5º SIMPOSIO LATINOAMERICANO DE QUÍMICA DE COORDINACIÓN Y ORGANOMETÁLICA

5th LATIN AMERICAN SYMPOSIUM ON COORDINATION AND ORGANOMETALLIC CHEMISTRY

BOOK OF ABSTRACTS

TRACK 1

Coordination / Bioinorganic Chemistry, and Inorganic Materials / Related Areas

http://silqcom2015.com.br/

SPONSORS

ORGANIZATION

SUPPORT

ORGANIZING COMMITTES

Organizing Committee of SILQCOM Chairs: Prof. Eduardo Nicolau dos Santos - Federal University of Minas Gerais - Brazil Prof. Jairton Dupont - Federal University of Rio Grande do Sul - Brazil Prof. Maria D. Vargas - Fluminense Federal University - Brazil Members: Prof. Dalmo Mandeli - Federal University of ABC - Brazil Prof. Marciela Scarpellini - Federal University of Rio de Janeiro - Brazil Prof. Maria Helena Araújo - Federal University of Minas Gerais - Brazil Prof. Maurício Lanznaster - Fluminense Federal University - Brazil Prof. Tiago A. S. Brandão (Secretary) - Federal University of Minas Gerais – Brazil

Organizing Committee of Brazil-France Bilateral Workshop Prof. Dalmo Mandeli - Federal University of ABC - Brazil Prof. Pierre Dixneuf - University of Rennes – France

Scientific Committee of SILQCOM Prof. Anellise Casellato - Federal University of Rio de Janeiro - Brazil Prof. Ademir Neves - Federal University of Santa Catarina - Brazil Prof. Claudio N. Verani - Wayne State University - USA Prof. Elena V. Gusevskaya - Federal University of Minas Gerais - Brazil Prof. Humberto O. Stumpf - Federal University of Minas Gerais - Brazil Prof. Liani Rossi - University of São Paulo - Brazil Prof. Osvaldo Casagrande Jr. - Federal University of Rio Grande do Sul - Brazil

Permanent International Committee of SILQCOM Prof. Fabio Doctorovich - University of Buenos Aires – Argentina Prof. Eduardo N. dos Santos - Federal University of Minas Gerais - Brazil Prof. Pedro Aguirre - University of Chile - Chile Prof. Ana Esperanza Burgos - National University of Colombia - Colombia Prof. Eduardo Peris - University of Jaume - Spain Dr. Maurizio Peruzzini - ICCOM - National Research Council - Italy Prof. Hiroshi Nakazawa - Osaka City University - Japan Prof. Ivan Castillo - Autonomous National University of Mexico - Mexico Prof. Wilfredo Hernández - Lima University - Peru Dr. Luca Fadini - Helsinn Healthcare - Switzerland Prof. Roberto Sánchez Delgado - City University of New York - USA Prof. Dinorah Gambino - University of Republic - Uruguay Prof. Pablo Barricelli - University of Carabobo - Venezuela

CONTENTS

General Information i

Scientific Program ii

Abstracts of Invited Lectures 1

Abstracts of Oral Invited Lectures 18

Abstracts of Oral Communications 30

Abstracts of Posters 43

Author Index 88

i

GENERAL INFORMATION

Instructions to Authors

Speakers It is suggested that speakers turn in their CD, USB drive or slides, properly numbered to the projector operator before the beginning of the session during which their communication will be given.

Posters Authors of posters are required to mount their posters on the board marked with their poster-number, in the morning preceding the poster session, and to remove them at the end of the session.

ii

SCIENTIFIC PROGRAM TRACK 1

SUNDAY, OCTOBER 18

14:30 - 17:30

Registration

18:00 - 20:00

Opening Ceremony

IL11/2 David Cole-Hamilton The Catalytic Production of Chemicals from

Waste Bio-Oils

IL21/2 Ademir Neves The Role of Secondary Effects on the Catalytic

Activity of Metallohydrolases Biomimetics

21:00 - 22:30

Welcome mixer

IL = Invited Lecture (45 min); SL = Short Invited Lecture (30 min); OC = Oral Communic

MONDAY, OCTOBER 19

9:45 - 10:30 IL31 Koiti Araki From Molecular to Nanostructured

Electrocatalysts

10:35 - 11:00

Coffee-break

11:00 - 11:45 IL41 Miguel A. Novak Molecular Chain “Magnets”

11:45 - 12:15 SL11 Celia M. Ronconi Hybrid Materials: Synthesis and Applications

12:15 - 12:35 OC11 Pablo Fuentealba Analysis of Magnetic Behavior of Composites

Based on the Layered Manganese(II) Thiophosphate Phase

12:35 - 14:30

Lunch

14:30 - 15:15 IL51 Fabio Doctorovich Quantification of HNO in Real Time: NO/HNO

Interconversion

15:15 - 15:45 SL21 Roberto S. da Silva Emerging Applications of Ruthenium Compounds as Modulators of Nitric Oxide Singlet Oxygen by

Light Irradiation. Use Against Cancer Cells

15:45 - 16:05 OC21 Brenda Eguía Biomimetic Approach to PHM Monooxygenase

Active Site with Triplet Cupric-Superoxo Complexes

16:05 - 16:30

Coffee-break

16:30 - 17:00 SL31 Ronan Le Lagadec Regulation of Oxidoreductase Activity by Cytotoxic

Ruthenium and Osmium Complexes

iii

17:00 - 17:30 SL41 Julio S. Rebouças On the Design of Mn(III) N-Pyridylporphyrin-Based Biomimetic Models of Oxidoreductase

Enzymes

17:30 - 19:00

Poster session (odd numbers)

IL = Invited Lecture (45 min); SL = Short Invited Lecture (30 min); OC = Oral Communication (20 min)

TUESDAY, OCTOBER 20

9:00 - 9:45 IL61 Heloisa Beraldo Schiff Base-Derived Ligands and Metal

Complexes: Relevance in Medicinal Inorganic Chemistry

9:45 - 10:15 SL51 Maribel Navarro Metal-Based Agents Against Sporothrix schenckii

10:15 - 10:35 OC31 Willian R. Rocha Reaction Mechanism for Methane Oxidation

Reaction Promoted by a Structural Model of the PMMO Enzyme

10:35 - 11:00

Coffee-break

11:00 - 11:45 IL71 Katherine Franz Conditional Surrender: Designing Molecules to

Put Biological Metals in Their Place

11:45 - 12:15 SL61 Peter G. Edwards Facially Capping P-Macrocycles - The Control of

Lability in Metal-Phosphine Complexes and Applications in Reactivity

12:15 - 12:35 OC41 Willian Xerxes Niobium(V) as Bridge for Magnetic Coupling in a

Cr(III)2Nb(V)2 Molecular Square

12:35 - 14:30

Lunch

14:30 - 15:15 IL81 Daniel H. Murgida Determinants of Electron Transfer Efficiency and Gain of Alternative Functions in Redox

Metalloproteins

15:15 - 15:45 SL71 Maria Contel Potential Cancer Chemotherapeutics Based on

Heterometallic Titanium-Gold and Ruthenium-Gold Scaffolds

15:45 - 16:05 OC51 Nicholas Chilton The Electronic Structure of Molecular Uranium(V)

Nitrides

16:05 - 16:30

Coffee-break

16:30 - 16:50 OC61 Luke A. Wilkinson Mechanistic Insight Into Proton Coupled Mixed

Valency

16:50 - 17:10 OC71 Brenda Ruiz Adsorption Process Induced by Supramolecular

Interactions

17:10 - 17:30 OC81 Javier Gomez Stability in Aqueous Solution of Novel [(para-

Cymene)Ru(II)(Aza-Chalcone)Cl]+ Complexes: Unexpected Alkene Hydration Reaction

17:30 - 19:00 Poster session (even numbers)

IL = Invited Lecture (45 min); SL = Short Invited Lecture (30 min); OC = Oral Communication (20 min)

iv

WEDNESDAY, OCTOBER 21

9:00 - 9:45 IL91 Daniela Buccella Illuminating Metals: Fluorescent Tools for the

Study of Magnesium Homeostasis

9:45 - 10:15 SL81 Victor M. Deflon Metal Complexes Aiming Application as

Radiopharmaceuticals

10:15 - 10:35 OC91 Cynthia Demicheli New Antimony Complexes as Potential

Antileishmanial Agents Against Sb(III)-Sensitive and -Resistant Parasites

10:35 - 11:00

Coffee-break

11:00 - 11:45 IL101 Ebbe Nordlander High Valent Iron Oxo Complexes as

Catalysts for the Oxidation of Alkanes and Alkenes

11:45 - 12:15 SL91 Ivan Castillo Biologically-Inspired Nickel and Iron Complexes with Chelating Aminodi- and Trithiophenolates

12:15 - 12:35 OC101 Elene Maia Photoinduced Cytotoxicity and DNA Cleavage by

Novel Ru(II) Complexes

12:35 - 14:30

Lunch

14:30 - 19:00

Free afternoon

IL = Invited Lecture (45 min); SL = Short Invited Lecture (30 min); OC = Oral Communication (20 min)

THURSDAY, OCTOBER 22

9:00 - 9:45 IL111 Ana Ferreira Kinases as Targets for Oxindolimine Metal

Complexes with Antitumor Activity

9:45 - 10:15 SL101 Marciela Scarpellini Triazolic Cobalt(III) Compounds as Carrier

Prototypes for Antitumor Prodrugs

10:15 - 10:35 OC111 Tiago Pacheco Phosphatase-Like Activity in non Symmetrical FeZn

Complexes: Tunning the Second Coordination Sphere Effects in the Phosphate Ester Hydrolysis

10:35 - 11:00

Coffee-break

11:00 - 11:45 IL121 Ines Batinic-Haberle Design of Manganese Porphyrin-Based SOD Mimics as Powerful Anticancer Drugs and

Radioprotectors

11:45 - 12:15 SL111 Flávia C. Machado Lanthanide Compounds Used in OLEDs

Construction

12:15 - 12:35 OC121 James Pankhurst Macrocyclic Transition Metal Complexes for

Electrochemical Reduction of Carbon Dioxide

12:35 - 14:30

Lunch

14:30 - 15:15 IL131 Liane M. Rossi Organometallic Preparation of Metal

Nanoparticles for the Design of Supported Catalysts

v

15:15 - 16:00 IL141 Faruk Nome Zwitterionic Surfactant Stabilized Palladium

Nanoparticles as Catalysts

16:05 - 16:30

Coffee-break

16:30 - 17:15 IL151 Pedro T. Gomes Tuning the Luminescence of Tetracoordinated

Organoboron Complexes with Iminopyrrolyl Bidentate Ligands

17:15 - 18:00 IL161 Maurizio Peruzzini Recent Advances in Phosphorus Coordination

and Organometallic Chemistry

18:00 - 18:30

Closing Ceremony

21:00 - 23:00

Farewell party

IL = Invited Lecture (45 min); SL = Short Invited Lecture (30 min); OC = Oral Communication (20 min)

1

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2

IL11/2

THE CATALYTIC PRODUCTION OF CHEMICALS FROM WASTE BIO - OILS

David J. Cole-Hamilton,a* Ruben Duque Garcia,a Ronan le Goff,a Marc Furst,a Juma

Mmongoyo,b James Mgaya,b Jennifer Julisa Stuart Bartletta Sabrina Baaderc and Quintino

Mganib

a EaStCHEM, School of Chemistry, University of St. Andrews, St. Andrews, Fife, KY16 9ST, Scotland, UK

bUniversity of Dar es Salaam, Chemistry Department, P.O.Box 35061, Dar es Salaam, Tanzania c Fachbereich Chemie, Organische Chemie, TU Kaiserslautern, Erwin-Schrödinger-Straße 54, 67663

Kaiserslautern, Germany

*Tel: +44-1334-463805; Fax: +44-1334-463808; E-mail: djc@st-and.ac.uk

As oil supplies dwindle and the price increases, it is essential to find new ways of making the many chemicals on which the quality of our lives depends. One approach is to use renewable resources which can be grown. However, there is a tension between using land for fuel or chemicals production and the need to use land to produce food for the rapidly increasing world population. One possible solution is to use waste products for the manufacture of chemicals. In this presentation, we shall discuss the conversion of methyl oleate and oleic acid, a major component of Tall Oil, a waste from wood processing, into polymer precursors. We shall also discuss the synthesis of a range of important chemicals from cashew nut shell liquid (CNSL), a waste from cashew nut processing.

We shall show how homogeneous carbonylation,[1] metathesis, and reductive amination[2] can be used to make difunctional esters acids, alcohols and amines[1a, 3] for polymer formation[4] from unpurified natural oils containing oleate residues.

