romain, C. ........................................... 11 Romão, C. C. .......................... 2, 101, 107 Romão, M. J. ...................................... 107 Rosa, V. .................................... 47, 49, 56

Participants List

112

Roseiro, A. P. S. ................................... 74 Rovira, C. ............................................ 100 Roy, S. .................................................. 31 Royo, B. .......................................... 12, 81 Ruivo, A. ....................................... 63, 108 Ruiz-Molina, D. ....................................... 6 Rutkowski, P. X. .................................... 69 Sakharov, S. G. .................................... 62 Santos, C. I. ........................ 45, 65, 67, 73 Santos, H. M. ............................ 65, 67, 73 Santos, I. ......................................... 30, 80 Santos, I. C. .................... 30, 55, 100, 102 Santos, M. F. A. ............................ 31, 107 Santos, S. M. .................................. 45, 67 Santos, T. ............................................. 70 Santos-Silva, T. ............................ 31, 107 Saraiva, M. S. ....................................... 86 Schlagel, D.L. ....................................... 19 Seixas, J. D. ........................................ 107 Serra, O. A. ........................................... 20 Silva, M. ................................................ 28 Silva, M. C. ........................................... 58 Silva, M. F. C. G. ...................... 89, 91, 99 Silva, N. J. O. ........................................ 97 Silva, R.A.L. ........................................ 100 Silva, S. M. ............................................ 38 Silveira, C.M. ........................................ 33

Smoleński, P. ....................................... 91 Soares, C. O. ....................................... 59 Soares, M. P. ..................................... 102 Soares, O.S.G.P. ............................44, 61 Solntsev, K. A. ..................................... 62 Sousa, C. ............................................. 44 Sousa, C.M. ......................................... 44 Sousa, V. ........................................... 102 Staroniewicz, Z. ................................... 91 Suresh, D. ............................................ 78 Tempera, C. ....................................... 103 Todorovic, S. ........................................ 33 Toth, E. ................................................ 15 Trindade,T. ........................................... 16 Valente, A. A. ..................................... 101 Vaz, P. ................................................. 34 Vaz, P. D. .................................. 34, 53, 84 Veiros, L. F. ................................... 40, 107 Vicente, A. I. ......................................... 75 Vila-Viçosa, D. ..................................... 25 Wedd, A.G. ............................................ 8 Wenseleers, W. .................................... 21 Wolff, M. ............................................... 95 Wust, A. ............................................... 33 Yurkov, G. ............................................ 98 Zarkesh, R. A. ........................................ 9

Participants List

113

PARTICIPANTS LIST

Adão, P. Instituto Superior Técnico, Universidade de Lisboa, Portugal Almeida, M. Instituto Superior Técnico, Universidade de Lisboa, Portugal Alves, A. Faculdade de Ciências, Universidade de Lisboa, Portugal Alves, L. G. Instituto Superior Técnico, Universidade de Lisboa, Portugal Andrade, M. Faculdade de Ciências, Universidade de Lisboa, Portugal Anisimova, T. IST-ID, Portugal Araújo, M. Faculdade de Ciências, Universidade do Porto, Portugal Avilés, T. FCT, Universidade Nova de Lisboa, Portugal Baleizão, C. Instituto Superior Técnico, Universidade de Lisboa, Portugal Barroso, S. Instituto Superior Técnico, Universidade de Lisboa, Portugal Bentes, R. Instituto Superior de Engenharia de Lisboa, Portugal Bernardo, J. R. Instituto Superior Técnico, Universidade de Lisboa, Portugal Biriukova, M. A.Baikov Institute of Metallurgy and Materials Science RAS Branco, L.C. REQUIMTE, FCT, Universidade Nova de Lisboa, Portugal Brites, C. D. S. Universidade de Aveiro Cardoso, B. P. CQB, Faculdade de Ciências, Universidade de Lisboa, Portugal Carrilho, R. M. B. Universidade de Coimbra, Portugal Carvalho, F. IST-ID, Portugal Carvalho, M. D. CQB, Faculdade de Ciências, Universidade de Lisboa, Portugal Coelho, A. Instituto Superior Técnico, Universidade de Lisboa, Portugal Coelho, C. Universidade de Évora, Portugal Costa, S. FCT, Universidade Nova de Lisboa, Portugal Cruz, T. F. C. Instituto Superior Técnico, Universidade de Lisboa,l Portugal Cunha, S. Instituto Superior Técnico, Universidade de Lisboa, Portugal Dagorne, S. CNRS, University of Strasbourg, France Dalto, F. Universidade do Porto, Portugal Diniz, A. M. FCT, Universidade Nova de Lisboa, Portugal Einsle, O. Institute for Biochemistry, Germany Espadinha, M. FCT, Universidade Nova de Lisboa, Portugal Fateixa, S. Universidade de Aveiro, Portugal Fernandes, C. I. Faculdade de Ciências, Universidade de Lisboa, Portugal Fernandes, T. A. Instituto Superior Técnico, Universidade de Lisboa, Portugal Fernández-Lodeiro, A. FCT, Universidade Nova de Lisboa, Portugal