Since homogeneous catalysts suffer the potential difficulty of product-catalyst separation, we shall show how supported ionic liquid phase SILP) catalysts with carbon dioxide flow (see Figure 1) allow the ready separation of the products from the catalyst, thus overcoming one of the major difficulties associated with scaling up and using homogeneous catalysts commercially. We shall describe our developments on metathesis[5] and other reactions using these systems.

Cashew nut shell liquid contains interesting phenols meta substituted with an unsaturated C15 chain. We shall described how it can be used to synthesise tse-tse fly attractants, potentially safe detergents, polymer additives, monomers for polymerisation and large ring macrocyclic lactones.[6] (Figure 1).

[1] a) C. Jiménez-Rodriguez, G. R. Eastham, D. J. Cole-Hamilton, Inorg. Chem. Commun. 2005, 8, 878-881; b) C. J. Rodriguez, D. F. Foster, G. R. Eastham, D. J. Cole-Hamilton, Chem. Commun. 2004, 1720-1721.

[2] A. A. Nunez Magro, G. R. Eastham, D. J. Cole-Hamilton, Chem. Commun. 2007, 3154-3156. [3] a) M. R. L. Furst, R. le Goff, D. Quinzler, S. Mecking, D. J. Cole-Hamilton, Green Chem. 2011, 14, 472-477; b) M. R. L. Furst, T. Seidensticker, D. J.

Cole-Hamilton, Green Chem. 2013, 15, 1218 - 1225. [4] a) D. Quinzler, S. Mecking, Angew. Chem. Int. Ed. 2010, 49, 4306-4308; b) F. Stempfle, D. Quinzler, I. Heckler, S. Mecking, Macromolecules

2011, 44, 4159-4166. [5] R. Duque, E. Ochsner, H. Clavier, F. Caijo, S. P. Nolan, M. Mauduit, D. J. Cole-Hamilton, Green Chem. 2011, 13, 1187-1195. [6] a) J. A. Mmongoyo, Q. A. Mgani, J. M. Mdachi, P. J. Pogorzelec, D. J. Cole-Hamilton, Eur. J. Lipid. Sci. Technol. 2012, 114, 1183-1192; b) S.

Baader, P. E. Podsiadly, D. J. Cole-Hamilton, L. J. Goossen, Green Chem., 16, 4885-4890; c) J. Julis, S. A. Bartlett, S. Baader, N. Beresford, E. J. Routledge, C. S. J. Cazin, D. J. Cole-Hamilton, Green Chem. 2014, 16, 2846-2856; d) J. E. Mgaya, E. B. Mubofu, Q. A. Mgani, D. B. Cordes, A. M. Slawin, D. J. Cole-Hamilton, Eur. J. Lipid. Sci. Technol. 2015, 117, 190-199.

Fig. 1 Chemicals from cashew nut shell liquid

3

IL21/2

THE ROLE OF SECONDARY EFFECTS ON THE CATALYTIC ACTIVITY OF METALLOHYDROLASES BIOMIMETICS

Ademir Neves

UFSC - Universidade Federal de Santa Catarina

Keywords: Metalloydrolases, Biomimetics, DNA intercalation

Phosphatases, oxidases and a variety of other enzymes have been successfully modeled through metal complexes that can reproduce their physico-chemical properties and even their catalytic activity, however with a much lower efficiency. As has been suggested, these discrepancies in catalytic efficiency between model compounds and true enzymes are, by a large extent, due to the lack of many important intramolecular interactions in the second-coordination sphere of the model systems in comparison to the enzyme. In this work we propose a new extension of dinuclear hydrolases models by binding the FeIIIMII ((MII = Zn, Cu) catalytic unit to a small polyethyleneimine chain (PEI, 1200 Da) that can emulate the enzyme microenvironment around the active site. In addition we also present the synthesis, characterization and hydrolase-like activity of conjugates in which the well known DNA intercalator pyrene is covalently linked to the FeIIIMII catalytic center.

4

IL31

From Molecular to Nanostructured Electrocatalysts

Koiti Araki

University of Sao Paulo, Department of Fundamental Chemistry, Sao Paulo, SP, 05508-000, Brazil (email: koiaraki@iq.usp.br)

The electrocalytic properties of metalloporphyrins can be enhanced by coordination of transition metal complexes, such as ruthenium polypyridines and ruthenium acetate triangular clusters, to the ring periphery. Their redox state can be electrochemically modified, or can adjust by themself to the electrochemical potential of the environment, inducing electronic effects stabilizing and activating the metalloporphyrin for multielectron redox reactions such as the tetra-electronic reduction of dioxygen to water or the oxidation of organic substrates, respectively mimicking the activity of cytochrome c oxidase and cytochrome P450.

On the other hand, [NiTPyP{Ru(bpy)2Cl}4] species can be electropolymerized generating electrodes modified with a polymeric material exhibiting nickel hydroxide like electrochemical and electrocatalytic properties. Other nickel macrocycles exhibit similar behavior but the actual structure of the product is still a matter of controversy. Recently, the structure of such poly-tetraruthenated nickel porphyrin was revealed for the first time to be a µ-peroxo (Ni-O-O-Ni) bridged coordination polymer, by electrochemistry, Raman spectroelectrochemistry and hydroxyl radical trapping assay. The electropolymerization process seems to involve hydroxyl radicals (as confirmed by the characteristic set of DMPO/•OH adduct EPR peaks) electrocatalytically generated on the electrode surface, and hydroxide anions coordinated to the nickel porphyrin axial positions. Finally, its electrochemical properties will be compared with that of nickel hydroxide nanoparticles, more specifically the more active but meta-stable alpha-polymorph. Enhanced electrocatalytic properties for oxidation of organic substrates such as sugar and alcohols, and their application in amperometric sensors, will be discussed.

REFERENCES

1. Supramolecular Porphyrins as Electrocatalysts”, Koiti Araki e Henrique Eisi Toma, in N4-Macrocyclic Metal Complexes; J. Zagal, F. Bedioui e J. P. Dodelet (Eds.), Springer, NY, 2006, cap. 6, 255-314, ISBN 13: 978-0387-28429-3.

2. Luis MC Ferreira, Daniel Grasseschi, Mauro SF Santos, Paulo R Martins, Ivano GR Gutz, Ana Maria C Ferreira, Koiti Araki, Henrique E. Toma e Lúcio Angnes, “Unveiling the Structure of Poly-Tetraruthenated Nickel Porphyrin by Raman Spectroelectrochemistry”, Langmuir 31(2015)4351-4360.

3. Maria do Socorro Maia Quintino, Herbert Winnischofer, Marcelo Nakamura, Koiti Araki, Henrique Eisi Toma and Lúcio Angnes, “Amperometric Sensor for Glucose Based on Electrochemically Polymerized Tetraruthenated Nickel-Porphyrin”, Anal. Chim. Acta. 539 (2005) 215–222

4. Paulo Roberto Martins, Sergio Hiroshi Toma, Marcelo Nakamura, Henrique Eisi Toma and Koiti Araki, “Thermodynamic Stabilization of Nanostructured Alpha-Ni1-xCox(OH)2 for High Efficiency Batteries and Devices”, RSC Advances 03 (2013) 20261-20266.

5. Paulo Roberto Martins, André Luis Araújo Parussulo, Sergio Hiroshi Toma, Michele Aparecida Rocha, Henrique Eisi Toma and Koiti Araki, "Highly Stabilized Alpha-NiCo(OH)2 Nanomaterials for High Performance Device Application", J. Power Sources 218 (2012) 1-4.

5

IL41

MOLECULAR CHAIN “MAGNETS”

Miguel A. Novak*1, Rafael A. Cassaro2, Maria G. F. Vaz3

1Institute of Physics, Federal University of Rio de Janeiro; 2Institute of Chemistry, Federal University of Rio de Janeiro; 3Institute of Chemistry, Fluminense Federal University.

Linear magnetic chains have interacting individual magnetic moments magnetically correlated along one direction. They have been studied since the early 60’s as the first experimental results on transition metal oxalates appeared. Theoretical models and methods were developed and were used successfully for one-dimensional (1D) model Hamiltonians with high anisotropy (Ising limit) or isotropic Heisenberg model. Since then low dimensional magnetic systems challenged physicist and chemists to explain results from a growing number of inorganic systems. More recently, chemists making use of supramolecular techniques contributed to the enlargement of 1D magnetic systems with a large variety of spin topologies forming ferromagnetic, ferromagnetic and alternating chains. These chains were modeled using Hamiltonians solved numerically in finite size and extrapolated to infinite size, and explained successfully the magnetic properties of many experimental systems. A new burst of interest on 1-D magnetic molecular based systems started with the discovery of slow relaxation of the magnetization and magnetic hysteresis at the beginning of this millennium in a Co-Radical Ferrimagnetic chain[1]. This system named as “Single Chain Magnet” (SCM) following the designation of Single Molecule Magnet (SMM) discovered a decade before. SMMs and SCMs, as well as the more recent discovery of hysteresis on magnetically isolated mononuclear Rare Earth coordination compounds known as Single Ion Magnets (SIM) became very interesting, are considered as the ultimate magnetic memory elements as well as Qubits for use in quantum information. We will present after reviewing shortly this story, our recent results for Co-Radical ferrimagnetic chains which present record high blocking temperatures as well as record high coercivity at low temperatures [2.3]. Finite size effects due to defects play a fundamental role in the description of these systems. We will describe the structure and magnetic properties of these chains and discuss the origin of the slow magnetic relaxation of them.

References:

1. Caneschi, A.; Gatteschi, D.; Lalioti, N.; Sangregorio, C.; Sessoli, R.; Venturi, G.; Vindigni, A.; Rettori, A.; Pini, M. G.; Novak, M. A.; Cobalt(ii)-Nitronyl Nitroxide Chains as Molecular Magnetic Nanowires Angew. Chem. Int. Ed. V.40, p. 1760-1763, 2001.

2. Vaz, M. G. F., Cassaro, R. A. A., Akpinar, H., Schlueter, J. A., Lahti, P. M., Novak, M. A. A Cobalt Pyrenylnitronylnitroxide Single-Chain Magnet with High Coercivity and Record Blocking Temperature. Chemistry - A European Journal. , v.20, p.5460 - 5467, 2014.

3. Cassaro, R. A. A.; Reis, S. G.; Araujo, T. S.; Lahti, P. M.; Novak, M. A; Vaz, M. G. F., A Single-Chain Magnet with a Very High Blocking Temperature and a Strong Coercive Field Inorg. Chem. DOI: 10.1021/acs.inorgchem.5b01431 (2015)

CAPES, CNPQ, FAPERJ

6

IL51

QUANTIFICATION OF HNO IN REAL TIME: NO/HNO INTERCONVERSION

Fabio Doctorovich

UBA - INQUIMAE-CONICET, DQIAQF-FCEYN

Keywords: Nitroxyl, Nitric oxide, Metalloporphyrin

In the last few years several methods have been developed to detect and quantify HNO. The most useful methods rely on optical or electrochemical measurements.(1) A Co-porphyrin modified electrode was developed and calibrated,(2) being able to detect down to 1 nM [HNO]. As a comparison, the initial [HNO] produced by 1 mM HNO donors at rt. is ca. 100 nM. Moreover, the sensor discriminates HNO from NO, and responds to repeated additions of an HNO donor, without signal loss. In the presence of O2 the amount of HNO detected diminishes due to the reaction of HNO with O2, but interfering species, such as H2O2, do not affect the measurements. Also, the detection can be achieved in real time i.e., the sensor has a fast response to changes in [HNO], so that the instant concentration of HNO can be monitored. Recent evidence suggests that HNO could be involved in biological processes, some of which are attributed to NO. In this context, one of the most important and yet unanswered questions is whether HNO is produced in vivo. Possible routes concern chemical or enzymatic reduction of NO. Experiments with the sensor show that HNO is produced from NO by alcohols with moderate reducing capacity, such as the biologically relevant vitamin C.(3) The proposed mechanism involves nucleophilic attack to NO by the alcohol, coupled to proton transfer and subsequent decomposition of the so-produced radical to yield HNO and an alkoxyl radical. NO reduction by other biologically relevant compounds such as amines and thiols will also be discussed.

REFERENCES

1. Doctorovich, F.; Bikiel, D.; Pellegrino, J.; Suárez, S.A.; Martí, M.A. ; Acc. Chem Res. 2014, 47, 2907-2916.

2. Suarez, S. A.; Bikiel, D.E.; Wetzler, D.; Martí, M.A.; Doctorovich, F.; Anal. Chem. 2013, 85,10262–10269.

3. Suarez, S.A.; Neuman, N.I.; Muñoz, M.; Alvarez,L.; Bikiel, D.; Brondino, C.;Ivanovic-Burmazovic, I.; Miljkovic, J.L.; Filipovic, M.R.; Martí, M.A.; Doctorovich, F. ; J. Am. Chem. Soc. 2015, 137, 4720-4727.

7

IL61

SCHIFF BASE-DERIVED LIGANDS AND METAL COMPLEXES: RELEVANCE IN MEDICINAL INORGANIC CHEMISTRY

Heloisa Beraldo

Departamento de Química, Universidade Federal de Minas Gerais, Brazil

Schiff base derivatives comprise several classes of compounds with wide pharmacological profile, which have applications in therapeutics and medical diagnosis. Strategies for the design of Schiff base-derived ligands and metal complexes with potential applications in cancer therapeutics will be discussed, as well as the design of Schiff base metal binding agents as drug candidates for the treatment of Alzheimer’s disease. Schiff base derivatives play an important role in Medicinal Inorganic Chemistry and make up a valuable platform in the discovery of new lead scaffolds.

8

IL71

CONDITIONAL SURRENDER: DESIGNING MOLECULES TO PUT BIOLOGICAL METALS IN THEIR PLACE

Katherine J. Franz

Duke University

Durham, NC

Metal ions are required nutrients for many organisms but also potential toxins. The distribution networks of inorganic elements are therefore strategic battlegrounds in a wide range of diseases, including neurodegeneration, cancer, and infection. Metal chelators are attractive agents for readjusting cellular metal loads, but targeting a specific metal ion at the exclusion of others and without inhibiting metalloproteins can be challenging. Furthermore, because ligands influence the chemical properties of their coordinated metals, chelating agents used intracellularly can alter not only the location but also the reactivity of metals, especially iron, copper and zinc. In this talk, I will present our efforts to develop chelating agents that can be triggered by specific stimuli to change their metal binding capacity and reactivity. In particular, we will discuss prochelators that are activated by either hydrogen peroxide or light to bind iron and copper and thereby influence cell survival.

9

IL81

DETERMINANTS OF ELECTRON TRANSFER EFFICIENCY AND GAIN OF ALTERNATIVE FUNCTIONS IN REDOX METALLOPROTEINS

Daniel Murgida

UBA - Universidad De Buenos Aires

Keywords: electron transfer, CuA, cytochrome

Electron-transfer (ET) constitutes the basis of energy transduction in living organisms and involve a plethora of fine-tuning mechanisms that arise from the complexity of the redox proteins. In this lecture I will present recent studies on the redox couple cytochrome c (Cyt) / CuA. The CuA site of cytochrome c oxidase is a redox hub that participates in rapid ET with two redox cofactors in nearly perpendicular orientations. The electronic structure of CuA can be described by a double-well potential, where the energy minima correspond to two alternative ground states.(1) The energy gap between these two states can be modulated by first- and second-sphere mutations, as well as pH, thus allowing to experimentally probing reversible switching and ET from the individual states.(1-4)

Experiments and calculations indicate that the formation of the transient complex between Cyt and CuA activates a low reorganization energy (λ) form of Cyt,(5) thus optimizing ET to the higher energy ground state of CuA. Subsequent ET from CuA to heme a is optimized from the lower lying state, thus conferring directionality.(6) Alternation between electronic states and conformations with low and high λ is modulated by local electric fields. Moreover, electric fields and post-translational modifications may induce the loss of electron transport capability concomitant with the gain of new functions, such as peroxidase activity of Cyt, thus alternating between life sustaining and apoptotic functions.(7,8)

1. Abriata et. al. Proc. Natl. Acad. Sci. USA 2012, 109, 17348.

2. Alvarez-Paggi et. al. Chem. Comm. 2013, 49, 5381.

3. Morgada et. al. Angew. Chem. Int. Ed. 2014, 53, 6188.

4. Zitare et. al. Angew. Chem. Int. Ed. 2015, in press, DOI: 10.1002/anie.201504188 5. Alvarez-Paggi et. al. J. Am. Chem. Soc. 2013, 135, 4389.

6. Álvarez-Paggi et.al BBA-Bioenergetics 2014, 1837, 1196.

7. Capdevila et. al. Chem. Science 2015, 6, 705.

8. Capdevila et. al. Chem. Comm. 2014, 50, 2592.

10

IL91

ILLUMINATING METALS: FLUORESCENT TOOLS FOR THE STUDY OF MAGNESIUM HOMEOSTASIS

Daniela Buccella, Mohammad Afzal, Jessica Gruskos, Qitian Lin, Brismar Pinto-Pacheco, Jean-Philippe Pitteloud, Guangqian Zhang

NYU - New York University

Keywords: Magnesium, Fluorescence Indicators, Cellular Imaging

Mg2+ is the most abundant divalent cation in mammalian cells and plays a role in numerous processes that are key for proper cellular function.1 Abnormal levels of magnesium have been associated with a variety of diseases, including cardiovascular disease and cancer,2 yet the underlying mechanisms involving this ion in the development of these pathologies are still far from clear. Fluorescence imaging has emerged as an effective tool for the study of intracellular Mg2+, but currently available indicators lack the combination of selectivity and spatial resolution required to study compartmentalization and trafficking of this ion in the context of physiological and pathological processes. In this context, we have developed new triazole-based ‘clickable’ ratiometric fluorescent probes for the detection of Mg2+ in specific intracellular compartments by fluorescent microscopy. The new sensors, with dissociation constant in the low millimolar range, are suitable for the detection of typical levels of intracellular free magnesium, and have enabled direct observation of fluctuations of this involved in early stages of apoptosis. General strategies for targeting small-molecule sensors to specific organelles, and new low-denticity sensor designs aimed at achieving selective detection of free Mg2+ in the complex matrix of the cell will be discussed as well.

References:

1. Cowan, J.A, .The Biological Chemistry of Magnesium,1995, 1

2. Romani, A.M.P, Interrelations Between Metal Ions and Human Diseases, Vol 13, 2013, 49. This work was conducted with support from New York University

11

IL101

HIGH VALENT IRON OXO COMPLEXES AS CATALYSTS FOR THE OXIDATION OF ALKANES AND ALKENES

Mainak Mitra1, Biswanath Das1, Satish Bhat1, Sergey Malinkin1, Miquel Costas2, Ebbe Nordlander*1

1Chemical Physics, Department of Chemistry, Lund University, Box 124, SE-221 00 Lund,

Sweden); 2 Department of Chemistry and Institute of Computational Chemistry and Catalysis (IQCC), University of Girona, Campus Montilivi, 17071 Girona, Spain

.

This lecture will describe a number of mononuclear Fe(II), Fe(IV)=O (ferryl) and Fe(V)=O (perferryl) complexes,1,2 as well as dinuclear Fe(III)-O-Fe(III) complexes,3,4 that function as catalysts or precatalysts for (i) hydroxylation of alkanes and alkenes via hydrogen atom transfer (HAT) and oxygen atom transfer (OAT) mechanisms (ii) oxidation of substrates via OAT (iii) (asymmetric) epoxidation of prochiral alkenes. Reactivity studies on the various complexes that aid the elucidation of mechanistic aspects of the oxidation reactions will be described.

References:

1. Mitra, M.; Lloret-Fillol, J; Haukka, M.; Costas, M.; Nordlander, E. , A.B; Santos, C.D.Chem. Commun.., 50ª ed., 2014, 1408.

2. Mitra, M., Nimir, H.; Demeshko, S.; Bhat, S.S.; Malinkin, S.O.; Haukka, M.; Lloret-Fillol, J.; Lisensky, G.C.; Meyer, F.; Shteinman, A.A.; Browne, W.R.; Hrovat, D.A.; Richmond, M.G.; Costas, M.; Nordlander, E..Inorg. Chem., 54o ed., 2015, 7152.

3. Jarenmark, M.; Tsuritsyna, E.A..; Haukka, M.; Shteinman, A.A., Shteinman, A.A., Nordlander, E. New. J. Chem., 34o ed, 2010, 2118.

4. Das. B., Al-Hunaiti, A.; Haukka, M.; Demeshko, S.; Meyer, S.; Shteinman, A.A.; Meyer, F.; Repo, T.; Nordlander, E.; Eur. J. Inorg. Chem., 2015, 3590.

12

IL111

KINASES AS TARGETS FOR OXINDOLIMINE METAL COMPLEXES WITH ANTITUMOR ACTIVITY

Ana Maria da Costa Ferreira

IQ-USP - Instituto De Química, Universidade De São Paulo

Keywords: metallodrugs, copper complexes, oxindolimines, antitumor activity, kinase proteins

Studies on the inhibition of kinases by some oxindolimine ligands and corresponding metal complexes were carried out to better elucidate their mechanism of action as antitumor agents. These ligands were designed based on oxindole derivatives (as SU9516) already tested clinically as antitumor compounds. Copper(II) and the analogous zinc(II) complexes with different Schiff-base ligands derived from 2,3-dioxindole [1] showed significant inhibition of CDK1, activated by cyclin B, in phosphorylation of histone H1. Copper species were more active than the corresponding zinc with the same ligand. The free ligand was also tested and showed to be less active than the metallated species, indicating a major influence of coordination in the process. Further, the inhibition is also dependent on the coordinated ligand structure. The metal ion introduces charge in the indole species, giving a more rigid conformation to the coordinated ligand that then becomes more effective in its interactions with the active site in the protein. Molecular docking and classical molecular dynamics were applied to provide a better understanding of the effectiveness and the inhibition mechanism of CDK1/cyclin B by the oxindolimine ligand and corresponding metal complexes. Indeed, theoretical simulations including molecular docking show that the metal ion provides a stronger interaction with the ATP binding-active site. Analogously, these metal complexes were tested regarding alkaline phosphatase inhibition, resulting in no significant effect. These results can explain the previously verified cytotoxicity of such metal complexes towards different tumor cells [2], efficiently inducing apoptosis.

1. G. Filomeni, S. Piccirillo, I. Graziani, S. Cardaci, A.M.D. Costa Ferreira, G. Rotilio, M.R. Ciriolo (2009) Carcinogenesis, 30(7): 1115-1124.

2. G. Filomeni, S. Cardaci, A.M.D. Costa Ferreira, G. Rotilio, M.R. Ciriolo (2011) Biochem. J. 437:443-453. Supported by: FAPESP, CEPID Redoxoma, CNPq, CAPES.

13

IL121

DESIGN OF MANGANESE PORPHYRIN-BASED SOD MIMICS AS POWERFUL ANTICANCER DRUGS AND RADIOPROTECTORS

Ines Batinic-Haberle , Artak Tovmasyan ,Ivan Spasojevic

DUMC - Duke University Medical Center

Keywords: Mn porphyrins, SOD mimics, GPx mimics, radioprotectors, anticancer drugs

Based on structure-activity relationships between kinetics and thermodynamics of the catalysis of superoxide dismutation, we have developed cationic ortho isomeric Mn(III) N-substituted porphyrins as powerful SOD mimics. Our studies on their in vivo actions taught us that, in addition to mimicking SOD enzymes, their actions are also H2O2-driven, and are frequently coupled with cellular reductants such as ascorbate and thiols. While they have insignificant catalase-like activity, MnPs possess high glutathione peroxidase- and thiol oxidase-like activities. We have provided evidence that (i) such actions of MnPs are dependent upon the metal-centered reduction potential; (ii) thus parallel each other, and (iii) parallel also their therapeutic efficacies. Actions of MnPs affect cellular transcriptional pathways; among those, H2O2-driven oxidation/S-glutathionylation of NF-kB thiols has been mostly studied. Oxidation of master transcription factor (mostly anti-apoptotic), NF-kB, results in its inactivation and in turn suppression of inflammation and healing of normal cell/tissue. Impact of MnPs on mitochondrial electron transport protein thiols was also reported. Based on in vivo data, Nrf2 transcription factor has been implicated as well. In cancer, though, due to excessive H2O2 levels, massive suppression of NF-kB, leads to cancer cell death. Effect is vastly enhanced with systems that could increase H2O2 production, such as radiation, chemotherapy or ascorbate. Cytotoxicity of MnP/ascorbate system was demonstrated in cellular studies. In vivo studies on mouse bearing mammary flank tumors showed a profound tumor growth inhibition with MnP/RT/ascorbate system. Around 10-fold higher accumulation of MnPs in tumor vs normal tissue support such data. A lead MnP, MnTnBuOE-2-PyP5+ (BMX-001) is entering Phase I/II Clinical Trials at Duke University as a radioprotector on head and neck and glioma cancer patients (1R03-NS082704-01, CNPq/CAPES, NIH U19AI067798, 5-P30-CA14236-29).