Ferreira, R. R. FCT, Universidade Nova de Lisboa, Portugal Figueira, C. A. Instituto Superior Técnico, Universidade de Lisboa, Portugal Fliedel, C. FCT, Universidade Nova de Lisboa, Portugal Florindo, P. Instituto Superior Técnico, Universidade de Lisboa, Portugal Forte, A. FCT, Universidade Nova de Lisboa, Portugal Franco, R. REQUIMTE, FCT, Universidade Nova de Lisboa, Portugal Freire, C. Faculdade de Ciências, Universidade do Porto, Portugal Gago, S. FCT, Universidade Nova de Lisboa, Portugal Galhetas, M. Faculdade de Ciências, Universidade de Lisboa, Portugal Gamelas, C. Instituto Politécnico de Setúbal, Portugal Gasche, T. A. Instituto Superior Técnico, Universidade de Lisboa, Portugal

Participants List

114

Geraldes, C. Universidade de Coimbra, Portugal Gil, A. Universidade de Lisboa, Portugal Gomes, C. S. B. Instituto Superior Técnico, Universidade de Lisboa, Portugal Gomes, J. Instituto Superior Técnico, Universidade de Lisboa, Portugal Gomes, P. T. Instituto Superior Técnico, Universidade de Lisboa, Portugal Granadeiro, C. Faculdade de Ciências, Universidade do Porto, Portugal Jardim, M. G. Universidade da Madeira, Portugal Jaros , S. W. Universidade de Lisboa, Portugal Jarrais, B. Faculdade de Ciências, Universidade do Porto, Portugal Julião, D. REQUIMTE, Faculdade de Ciências, Universidade do Porto, Portugal Laia, C. A.T. REQUIMTE, FCT, Universidade Nova de Lisboa, Portugal Lima, J.C. FCT, Universidade Nova de Lisboa, Portugal Lima, P. Universidade de Aveiro, Portugal Lodeiro, C. BIOSCOPE Group, REQUIMTE, FCT, Universidade Nova de Lisboa, Portugal Lopes, P. Instituto Superior Técnico, Universidade de Lisboa, Portugal Lopes, R. FCT, Universidade Nova de Lisboa, Portugal Lucena, A. F. CTN/IST, Universidade de Lisboa, Portugal Madeira, F. Instituto Superior Técnico, Universidade de Lisboa, Portugal Magalhães, C. Universidade de Aveiro, Portugal Marçalo, J. Instituto Superior Técnico, Universidade de Lisboa, Portugal Marreiros, J. Faculdade de Ciências, Universidade de Lisboa, Portugal Martinho, P. N. CQB, Faculdade de Ciências, Universidade de Lisboa, Portugal Martins, A. M. Instituto Superior Técnico, Universidade de Lisboa, Portugal Mateus, P. ITQB, Universidade de Lisboa, Portugal Mendo, S. Faculdade de Ciências, Universidade de Lisboa, Portugal Mesquita, L. M. ITQB, Universidade de Lisboa, Portugal Mestre, A. S. Faculdade de Ciências, Universidade de Lisboa, Portugal Moura, J. FCT, Universidade Nova de Lisboa, Portugal Moura, N. M. BIOSCOPE Group, REQUIMTE, FCT, Universidade Nova de Lisboa, Portugal Munhá, R. University of California Irvine, United States Nolasco, M. Universidade de Aveiro, Portugal Nunes, C. D. CQB, Faculdade de Ciências, Universidade de Lisboa, Portugal Nuñez, C. BIOSCOPE Group, REQUIMTE, FCT, Universidade Nova de Lisboa, Portugal

Ogarkov, A. Baikov Institute of Metallurgy and Materials Science, Russian Academy of Sciences