14

IL131

ZWITTERIONIC SURFACTANT STABILIZED PALLADIUM NANOPARTICLES AS CATALYSTS

F. Nome*, H. D. Fiedler, F. D. Souza

Department of Chemistry, Federal University of Santa Catarina

Replacement of the ammonium group of sulfobetaines by an imidazolium ring generates a series of zwitterionic surfactants of the type 3-(1-alkyl-3-imidazolio)propane-sulfonate (ImS3-n), with n = 10, 12, 14 and 16.1-3 A special feature of these surfactants is the ability to stabilize metallic nanoparticles (NPs), whose size may be tuned by the amount of water dissolved. The use of ImS3-14 as stabilizer of metallic nanoparticles in biphasic catalysis, affects the role of mass transfer between the two phases. In addition, interactions of surfactant molecules with NPs may modify catalytic activity and selectivity of NPs. Transmission electron microscopy shows well dispersed NPs, with no sign of aggregation, and an average diameter of 3.4 nm. The surfactant forms a double layer around the PdNPs, with the imidazolium and the sulfonate group close to Pd, minimizing the interactions between PdNPs. Palladium NPs stabilized by ImS3-14, are good catalysts for the reduction for a large number of substituted aromatic nitro compounds. Furthermore, the stabilized PdNPs show significant catalytic activity in a series of reaction which includes the hydrogenation of alkenes, reductive amination of benzaldehydes and in a variety of coupling reactions, with negligible leeching of the Pd from the nanoparticles to the organic phase. In fact, Pd/ImS3-12 NPs, adsorbed onto basic aluminium oxide (Al2O3), can be used in the hydrogenation of biodiesel. Based on evidence obtained applying ESI-MS(/MS) spectroscopy to monitor the reactions and detect intermediates, mechanisms for several reactions have been studied in detail. Furthermore, Pd NPs stabilized by ImS3-14 showed efficient catalytic activities for the reduction of aromatic nitro compounds, with high conversion and good selectivity. In terms of environmental impact this is a good result because Pd nanoparticles showed high catalytic activity even using very low loadings of expensive metal.

References:

1. Drinkel, E.; Souza, F. D.; Fiedler, H. D.; Nome, F. Curr Opin Colloid Interf Sci 2013, 18, 26.

2. Souza, F. D.; Souza, B. S.; Tondo, D. W.; Leopoldino, E. C.; Fiedler, H. D.; Nome, F. Langmuir 2015, 31, 3587.

3. Fiedler, H. D.; Drinkel, E. E.; Orzechovicz, B.; Leopoldino, E. C.; Souza, F. D.; Almerindo, G. I.; Perdona, C.; Nome, F. Anal Chem 2013, 85, 10142.

CAPES, CNPQ, FAPESC

15

IL141

ORGANOMETALLIC PREPARATION OF METAL NANOPARTICLES FOR THE DESIGN OF SUPPORTED CATALYSTS

L. L. R. Vono,1 N. J. S. Costa,1 C. Broicher,1 K Philippot,2 L. M. Rossi1*

1Dept. of Fundamental Chemistry, Institute of Chemistry, University of São Paulo, São Paulo, Brazil; 2CNRS, LCC (Laboratoire de Chimie de Coordination), Universite de

Toulouse; UPS, INPT, Toulouse, France

*e-mail: lrossi@iq.usp.br.

Metal nanoparticles have received attention as components for the rational design of heterogeneous catalysts. Nanoparticles are able to develop catalytic activities not seen in the corresponding bulk materials and high selectivity in catalytic transformations. The preparation of well-defined catalyst particles (size, shape, composition) is of pivotal importance for catalytic studies and future applications. We still need to learn how to: i) stabilize metal nanoparticles over solid supports for large scale applications, ii) keep control on particle size during preparation (dial up active sites) and avoid sintering under reaction conditions, iii) obtain a uniform dispersion of the metal nanoparticles over solid surfaces, and finally iv) find ways to avoid metal leaching under real reaction conditions. Here we will discuss the strategies under development in our research group that involves two steps: the preparation of size-controlled metal nanoparticles (Ni, Pd, Rh and Ru) and then their immobilization on solid supports. The metal nanoparticles were prepared by decomposition of organometallic precursors, which has emerged as an efficient and reproducible approach toward the preparation of well-controlled metal nanoparticles in terms of dispersion, size distribution, and composition.1 Preferable precursors are based on olefinic organometallic complexes that decompose easily under a dihydrogen atmosphere, via hydrogenation of the olefinic ligands, into corresponding alkanes that are inert toward the metallic surface.2 Thus, the only molecules present on the surface are the polymers or ligands used for their stabilization. As a result, the organometallic approach has been suitable for preparing nanomaterials for catalytic applications. We will highlight the preparation of magnetically recoverable catalysts3 and their application in liquid phase hydrogenations.

References:

1. Phillipot, K.; Chaudret, B. In Comprehensive Organometallic Chemistry III; Crabtree, R. H., Mingos, M. P., Eds.; Elsevier:Amsterdam, 2007; p 71.

2. Lara, P.; Philippot, K.; Chaudret, B. ChemCatChem. 2013, 5, 28.

3. Rossi, L. M.; Garcia, M. A. S.; Vono, L. L. R. J. Brazil. Chem. Soc.2012, 23, 1959.

16

IL151

TUNING THE LUMINESCENCE OF TETRACOORDINATED ORGANOBORON COMPLEXES WITH IMINOPYRROLYL BIDENTATE LIGANDS

Pedro T. Gomes

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

Luminescent organic/organometallic complexes have been considered important materials due to their potential use in various applications such as photo- or electroluminescent devices, including organic light emitting diodes (OLEDs). Among these materials, tetracoordinate organoboron compounds are receiving increasing attention.1

In this communication, we present a family of tunable fluorophores based on 2-iminopyrrolyl chelates of diphenylboron. Several aspects of the synthesis, molecular structure, and photophysical characterization of these complexes will be presented. Diverse strategies used for the fine-tuning of the emission colours of these compounds will be discussed: a) employment of N-aryl substituents with different electronic or steric natures; b) extension of the π-conjugated system through the use of bis- or tris-iminopyrrolyl-bridged ligands, leading to polynuclear boron compounds; or c) extension of the π-conjugation by fusing aromatic rings onto one of the pyrrolyl ring C-C bonds.

Some features of the application of these complexes in electroluminescent layers of OLEDs will also be described, leading to devices with luminances as high as 2400 cd m-2, for single layer devices, increasing to 4400 cd m-2 when a hole-transporting layer is used.

References:

1. Frath, D;. Massue, J.; Ulrich, G.; Ziessel, R. Angew. Chem. Int. Ed., 2014, 53, 2290. 2. Suresh, D.; et al.; Dalton Trans. 2012, 41, 8502; Suresh, D.; et al.; Chem. Eur. J. 2014, 20, 4126. 3. Suresh, D.; et al.; Chem.Eur. J. 2015, 21, 0000.

We thank the FCT, Portugal, for financial support (Project UID/QUI/00100/2013).

17

IL161

RECENT ADVANCES IN PHOSPHORUS COORDINATION AND ORGANOMETALLIC CHEMISTRY

Maurizio Peruzzini

CNR - ICCOM - Istituto Di Chimica Dei Composti Organometallici

Keywords: Phosphorus chemistry, Organoruthenium Chemistry, 2D-materials, Hydrolysis

In this lecture the most recent achievements in the area of elemental phosphorus' reactivity deriving from the author’s own research in Florence (Italy), will be presented and discussed. Topics of the presentation will include: i) the activation of white phosphorus mediated by late-transition metal complexes with particular emphasis to the unusual hydrolysis of the P4 molecule following its η1-coordination to ruthenium, which result in a variety of unusual Px fragments (x ≤ 4), such as P-oxyacids, phosphanes and hydroxyphosphanes, stabilised by metal-coordination at ruthenium [1]; ii) the light induced dissociation of water at high pressure using near-UV photons in the presence of red phosphorus, which results in the formation of H2 together with PH3, H3PO2, H3PO3, and H3PO4; [2] iii) our preliminary exploration of the chemistry of the less reactive allotrope of the element, i.e. black phosphorus, which provides easy access to two dimensional flakes of phosphorene (the all-P analogue of graphene).[3] MP thanks all the coworkers listed in the references. Thanks are expressed for funding this research to EC through the SUSPHOS project, grant RFP7-PEOPLE-2012-ITN – 317404 and to the European Research Council through the project PHOSFUN, proposal n° 670173 ERC-ADG-2014.

References:

1. Barbaro P., Bazzicalupi C., Peruzzini M., Seniori Costantini S., Stoppioni P. Angew. Chem. Int. Ed. 2012, 51, 8628 - 8631 and references therein

2. Ceppatelli M., Bini R., Caporali M., Peruzzini M. Angew. Chem. Int. Ed. 2013, 52, 2313 –2317.

3. Serrano Ruiz M., Caporali M., Heun S., Ienco A., Manca G., unpublished results.

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19

SL11

HYBRID MATERIALS: SYNTHESIS AND APPLICATIONS

C.M. Ronconi

cmronconi@id.uff.br

Dept. of Inorganic Chemistry, Institute of Chemistry, Fluminense Federal University, Outeiro de São João Batista, s/n, Campus do Valonguinho, Centro, 24020-141, Niterói,

RJ, Brazil

Hybrid materials comprise both, inorganic and organic components, closely mixture. I the field of hybrid materials, at nano and microscale, we are able to design and construct solid materials and structures with different functionalities and tuned properties. Mesoporous silica nanoparticles (MCM-41 and SBA-15) and magnetic nanoparticles (Fe3O4, Fe2O3) can be covalently functionalized, linking various organic molecules to the surface, thus yielding materials that can be applied as drug delivery systems, catalysts and selective gas sorbents.1-3 Extended networks, another class of hybrid materials, have attracted much attention due to the degree of structural diversity and functionality.4 The properties of the extended networks can be modulated via ligand flexibility or rigidity, functional groups, as well as by the coordination sphere around the metal centers. In this talk, I will show some of our ongoing research in this area and I will discuss some future directions.

References:

1. Santos, T.C.; Bourrelly, S.; Llewellyn, P.L.; Carneiro, J. W. M.; Ronconi, C.M. Phys. Chem. Chem. Phys., 2015, 17, 11095.

2. Silveira, G.Q.; Roberto S. da S., Lilian P. Franco, L.P.; Vargas, M.D.; Ronconi, C.M. Microporous and Mesoporous Mater., 2015, 206, 226.

3. Santos, E.C.S.; Santos, T.C.; Guimarães, R.; Ishida, L.; Freitas, R.S.; Ronconi, C.M. RSC Advances, 2015, 5, 48031.

4. Matos, C.R.M.O.; Miranda, F.S.; Carneiro, J.W.M.; Pinheiro, C.B.; Ronconi, C.M. Phys. Chem. Chem. Phys., 2013, 15, 13013.

CAPES, CNPQ, FAPERJ

20

SL21

EMERGING APPLICATIONS OF RUTHENIUM COMPOUNDS AS MODULATORS OF NITRIC OXIDE AND SINGLET OXYGEN BY LIGHT IRRADIATION. USE AGAINST

CANCER CELLS

Roberto Santana da Silva

University of Sao Paulo, Brazil Several compounds have being used as anticancer agents; however, many of them are non-selective and have side effects to patients. In this perspective, the development of alternative cancer therapies less harmful has emerged including Photodynamic therapy (PDT). Essentially PDT involves production of reactive oxygen species (ROS) that induces the cytotoxicity. However, PDT has been found to fail in hypoxic region. Based on this, the aim of this work is describe the fully physical and photochemical characterization as well the cytotoxicity properties of nitrosyl ruthenium-phthalocyanines complexes – [RuNO(Pc-R)Cl] - as singlet oxygen and nitric oxide producers. All the ruthenium-phthalocyanines complexes were synthesized with either one or four carboxyl groups using microwave techniques. They were characterized by UV-visible, infrared, nuclear magnetic resonance, fluorescence and mass spectroscopy. The cellular viability of the compounds was evaluated using the MTT and flux cytometer assays with B16F10 as a model of tumor cell and L929 as a model of healthy cell. The protein expression was evaluated by Western Blot tests. The cell viability was found between 10-25 % with 5 J/cm of potency in light irradiation. The cell death is mainly attributed to the apoptosis mechanism. The initial studies suggested us the NO production increases the sensitivity of the cells to singlet oxygen. Western Blotting assays have been used to investigate the expression of different proteins which will direct our future tests to understand the cellular proliferation and death mechanism. Fluorescent microscopy images showed the complexes penetrated in B16F10 cell line (10 µM, 30 minutes of incubation). The synergistic effect of NO and 1O2 may improve Photodynamic Therapy. Acknowledgments: FAPESP, CNPq, CAPES and photochem NAP

21

SL31

REGULATION OF OXIDOREDUCTASE ACTIVITY BY CYTOTOXIC RUTHENIUM AND OSMIUM COMPLEXES

Hugo Rico, Ronan Le Lagadec

UNAM - Universidad Nacional Autónoma De México

Keywords: Cyclometalated complexes, Oxidoreductase, Mechanism

Many ruthenium compounds have been developed for anticancer treatment and displayed in vitro cytotoxicity and in vivo anticancer activity. The side effects are usually reduced compared to platinum drugs, as the resistance mechanisms. However, their development has been stopped in phase II of the clinical trial, mainly due insufficient efficacy in human and a lack of information on their exact mode of action. Our group has prepared series of structurally similar cyclometalated complexes of the general formula [M(C~N)x(N~N)3-x]m+ (M = Ru, Os; C~N = o-2-phenylpyridinato; N~N = 2,2’-bipyridine; x = 0 – 3), that have displayed cytotoxicity [1,2]. Their redox potentials, charges and lipophilicities change drastically from one to another, as the antitumour activity. However, the mode of action, meaning the direct targets, and the crucial physicochemical determinants for their biological properties remain mostly unknown. On the other hand, our metalacycles can also act as regulators of redox proteins [3]. Recent results have demonstrated that various oxidoreductases can be associated with the development of certain cancers, so it is thought that the route of action of our derivatives may be due to the interaction with such enzymes. In this work, in order to shed light on how the complexes can interact with oxidoreductases, we have studied the effects on the in vitro activity of oxidoreductases such as lactate dehydrogenase, peroxidase and glucose oxidase. Kinetic parameters, as well as the influence of the redox potentials and the oxidation state will be discussed. Theoretical docking simulations will also be presented.

References:

1. Cerón, R.; Morales, D.; Hernández, S.; Le Lagadec, R.; Ryabov, A.D. Inorg. Chem. 2008, 47, 4988.

2. Boff, B.; Gaiddon, C.; Pfeffer, M. Inorg. Chem. 2013, 52, 2705.

3. Saavedra-Díaz, O.; Le Lagadec, R.; Ryabov, A.D. J.Biol. Inorg. Chem. 2013, 18, 547. Financial support from CONACyT (Project 153151) is acknowledged.

22

SL41

ON THE DESIGN OF Mn(III) N-PYRIDYLPORPHYRIN-BASED BIOMIMETIC MODELS OF OXIDOREDUCTASE ENZYMES

N.K.S.M. Falcão,1 V.H.A. Pinto,1 J.F. Sarmento-Neto,1 J.C. Bueno-Janice,1 C.G.C. Maia,1 W.D. Fragoso,1 M.G. da Fonseca,1 Y.M. Idemori,2 A. Tovmasyan,3 I. Spasojević,4 I.

Batinić-Haberle,3 J.S. Rebouças1*

1Depto. de Química, CCEN, Universidade Federal da Paraíba, Brazil; 2Depto. de Química, ICEx, Universidade Federal de Minas Gerais, Brazil; 3Dept. of Radiation Oncology and

4Dept. of Medicine, Duke University Medical Center, USA.

Mn porphyhrins (MnPs) are long-known chemical models for oxidoreductase enzymes, such as cytochromes P450, peroxidases, catalases, and superoxide dismutases (SOD).1,2,3 The presentation will focus on our recent efforts toward the development of P450 biomimetic models and SOD mimics by exploring the chemistry of N-pyridylporphyrins. The synthesis of 2-N-pyridylporphyrin, which is a synthon for the preparation the most potent water-soluble, cationic SOD mimics, was chemometrically optimized. All isomers of N-pyridyl-based MnPs were covalently or electrostatically immobilized onto inert supports (e.g., silica gel or vermiculite clay mineral) to yield organic-inorganic hybrid materials as efficient P450 models for hydroxylation reactions, with excellent recyclability. The supports mimicked P450 apoprotein by increasing MnP oxidative stability. While MnPs (and their Fe counterparts) are able to carry out the dismutation of H2O2, their low activities preclude their use as catalase mimics of therapeutic relevance. The success of MnPs as SOD mimics and experimental therapeutics in many oxidative stress-related diseases and injuries requires not only the preparation of compounds of intrinsically high antioxidant potency (e.g., SOD activity), but also the fine-tuning of factors such as bioavailability, biodistribution, and toxicity. Whereas the optimization of the biological aspects of MnP-based therapeutics has been actively sought by the controlled modification of the side-chain pyridinium moieties, we are also exploring strategies based on non-symmetrical A3B-type porphyrins for achieving independent control of lipophilicity and electrostatic facilitation toward the development of oxidoreductase models.

References:

1. Meunier, B., Chem. Rev., 92, 1992, 1411-1456. 2. Batinic-Haberle, I.; Rebouças, J. S.; Spasojevic, I. Antiox. Redox Signal., 13, 2010, 877-918. 3. Nakagaki, S.; Ferreira, G.K.B.; Marcalb, A.L.; Ciuffi, K.J. Curr. Org. Synth., 11, 2014, 67-88.

CAPES, CNPq, FINEP, FAPEMIG, NIH1R03-NS082704, NIH-U19AI067798, NIH/NCI-5-P30-CA14236

23

SL51

METAL-BASED AGENTS AGAINST SPOROTHRIX SCHENCKII

M. Navarro*1, G. Visbal1, L. Colina2, W. Villarreal2, A. Higuera3, W. de Souza4, A. Batista2, T. Gagini4, L. P. Borba-Santos4, S. Rozental4

1Division Diretoria de Metrologia Aplicada às Ciências da Vida, Instituto Nacional de

Metrologia, Qualidade e Tecnologia, Brazil 2Universidade Federal de São Carlos, Brazil

3Intituto Venezolano de Investigaciones Cientificas (IVIC), Venezuela 4Universidade Federal de Rio de Janeiro, Brazil.

Sporotrichosis is a subcutaneous mycosis of humans and mammals that has a worldwide distribution. This infection is caused by a complex of various species of dimorphic fungus, Sporothrix schenckii; particularly, in Brazil there are increasing reports of sporotrichosis, with a zoonotic transmission by cats. Traditionally, this infection has been treated with potassium iodide, due to the adverse effects, itraconazole has replaced it as first-choice of treatment,1 limitations including long periods of treatment, severe side effects, high costs, and the emergence of unresponsive clinical cases or with low susceptibility, make urgently the search for new and more effective therapy against this fungal infection. Continuining with our strategy using the synergistic concept,2 based on the modification of organic compounds with known biological activity through the incorporation of the metal-containing fragments, in order to develop new metallodrugs that combine high activity and low toxicity. In this presentation will be summarized our efforts to increase the biological activity of clotrimazol, ketoconazole, fluconazole and sterol hydrazone through incorporation of transition metals such as Ru, Cu, Pt, Zn and Au into its structure as a strategy for the development of alternative metal based drugs against Sporothrix schenckii.

The outcomes indicated that in general S. schenckii and S. brasiliensis were significantly more sensitive to metal-based drugs than the organic drugs alone, particularly those ones based on gold and zinc, showing that our strategy is a promissory approach to provide effective treatment for sporotrichosis.

References:

1. V.K. Mahajan Dermatol Res Pract, 2014, 13 pages

2. M. Navarro, G. Visbal. Metal-Based Antiparasitic Therapeutics In: Heavy Metals and Infectious Diseases, ed. J. O. Nriagu and E. P. Skaar. Strüngmann Forum Reports, vol. 16, J. Lupp, series editor. Cambridge, MA: MIT Press. Chapter 10, 161-172.

FAPERJ, CAPES, CNPQ

24

SL61

FACIALLY CAPPING P-MACROCYCLES - THE CONTROL OF LABILITY IN METAL-PHOSPHINE COMPLEXES AND APPLICATIONS IN REACTIVITY

Peter Edwards

CU - Cardiff University

Keywords: phosphorus macrocycles, coordination chemistry, homogeneous catalysis

We have addressed alternative approaches to the control of excessive ligand dissociation in transition metal phosphine complexes by the design of ligand systems that form intrinsically robust metal-ligand units. Our choice of ligand system is based upon macrocycles with P- and C-donors which have properties that restrict their mode of coordination to facially capping with the aim that they will also enable access to available reaction sites within the metal’s coordination sphere. This feature results in a potentially very robust metal-macrocycle fragment that remains intact during subsequent reactions, but which has labile sites that are available for other transformations (such as in catalysis). There is now good evidence that this principle is valid and unusual reactivity can result. A difficulty with this approach is the scarcity of suitable ligands, phosphorus macrocycles available as free ligands are extremely rare. Consequently, we have studied synthetic routes to suitable ligands. We have developed a number of new template methods including some based upon Mn(I) and Re(I) which lead to new P-macrocycles and hybrid carbene-phosphine analogues. In particular, we are interested in exploring the reactivity arising from the availability of cooordination sites trans to the macrocycle donors, and exploiting the intrinsic robustness of reaction intermediates arising from the macrocylic coordination effect. Early studies indicate that these facially capping P-macrocycles support exciting and new catalytic behaviour. In this presentation, we will discuss these results and the general chemistry of a series of new P-macrocycle complexes

25

SL71

POTENTIAL CANCER CHEMOTHERAPEUTICS BASED ON HETEROMETALLIC TITANIUM-GOLD AND RUTHENIUM-GOLD SCAFFOLDS

Maria Contel*1,2

1 Chemistry Department, Brooklyn College, and 2 Chemistry and Biology PhD Programs, Graduate Center, The City University of New York, New York, NY, US.

Heterometallic complexes are arising as promising metallodrugs with potential as cancer chemotherapeutics due to improved properties with respect to their monometallic counterparts (either alone or in combination). Our group has reported on the applications of heterobimetallic complexes containing organometallic titanocene and gold-carboxylate or thiolate fragments as potential chemotherapeutics for renal cancer.1-3 These compounds are extremely active in vitro against human renal cancer cell lines while being less toxic to no-cancerous cells. Preliminary mechanistic studies on these compounds demonstrated that they do not interact with DNA but that they inhibit protein kinases of the MAPKAPK2/3 families.2,3 Moreover, we found an impressive in vivo tumor reduction in mice for one of these compounds [(η-C5H5)2Ti{OC(O)C6H4SAu(PPh3)] and confirmed the in vitro inhibition of MAPKAPK2/3 and thioredoxin reductase in human Caki-1 cells.3 We have also designed heterobimetallic ruthenium-gold compounds with a diphosphane (dppm) linker which display relevant anticancer properties.4 We will report on the synthesis and characterization of new Ti-Au and Ru-Au compounds containing different ligands (such as carbenes), their in vitro activity against human cancer cell lines, the study of their interaction with different biomolecular targets and preliminary mechanistic insights.

References:

1. González-Pantoja, J.F.; Stern, M.; Jarzecki, A.A.; Royo, E.; Robles-Escajeda, E.; Varela-Ramirez, A.; Aguilera, R.J.; Contel, M. Inorg. Chem. 2011, 50, 11099.

2. Fernández-Gallardo, J.; Elie, B.T.; Sulzmaier, F.; Sanaú, M.; Ramos, J.W.; Contel, M. Organometallics 2014, 33, 6669.

3. Fernández-Gallardo, J.; Elie, B.T.; Sadhukha, T.; Sanaú, M.; Prabha, S.: Rotenberg, S.; Ramos, J.W.; Contel, M. Chem. Sci. 2015, 6, 5269.

4. Massai, L.; Fernández-Gallardo, J.; Guerri, A.; Arcangelic, A.; Pillozzic, S.; Contel, M.; Messori, L. Dalton Trans. 2015, 44, 11067.

Funded by NCI (grant 1SC1CA182844)

26

SL81

METAL COMPLEXES AIMING APPLICATION AS RADIOPHARMACEUTICALS

V.M. Deflon

Institute of Chemistry of São Carlos, University of Sao Paulo

Radionuclides are widely used in nuclear medicine, including both cancer diagnosis and therapy.1 In this context, coordination compounds play an important role, since radioactive metal complexes can combine the necessary bio physicochemical properties to deliver the radionuclide to target organs, as single compounds or more specifically when coupled to a biomolecule.1 In this sense, the ligand syntheses have to be planned in order to provide stable complexes that should form rapidly, in high yield and under mild conditions.