Oliveira, E. BIOSCOPE Group, REQUIMTE, FCT, Universidade Nova de Lisboa, Portugal Oliveira, S. Instituto Superior Técnico, Universidade de Lisboa, Portugal Paramasivam, K. Instituto Superior Técnico, Universidade de Lisboa, Portugal Parola, A. J. FCT, Universidade Nova de Lisboa, Portugal Pauleta, S. REQUIMTE, FCT, Universidade Nova de Lisboa, Portugal Peixoto, A. F. Faculdade de Ciências, Universidade do Porto, Portugal Pereira, C. REQUIMTE, Faculdade de Ciências, Universidade do Porto, Portugal Pereira, M. M. Universidade de Coimbra, Portugal Pessoa, J. C. CQE, Instituto Superior Técnico, Universidade de Lisboa, Portugal Petronilho, A. University College Dublin, Ireland Pineiro, M. Universidade de Coimbra, Portugal Pinto, T. Faculdade de Ciências, Universidade do Porto, Portugal Pires, A. Universidade de Lisboa, Portugal

Participants List

115

Realista, S. CQB, Faculdade de Ciências, Universidade de Lisboa, Portugal Relvas, C. Universidade de Évora, Portugal Rocha, B. G. M. IST-ID, Portugal Rodrigues, I. Instituto Superior Técnico, Universidade de Lisboa, Portugal Rodríguez, L. Universitat de Barcelona, Spain Romão, C. C. ITQB, Universidade de Lisboa, Portugal Rosa, V. FCT, Universidade Nova de Lisboa, Portugal Royo, B. ITQB, Universidade de Lisboa, Portugal Ruivo, A. FCT, Universidade Nova de Lisboa, Portugal Ruiz-Molina, D. CSIC, Barcelona, Spain Santos, C.I.M. REQUIMTE, FCT, Universidade Nova de Lisboa, Portugal Santos, T. M. Universidade de Aveiro, Portugal Saraiva, M. S. Faculdade de Ciências da Universidade de Lisboa, Portugal Silva, M. Universidade de Coimbra, Portugal Silva, R.A.L. Instituto Superior Técnico, Universidade de Lisboa, Portugal Silveira, C. M. REQUIMTE, FCT, Universidade Nova de Lisboa, Portugal Soares, C. O. Instituto Superior Técnico, Universidade de Lisboa, Portugal Vaz, P. D. FCT, Universidade Nova de Lisboa, Portugal

Friday, April 11 Saturday, April 12

9:00 9:00

15 15

30 30

45 45

10:00 10:00

15 15

30 30

45 45

11:00 11:00

15 15

30 30

45 45

12:00 12:00

15 15

30 30

45 45

13:00 13:00

15 15

30 30

45 45

14:00 14:00

15 15

30 30

45 45

15:00 15:00

15 15

30 30

45 45

16:00 16:00

15 15

30 30

45 45

17:00 17:00

15 15

30 30

45 45

18:00 18:00

15 15

30 30

45 45

19:00 19:00

15 15

30 30

45 45

20:00 20:00

15 15

30 30

45 45

Beatriz ROYO 14:30 MANUEL ALMEIDA 14:30

DANIEL RUIZ-MOLINA 09:00

OLIVER EINSLE 11:30

Carlos M. GRANADEIRO 18:30

Org

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Manuel JARDIM 10:10

Lunch Break 13:10

Laura RODRIGUEZ 09:45

SPQ Inorg. Chem. Division Meeting 19:30

Poster - Flash Presentation 15:15

Coffee Break and 16:00

Posters Presentation

Rui F. MUNHÁ 17:30

Mis

cella

neou

s

Diana JULIÃO 18:15

Conference Dinner 20:30

Mat

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Carlos BALEIZÃO 10:25

Clara PEREIRA 12:40

Coffee Break and 10:40

Posters Presentation

Samuel DAGORNE 11:40

Ana PETRONILHO 12:05

Christophe FLIEDEL 12:35

Sónia BARROSO 12:50

Luís C. BRANCO 14:55

Pedro MATEUS 15:25

Mónica SILVA 15:10

Inês RODRIGUES 15:40

João C. PESSOA 15:55

Lunch Break 13:10

Sofia PAULETA 12:15

Mat

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Org

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Clara S.B. GOMES 12:20

Carlos GERALDES 12:55

Registration

Bio

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Alberto Romão Dias Prize 16:15

CARLOS C. ROMÃO

Closing Ceremony 17:00

Opening 11:15

Sara FATEIXA 18:00

M. Clara MAGALHÃES 19:00

Ana Lúcia PIRES 18:45

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