The design of new ligands as well as the corresponding model complexes with metals of interest in nuclear medical application, mainly rhenium, technetium, gallium and indium, is the theme of this research. The ligands include a macrocycle proposal but mainly polydentate acyclic thiosemicarbazones and structurally related derivatives. Labelling studies involving radionuclides are included for some new ligand systems.

References:

1. Gielen & Tiekink, Metallotherapeutic drugs & metal-based diagnostic agents - the use of metals in medicine, 1st ed., 2005.

CAPES, CNPQ, FAPESP

27

SL91

BIOLOGICALLY-INSPIRED NICKEL AND IRON COMPLEXES WITH CHELATING

AMINODI- AND TRITHIOPHENOLATES

Alexander Mondragón 1, Elvis Robles Marín 2, Ivan Castillo 2

1 UNIVALLE - Universidad Del Valle 2 UNAM - Universidad Nacional Autónoma De México

Keywords: Bioinorganic, Sulfur, Nickel, Iron In the active site of redox-active metalloenzymes, the intrinsic redox properties of transition metals is sometimes enhanced by redox non-innocent ligands. Sulfur-based donors are among these ligands, as evidenced by their presence in the active sites of redox intensitve enzymes such as nitrogenase. In this context, we have developed sterically encumbering thiophenolate ligands that provide steric protection to nickel and iron centers. Their incorporation to tri- and tetradentate N,S chelating ligands provides coordination environments similar to those observed in, for example, sulfur-rich hydrogenase and nitrogenase enzymes. We will present the synthesis, characterization, and properties of nickel and iron complexes, as well as their relevance to the aforementioned metalloenzymatic active sites.

28

SL101

TRIAZOLIC COBALT(III) COMPOUNDS AS CARRIER PROTOTYPES FOR ANTITUMOR PRODRUGS

Bianca Medeiros Pires 1, Rebecca Rodrigues Matos 1, Daniel Tadeu Gomes Gonzaga 2, Fernando de Carvalho da Silva 2, Jackson Antonio Lamounier Camargos Resende 2,

Roberto de Barros Faria 1, Marciela Scarpellini 1

1 UFRJ - Universidade Federal Do Rio De Janeiro 2 UFF - Universidade Federal Fluminense

Keywords: Cobalt, Prodrug, Cancer, Complex, Bioinorganic

Cobalt(III) compounds are well suited to be used as Prodrugs Activated by Hypoxia. The Co3+ electronic state assures highly inert complexes, ensuring the stability needed for a carrier, while Co2+ electronic state imparts the lability required for cytotoxic ligand release [1]. Herein, we present the syntheses and characterization of two new triazolic Co3+ compounds as carrier prototypes for antitumor prodrugs. Both were characterized by UV-Vis, IR, cyclic voltammetry, elemental analysis and monocrystal X-ray diffraction. Complexes were synthesized adding a solution of (bis(1-methylimidazol-2-yl)methyl)(2-(pyridyl-2-yl)ethyl)amine (L) to a solution of Co2+ salt (Co(BF4)2•6H2O for 1 and Co(ClO4)2•6H2O for 2), in methanol. The intermediate formed was oxidized adding 60 µL of H2O2 30%. After 30 minutes, methanolic solution of the triazolic ligand (1-(4-chlorophenyl)-1H-1,2,3-triazole-4-carbaldehyde oxime (TzCl) for 1 and 1-phenyl-1H-1,2,3-triazole-4-carbaldehyde oxime (Tz) for 2) was added and the solution was stirred for 30 minutes. After few days, single crystals suitable for X-ray analysis were obtained. The X-ray results showed that both are mononuclear complexes and the metal is coordinated to four nitrogen atoms of L and one nitrogen atom and one oxygen atom of TzCl or Tz for 1 or 2, respectively. Elemental analyses and infrared spectroscopies corroborated to the X-ray structure. Electronic spectra in CH3CN show one ILCT band around 240 nm (ε/L mol-1 cm-1 = 26879 for 1 and 36464 for 2) and one LMCT band around 370 nm (ε/L mol-1 cm-1 = 5208 for 1 and 7252 for 2). The ligand field transition for 2 was observed at 585 nm (ε/L mol-1 cm-1 = 178), while a shoulder was found in the spectrum of 1. In the same medium, the Epc values are -0.31 and -0.39 vs NHE for 1 and 2, respectively. Reactivity studies with ascorbic acid and cytotoxic assays are underway and will be presented. [1] Failes, T.W.; et. al. Dalt. Trans., 2006, 1895.

CAPES, CNPQ, FAPERJ

29

SL111

LANTHANIDE COMPOUNDS USED IN OLEDS CONSTRUCTION

Flávia Cavalieri Machado

Departamento de Química-ICE, Universidade Federal de Juiz de Fora, Juiz de Fora-MG, 36036–330, Brazil

Organic Light-Emitting Diodes (OLEDs) are electroluminescence devices used in displays of cell phones, televisions and computers. OLEDs have many components distributed in layers and lanthanide compounds can be applied as the emitting layer, since they present sharp emission bands in the visible range of the electromagnetic spectrum, producing pure color emission with high quantum efficiency. Lanthanide metal-organic frameworks (LnMOFs) as well as mono- and bimetallic lanthanide complexes and the construction of their OLED devices will be presented.

30

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31

OC11

ANALYSIS OF MAGNETIC BEHAVIOR OF COMPOSITES BASED ON THE LAYERED MANGANESE(II) THIOPHOSPHATE PHASE.

Pablo Fuentealba 1,2, Jorge Manzur 3,2, Claudio Jose Magon 4, Igor Danciaes Almeida Silva 4, Ricardo Costa de Santana 5, Veronica Paredes-Garcia 6,2, Diego Venegas-Yazigi

7,2, Evgenia Spodine 1,2

1Facultad de Ciencias Químicas Y Farmacéuticas, U. de Chile, 2 CEDENNA, Santiago, Chile., 3 FCFM, U. de Chile - 3Facultad de Ciencias Físicas y Mataméticas, U. de Chile, 4 IFSC-USP - 4instituto de Física de São Carlos, U. de São Paulo, 5 IF-UFG - 5Instituto de

Física, Universidade Federal de Goiás, 6 Dpto. Cs. Qcas. UNAB – 6Departamento de Ciencias Químicas, U. Andrés Bello, 7 Fac. Q. Y B. USACH – 7Facultad de Química y

Biología, U. de Santiago de Chile

Keywords: Layered Manganese(ii) Thiophosphate, Magnetic Behavior, Macrocyclic Complexes

Magnetic properties of MnPS3 phase and its composites derived from intercalation have received great attention due to the interesting changes in the magnetic behavior. Pristine MnPS3 phase is antiferromagnetic, but when monocations are intercalated, the obtained phase becomes ferromagnetic at 16 K. The K0.4Mn0.8PS3•H2O phase is useful for further intercalation reactions, being possible to intercalate macrocyclic complexes. In this work the magnetic properties of composites obtained by intercalation of a ZnII and a CuII macrocyclic complex are presented. The obtained composites were characterized by FTIR, powder X-ray diffraction and SEM-EDXS. Magnetic properties were studied by dc and ac magnetic susceptibility and EPR spectroscopy. In the FTIR spectra of both composites bands due to the host and the guest species are observed. Powder X-ray diffraction established that the interlamellar distance of both complexes is c.a. 10 Ǻ, therefore it is inferred that the guest complexes are parallel to the lamellae. SEM-EDXS showed that there is only a partial exchange of the interlayered hydrated potassium ions by the cationic macrocyclic complexes. For the dc data, the χT(T) plot for [Zn2L]0,04K0,32Mn0,8PS3, shows a less intense asymmetric curve with a maximum at 30 K, corresponding to the spontaneous magnetization, as the one observed in the K0.4Mn0.8PS3•H2O phase. Moreover, the same plot for [Cu2L]0,08K0,24Mn0,8PS3 shows two maxima of spontaneous magnetization, also less intense than that recorded for the potassium precursor. I both cases, the spontaneous magnetization is observed from 5 to 45 K. The ac measurements permit to infer the existence of spin canting in the layers. EPR spectra are strongly temperature dependent. Spectra obtained above 45 K show only a symmetric line, while spectra obtained at the temperature of the spontaneous magnetization, are asymmetric and dependent of the guest.

32

OC21

BIOMIMETIC APPROACH TO PHM MONOOXYGENASE ACTIVE SITE WITH TRIPLET CUPRIC-SUPEROXO COMPLEXES

Brenda Nataly Sánchez Eguía1, Maylis Orio2, Ivan Castillo Pérez1

1 UNAM - Instituto de Química,Universidad Nacional Autónoma de México, 2 AMU - AIX Marseille Université

Keywords: Copper monooxygenases, Cupric-superoxo complexes, N3S donor set

Copper monooxygenases use molecular oxygen (O2) to perform the insertion of one atom of this molecule to an organic substrate by oxidative cleavage of a secondary C-H bond1. In this context, recent studies aim at understanding the mechanism of methane monooxygenase (pMMO), polysaccharide monooxygenase (PLMO), dopamine-β-monooxygenase (DβM), and peptidylglycine α-hydroxylating monooxygenase (PHM), all of which possess Cu-based active sites effecting the reaction described with O2

2. DβM and PHM are of particular interest due to the presence of a methionine-derived thioether donor3. Inspired on the CuM active site of DβM and PHM, characterized by two ubiquitous histidine donors in addition to the methionine residue, we have developed a series of ligands that posses a N3S donor set, which have provided a unique electronic enviroment. Our copper complexes mimic the CuM site of copper monooxygenases and react with O2 affording side-on cupric–superoxo complexes capable of H-abstraction from dihydroanthracene and THF. Spectroscopic and DFT data of the Cu–superoxos support a spin triplet ground state for the side-on complexes, as well as a hemilabile thioether4. Extension of this platform to selenoether-based analogues will be discussed.

Refrerences:

1. Solomon, E.; Sundaram, U.; Machonkin, T.; Chem. Rev. 1996, 96, 2563.

2. Lee, J. Y.; Karlin, K. D.; Curr. Opin. Chem. Biol. 2015, 25, 184.

3. Karlin, K. D.; Itoh, S.; Copper-Oxygen Chemistry, 1st ed.; Willey:New Jersey, USA, 2011.

4. Sánchez-Eguía, B. N.; Flores-Álamo, M.; Orio, M.; Castillo, I.; Chem. Commun. 2015, 51, 11134. CONACYT, DGAPA

33

OC31

REACTION MECHANISM FOR METHANE OXIDATION REACTION PROMOTED BY A STRUCTURAL MODEL OF THE PMMO ENZYME

Willian R. Rocha

Departamento de Química-ICEX, Universidade Federal de Minas Gerais, 31270-901, Belo Horizonte – MG, Brazil, wrocha@ufmg.br

Over the past years the C-H bond activation of alkanes catalyzed by transition metal complexes has attracted much attention from the chemical community, mainly due to the considerable industrial importance and potential [1-4] since alkanes are the major constituents of natural gas and petroleum. Nevertheless, efficient, selective and direct functionalization of hydrocarbons under mild conditions remains one of the most important challenges to chemists even today. In this presentation the activation of alkanes by transition metal compounds in solution and using bioinspired models will be highlighted. Results of recent Density Functional Theory (DFT) calculations on the activation of methane by a structural model of the particulate Methane Monooxygenase (pMMO) enzyme, containing a binuclear copper active site, will be presented and discussed.

Acknowledgments: CNPq (Conselho Nacional de Desenvolvimento Científico e tecnológico), FAPEMIG (Fundação de Amparo à Pesquisa do Estado de Minas Gerais), INCT-Catálise (Intituto Nacional de Ciência e Tecnologia de Catálise em Sistemas Moleculares e Nanoestruturados)

References:

[1] See for instance: Proc Natl Acad Sci, Special issue on the coordination chemistry of satured molecules 104 (2007).

[2] Labinger, J. A.; Bercaw, J. E. Nature 417 (2002) 507.

[3] Lersch, M.; Tilset, M. Chem Rev. 105 (2005) 2471.

[4] J. Organomet. Chem. 793 (2015), Special issue on C-H bond activation

34

OC41

NIOBIUM(V) AS BRIDGE FOR MAGNETIC COUPLING IN A CR(III)2NB(V)2 MOLECULAR SQUARE

Willian X. C. Oliveira 1,2, Cynthia l. M. Pereira 1, Carlos B. Pinheiro 1, Joan Cano 2,3, Francesc Lloret 2, Miguel Julve 2

1 UFMG - Universidade Federal de Minas Gerais, 2 UV - Universitat de Valencia, 3 FGUV - Fundacion General de La Universitad de Valencia

Keywords: Niobium(V), Chromium(III), Molecular Magnetism, Crystal Strucuture, DFT calculations

The slow diffusion of [Cr(H2O)6](ClO4)2 in a MeOH-dmso solution containing (NH4)3[NbO(ox)3]∙6H2O and 2,9-dimethyl-1,10-phenantroline afforded a molecular square of formula [{Cr(dmso)4]2{Nb(μ-O)2(ox)2}2]∙2dmso (1) (ox = oxalate and dmso = dimethylsulfoxide). 1 was obtained as X-ray quality green crystals on standing at room temperature after several weeks. It crystallizes in triclinic P-1 space group and the structure consists of two [Cr(dmso)4]3+ units linked by the oxo groups of cis-NbO2(ox)2 produced in situ. The intramolecular Cr•••Cr distance is 5.349 Å, whereas the shortest intermolecular chromium-chromiun separation is 11.45 Å. The magnetic properties of 1 were investigated in the temperature range 2.0-300 K. At room temperature, χMT is equal to 3.65 cm3 mol-1 K, a value which is as expected for two non-interacting Cr(III) ions (SCr = 3/2). Upon cooling down, χMT continuously decreases to reach 0.21 cm3 mol-1 K at 2.0 K due to the occurrence of an antiferromagentic coupling between the Cr(III) ions. The magnetic data of 1 were analyzed through the spin Hamilonian H = -JSCr1∙SCr2 + βH (gCr1SCr1 + gCr2SCr2). The best-fit parameters are J = -12.0 cm-1 and gCr = 2.0. The DFT calculations revelaled an energy gap of the magnetic orbitals dx2-y2 of 4003 cm-1 and also the presence of a residual spin density around the cis -O-Nb-O- bridges which account for the J value1 and the overlap the magentic orbitals, respectively.The J value is twice that observed through the oxalate bridge in the complex (NBu4)4[Cr2(ox)5]∙2CHCl3 (J = -6.2 cm-1 with an intramolecular Cr•••Cr separation of 5.313 Å).2

References:

1. Hay, P. J.; Thibeault J. C.; Hoffmann, R. J. Am. Chem. Soc., 1975, 4884.

2. Masters, V. M.; Sharrad, C. A.; Bernhardt, P. V.; Gahan, L. R.; Moubaraki, B.; Murray, K. S. J. Chem. Soc., Dalton Trans. 1998, 413. CAPES, CNPQ, FAPEMIG, MICINN (Spain), Brazilian-Spanish Project HB2014-00024

35

OC51

THE ELECTRONIC STRUCTURE OF MOLECULAR URANIUM(V) NITRIDES

N.F. Chilton*, F. Tuna, E.J.L. McInnes and S.T. Liddle

School of Chemistry and Photon Science Institute, The University of Manchester, Manchester, M13 9PL, U.K.

The electronic structure of actinide complexes is generally a very complicated problem. This is because all the electronic interactions are not only very strong compared to other metals in the Periodic Table, but they are all on the same order of magnitude as one another. We present the most comprehensive and detailed picture of the electronic structure of a set of UV complexes to date, supported by spectroscopic and thermodynamic experiments as well as theoretical models. We show that ab initio calculations provide a very good estimate of the electronic and magnetic properties and that the entire set of experimental data can be fitted simultaneously with a deceptively simple crystal field model. These results are of fundamental importance for understanding the interactions actinide elements with their surroundings as well as the basic properties of actinide complexes.

RSC, EPSRC, EPSRC National EPR Facility at The University of Manchester

36

OC61

MECHANISTIC INSIGHT INTO PROTON COUPLED MIXED VALENCY

Wilkinson Luke 2,3, Patmore Nathan 3

2 UOS - University of Sheffield; 3 UOH - University of Huddersfield

Keywords: Mixed Valency, Proton Coupled Electron Transfer, Electron Transfer, Hydrogen Bonds, Coordination Chemistry

The term “mixed valency” is typically synonymous with an electronic coupling or superexchange mechanism. Recently, we have developed systems (based on M2 quadruply bonded paddlewheel-type dimers where M = Mo or W), in which mixed valency occurs across hydrogen bonded bridges without evidence of electronic coupling. From our studies, it appears that the mixed valency is dependent on the proton co-ordinate and occurs via a dipole-induced self-exchange mechanism. This “proton coupled mixed valency” is distinct from traditional electronic coupling and proton coupled electron transfer mechanisms and represents a new, poorly explored area of inorganic chemistry. We investigate this phenomenon with techniques such as cyclic voltammetry, spectroelectrochemical UV/Vis/NIR and IR techniques as well as EPR and 1H NMR spectroscopies, backed up with DFT calculations.

37

OC71

ADSORPTION PROCESS INDUCED BY SUPRAMOLECULAR INTERACTIONS

Brenda Lizette Ruiz Herrera, Marco Flores Alamo, Ruben Alfredo Toscano, Roberto Escudero, Martha E Sosa Torres

UNAM - Universidad Nacional Autonoma de Mexico

Keywords: macrocyclic complexes, Ni-tpmc complex, water vapor adsorption

Two novel structures of macrocycle compounds of nickel(II) were obtained.(1) Corresponding to coordination compounds with nitrates and tpmc (1,4,8,11-tetrakis-(2-methylpyridyl)-1,4,8,11-tetraazacyclotetradecane) as ligands. The resulting compounds are related through a highly sensitive and reversible adsorption process, where the adsorption of water vapor change the original blue color of the starting material into a violet for the final product. Single crystals of both compounds were isolated, before and after adsorption was carried out, so we observed the effect of water incorporation at the crystalline level. The presence of water molecules, nitrates and lithuim entities have a significant role in lattice stablization. When additional water molecules are incorporated, these caused a distortion an expantion of the original lattice giving place to a new layer structure. Water molecules are between these layers, stabilizing the lattice through hydrogen bonding interactions. The adsorption phenomenon was characterized by nitrogen isothermal measurements (BET) and water vapor sorption experiments. It was found that this Ni(II)-tpmc complex behaves as a mesoporous material, in which the adsorption of water correspond to a chemisorption process mediated by weak adsorbent-adsorbate correlations, involving Van der Waals and hydrogen bonding interactions between vapor phase molecules and the cavities where these are confined.

References (1) Ruiz-Herrera B. L., Flores-Álamo M., Toscano R. A., Escudero R., Sosa-Torres M. E., Inorganic chemistry 2015, submitted by its publication.

38

OC81

STABILITY IN AQUEOUS SOLUTION OF NOVEL [(PARA-CYMENE)RU(II)(AZA-CHALCONE)CL]+ COMPLEXES: UNEXPECTED ALKENE HYDRATION REACTION

Javier Alexander Gomez Gomez1, Fabio Da Silva Miranda1, Norberto Peporine Lopes2, Maria Domingues Vargas1

1 UFF - Fluminense Federal University, 2 USP - University of Sao Paulo

Keywords: Ruthenium-arene, Chalcone, Hydration of alkene

The chemistry of organometallic ruthenium-arene complexes have been widely studied, mainly for their therapeutic properties as anticancer agents. Two types of compounds have shown interesting anticancer activities, both in vitro and in vivo: either with coordinated ethylenediamine or phosphatriazaadamantane (pta) ligands. Novel ruthenium-arene compounds have been synthesized with a variety of other ligands, resulting in some cases in biological properties more pronounced than the original molecules.1 Herein, we report the synthesis of new (p-cym)RuCl complexes (cym = cymene) using aza-chalcone ligands as models for [(p-cym)Ru(quinoline-5,8-dione)Cl] compounds. This approach, combined with UV-Vis, 1H NMR and mass spectrometry, X-ray diffraction analysis and DFT calculations, provided useful information about the coordination sphere, the molecular behavior at electronic levels, and their chemistry and stability in aqueous solution. All complexes were synthetized from the reaction of [(p-cym)Ru(CH3CN)2].PF6 in CH2Cl2 with the aza-chalcone. Slow evaporation of the solution yielded the desired complexes as red crystalline solids. The X-ray molecular structures show that all complexes adopt the expected piano chair conformation with the chloride and aza-chalcone ligands as legs. IR, UV-Vis and 1H NMR data suggested strong back-donation from the ruthenium(II) center to the enone system, which explains the unexpected double bond activation that led to hydration of the alkene in aqueous solution. Alkene activation was also observed by time-dependence mass spectrometry studies in aqueous solution, strongly indicated by the presence of the alcohol molecular ion pattern. Furthermore, a six species equilibrium involving the [(p-cym)Ru(II)(aza-chalcone)Cl]+ complex and its aqua products was observed to exist in solution.

References:

1. Allardyce, C. S.; Dorcier, A.; Scolaro, C.; Dyson, P. J.; Appl. Organometal. Chem., 2005, 19, 1.

CAPES, PEC-PG, CNPQ, FAPERJ, FAPESP

39

OC91

NEW ANTIMONY COMPLEXES AS POTENTIAL ANTILEISHMANIAL AGENTS AGAINST Sb(III)-SENSITIVE AND –RESISTANT PARASITES

A. Islam1, B. H. R. do Prado1, V. Rubim1, B. L. Rodrigues1, J. S. Lanza2, F. Frézard2 and C. Demicheli *1

1Departamento de Quimica, 2Departamento de Fisiologia e Biofisica, Universidade Federal de Minas Gerais (UFMG), Belo Horizonte, Minas Gerais Brazil

Hydrophilic pentavalent antimony complexes with N-methylglucamine (meglumine antimonate or Glucantime®) or sodium gluconate (sodium stibogluconate or Pentostam®) are still first-choice medications in most developing countries to treat all forms of leishmaniasis. Because antimonial drugs require repeated parenteral injections and exert toxicities, patients frequently interrupt the treatment, causing resistant microorganisms to emerge. In this context, the World Health Organization has recommended the search for new drugs and formulations. In this work, novel organoantimony(V) complexes of the type M(L)2 were synthesized, in which L = deprotonated 3-(dimethylamino)benzoic acid (HL1) or deprotonated 2-acetylbenzoic acid (HL2) or α-tryptophanehydroxamic acid (HL3) and M = triphenylantimony(V) (M). Complexes, [M(L1)2] (1), [M(L2)2] (2)and [M(L3)2] (3) were characterized by elemental analysis, IR, UV-Vis and NMR. Crystal structures of solid state complexes 1 were determined by single crystal X-ray diffraction revealing that 1 adopted five-coordinated extremely distorted trigonal bipyramidal geometry. The organometallic complexes, metal precursors and free ligands were evaluated in vitro for their antiparasitic activity against Leishmania infantum and L. amazonensis promastigotes and their cytotoxicity towards murine macrophages. All the organometallic complexes showed good anti-leishmanial activity (IC50 in the range of 2-14 μM). Organoantimony(V) complexes 1 and 2 were further assessed for their activity against L. Infantum and L. amazonensis intracellular amastigotes in comparison to Glucantime®, as well as antimony-resistant L.

infantum and L. amazonensis promastigotes. 1 and 2 were active at ∼10 μM against amastigotes forms and at ∼10.0–24.0 μM concentration against antimony-resistant leishmania promastigotes. Both organoantimony(V) complexes were more active than Glucantime® against amastigote forms of both Leishmania strains. Thus, these compounds constitute promising antileishmanial drugs candidates.

CNPq, FAPEMIG and CAPES.

40

OC101

PHOTOINDUCED CYTOTOXICITY AND DNA CLEAVAGE BY NOVEL Ru(II) COMPLEXES

A.C.C. Melo1, J.M.S.V.P. Santana1, K.J.R.C. Nunes1, B.L. Rodrigues1, P. Gabriel2, H. Terenzi2 E.C. Pereira-Maia*1

1Dept. of Chemistry, Federal University of Minas Gerais; 2Dept. of Biochemistry, Federal University of Santa Catarina

We have been exploring the antitumoral potential and the DNA cleavage activity of metal compounds. Cu(II) complexes containing an antibiotic molecule and a heterocyclic nitrogen compound as ligands cleave DNA molecule in mild conditions. It is worth notifying that a correlation between cytotoxic activity, DNA binding and cleavage was found.1-3 Two new complexes of Ru(II) with mixed ligands were prepared: [Ru(byp)2smp](PF6) (1) and [Ru(phen)2smp](PF6) (2), in which smp = sulfamethoxypyridazine; bpy = 2,2-bipyridine; phen = 1,10-phenanthroline. The complexes were characterized by elemental analysis, conductivity analysis, ESI-MS, infrared and NMR spectroscopies, and X-ray diffraction of single crystal. The structural analyses reveal a distorted octahedral geometry around Ru(II), which is bound to two bpy (in 1) or two phen (in 2) via their two heterocyclic nitrogens and to sulfamethoxypyridazine through the nitrogen of the methoxypyridine ring and the sulfonamidic nitrogen. The stability of the compounds in aqueous solution was studied by spectrophotometry. After 10 min of photoirradiation with UV-light, complex 1 converts about 25% of supercoiled form (FI) of plasmid DNA to its open circular form (FII) while complex 2, 45%, in the same conditions. No cleavage was observed in dark conditions. UV-light exposure for 5 min increases the cytotoxic activities of 1 by 7 and 2 by 200 times, which make the compounds good candidates for photodynamic therapy.

References:

1. Silva, P.P.; Guerra, W.; Silveira, J.N.; Ferreira, A.M.C.; Bortolotto, T.; Fischer, F.L.; Terenzi, H.; Neves, A.; Pereira-Maia, E.C. Inorg. Chem., 2011, 50, 6414.

2. Silva, P.P.; Guerra, W.; Santos, G.C.; Fernandes, N.G.; Silveira, J.N.; Ferreira, A.M.C.; Bortolotto, T.; Terenzi, H.; Bortoluzzi, A.J.; Neves, A., Pereira-Maia, E.C., J. Inorg. Biochem., 2014, 132, 67.

3. Bortolotto, T.; Silva, P.P.; Neves, A.; Pereira-Maia, E.C.; Terenzi, H., Inorg. Chem., 2011, 50, 10519.

CNPQ, FAPEMIG, CAPES, INCT-CATÁLISE

41

OC111

PHOSPHATASE-LIKE ACTIVITY IN NON SYMMETRICAL FEZN COMPLEXES: TUNNING THE SECOND COORDINATION SPHERE EFFECTS IN THE PHOSPHATE

ESTER HYDROLYSIS

Tiago Pacheco Camargo, Cláudia Chaves, Rosely Peralta, Ademir Neves

UFSC - Universidade Federal de Santa Catarina

Keywords: FeZn Binuclear Complexes, Phosphatase-like Activity, Bioinorganic Chemistry

Enzymes are highly specialized catalysts; most of their catalytic power comes from the ability to bring substrates into a favorable position to promote stabilization of the transition state (TS). One of the main reason is the presence of non-covalent interactions able to interact with the substrate to approach it in a suitable orientation to receive the attack of a nucleophilic group. These effects are called second coordination sphere effects. 1 In coordination compounds these effects are not well known and the study of these effects on catalysis can generate highly active compounds with application in biotechnology. In this work we present the kinetic comparative study of hydrolysis of the phosphate diester substrate 2,4-bdnpp promoted by different FeZn complexes. The FeZnL1 (3) where the hydroxide group bonded to the FeIII center is responsible for the nucleophilic attack have been already described in the literature.2 Two further derivatives were prepared by introducing a side chain, the first containing a pyrene and a diaminebutane (FeZnLP1 - 1) and the second containing two pyrene groups and butanediamine (FeZnLP1 - 2). As the main result it was observed an increase in the complex/substrate association constant about 5 and 7 times for complexes 1 and 2 respectively. However there was a decrease in the catalytic constant (kcat) 2.1x10-4 , 2.8x10-4 s-1 for 1 and 2 when compared to 3 (9.0x10-4 s-1). One possible reason for this result can be the high energetic cost for the organization of the side chain in the transition state, which was reflected by the ΔS‡ values obtained from the Eyring plot for 1, 2 and 3 (-49,6 (1); 45,8 (2) e -33,2 (3) KJ.mol-1). Thus we can conclude that an increase in the rigidity of the side chain can generate the same effects and with lower energetic cost, which would lead to higher kcat values (lower ΔG‡).

References:

1. Meng, Z.; Chem. Soc. Rev., 2013, 8360

2. Piovezan, C.; et all., Inorg. Chem., 2010, 2580. CAPES, CNPQ, INCT

42

OC121

MACROCYCLIC TRANSITION METAL COMPLEXES FOR ELECTROCHEMICAL REDUCTION OF CARBON DIOXIDE

James R. Pankhurst, Thomas Cadenbach, Jason B. Love

Eastchem School of Chemistry, University of Edinburgh, UK

Keywords: Macrocycles, Electrochemistry, Carbon Dioxide, Reduction Chemistry

In March 2015, the concentration of carbon dioxide in the Earth’s atmosphere exceeded 400 ppm,1 having increased steadily from 280 ppm since the Industrial Revolution due to anthropogenic activity.2 The electrochemical reduction of CO2 to useful products is a viable method to be deployed in carbon-capture and utilisation (CCU) strategies, however the single-electron reduction of CO2, that occurs at -1.90 V vs. NHE, is kinetically disfavoured.3 There is therefore a requirement to design homogeneous systems that can function as electrocatalysts, to lower the kinetic barriers and required overpotential for CO2 reduction. We recently reported a pair of new polypyrrolic Schiff-base macrocycles that act as binucleating ligands for the late transition metals.4,5 These complexes fold into structures that offer a reactive cleft between the two metal centres. Their electrochemically reversible redox features, both in the reductive and oxidative directions from the +2 oxidation state, make their application in catalysis viable. Cyclic voltammetry has indicated that some of these complexes react with CO2 at moderate overpotentials of around -1.2 V vs NHE, using H2O as a proton source.

References:

1. Tans, P.; Keeling, R.; http://www.esrl.noaa.gov/gmd/ccgg/trends/ 30/05/2015

2. Neftel, A.; Moor, E.; Oeschger, H.; Stauffer, B.;Nature, 1985, 315;

3. Benson, E.E.; Kubiak, C.P.; Sathrum, A.J.; Smieja, J.M.;Chem. Soc. Rev., 2009, 38;

4. Pankhurst, J.R.;Cadenbach, T.;Betz, D.;Finn, C.; Love, J.B.;Dalton Trans., 2015, 44;

5. Cadenbach, T.; Pankhurst, J.R.;Hofmann, T.A.;Curcio, M.; Arnold, P.L.; Love, J.B.;Organometallics, 2015.

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44

P1

1D AND 2D COORDINATION POLYMERS BUILT UP WITH A VERSATILE PYRAZOLE-BASED LIGAND AS A SPACER

Cassiano Pedro Da Silva, Helen De Andrade Brito, Henrique De Castro Silva Jr, Antônio Gerson Bernardo Da Cruz, Guilherme Pereira Guedes

UFRRJ- Universidade Federal Rural Do Rio De Janeiro

Keywords: Coordination polymer, Pyrazole, Cristal Structure, Ciclic voltammetry

The crystal engineering has been used in the design and syntheses of new coordination polymers (CP), due to their potential technological applications in many areas1. Predicting the final crystal structure of a CP is a challenge nowadays2. Nevertheless, it is well know that the connectivity and dimensionality can be tuned by choosing the appropriate spacer. One of the current potential ligands used as spacer is the pyrazole, which can coordinate in many different ways, becoming it an interesting ligand to build extended coordination structures3. Moreover, it is possible to synthetize several derivatives, which can make it more versatile. In our work, we present two CPs synthetized from the assembly of the pyrazole-based ligand, 5-amino-1-phenyl-1H-pyrazole-4-potassium carboxylate (L), with copper(II) ions. The crystals were obtained by slow diffusion and characterized by IR and UV-vis spectroscopies, cyclic voltammetry and single-crystal X-ray diffraction. The CP1, 2∞[Cu2(L)4], in which the two copper(II) ions lie on the square-pyramidal geometry bridged by four L carboxylate groups, in a paddle-wheel motif4. The axial positions are occupied by pyrazole nitrogen from neighboring paddle-wheel entity, leading to a 2D architecture. In the CP2, 1∞[Cu2(L)2(phen)2](ClO4)2(H2O)3, each copper(II) ion is coordinated in the equatorial positions to one 1,10-phenanthroline molecule and two oxygen atoms, each one from a different L carboxylate groups, and in the axial position to a nitrogen atom from the pirazolyl ring, leading to a chain running along the crystallographic a axis. DFT calculations have been performed to evaluate the exchange magnetic coupling between metal centers and the magnetic dimensionality for both CPs

45

P2

SYNTHESIS AND CHARACTERIZATION OF COBALT(III) COMPLEXES CONTAINING 1,2,3-TRIAZOLE LIGANDS AS PROTOTYPES OF BIOREDUCTIVE PRODRUGS

Isabela Cristina Aguiar De Souza, Mauricio Lanznaster, Jackson Antonio Lamounier Camargos Resende

UFF - Universidade Federal Fluminense

Keywords: Hypoxic regions, Cobalt(III) complexes, 1,2,3-triazole ligands

The disordered growth of the tumor and consequent reduced blood flow creates regions of low O2 concentrations, called hypoxic regions. They differentiate from normoxic tissues mainly by a more reducing environment, a feature that has been exploited for the development of new therapeutic strategies.1 In this way, bioreductive prodrugs based on inert cobalt(III) complexes with biologically active molecules have been developed. These complexes are expected to be selectively activated in the hypoxic regions of the tumor by reduction of the inert cobalt(III) complex to its labile cobalt(II) form, releasing the drug.2 Based on this strategy, we describe the properties of four cobalt(III) complexes3 as prototypes of bioreductive prodrugs, named [Co(L1)(Tz-ph)](ClO4)2.CH3CN (1), [Co(L2)(Tz-ph)](ClO4)2 (2), [Co(L1)(Tz-Cl)](ClO4)2.CH3CN (3) e [Co(L2)(Tz-Cl)](ClO4)2.H2O (4), where Tz-ph and Tz-Cl are 1,2,3-triazole ligands and L1 e L2 are N4-auxiliary ligands. The complexes were characterized by Infrared and UV-visible spectroscopy, cyclic voltammetry, elemental analysis and X-ray diffraction. Electrochemical analysis of 1-4 shows half wave potentials between -0,17 and -0,38 V vs NHE for the Co3+/Co2+ redox pair, which is in the suitable range for reduction in biological conditions.1 Reactivity studies are being conducted to simulate the reduction of the complexes in physiological conditions to evaluate the dissociation kinetics of the (Tz-R)- ligands.

References: 1. Bustamante, F.L.S.; Miranda, F.S.; Castro, F.A.V.; Resende, J.A.L.C., Pereira, M.D.; Lanznaster, M. J. Inorg. Biochem., 2014, 132, 37. 2. Heffern, M.C.; Yamamoto, N.; Holbrook, R.J.; Eckermann, A.L.; Meade, T.J. Curr. Opin. Chem. Biol., 2013, 17, 1. 3. Souza, I. C. A. et al. XVII BMIC, 2014, (T104).

CAPES, CNPQ, FAPERJ, LAME-UFF, LDRX-UFF

46

P3

SYNTHESIS AND CHARACTERIZATION OF A NOVEL COBALT(III)–NAPHTHOQUINONE COMPLEX AS A PROTOTYPE FOR ANTITUMOR

METALLODRUGS

Marcos Vinícius Palmeira De Mello, Gerardo Cebrián-Torrejón, Mauricio Lanznaster

UFF - Universidade Federal Fluminense

Keywords: PDAHs, Cobalt Complex, Prodrugs, Hypoxia, Naphthoquinone

Conventional anticancer treatments such as chemo- and radio-therapy have limited efficiency in certain types of solid tumors, due to an inefficient vascularization that generates areas of low O2 concentrations, called hypoxic regions.1 An innovative approach is based on the development of prodrugs activated by hypoxia (PDAHs). PDAHs are capable of targeting hypoxic areas of the tumor, releasing the drug selectively in the reductive environment of hypoxic regions.2,3 In this context, cobalt complexes have been studied as potential PDAHs, due to the differences between the cobalt oxidation states: +3 (inert) and +2 (labile).2,3 Ideally, the coordination of a drug to Co3+ inhibits its toxicity and allows the complex circulate intact in the body. When the complex reaches the hypoxic environment of the tumor, the cobalt is reduced to its labile +2 form, releasing the drug to perform the expected pharmacologic effects.3,4 The present work describes the synthesis and characterization of a new complex [CoIII(py2en)(NQ1)](ClO4)2 (1), where NQ1 is de deprotonated form of 5-hydroxy-1,4-naphthoquinone and py2en is the ancillary ligand N,N''-bis(pyridin-2-ylmethyl)ethylenediamine. Electrochemical analysis showed a quasi-reversible process for the couple Co3+/Co2+ with E1/2 = -0,07 V vs. NHE, indicating that the complex can be reduced by reducing agents present in biological systems. Two additional processes are also observed and assigned to the naphthoquinone ligand. Stability studies, simulating the biological environment, and reactivity studies with ascorbic acid (biological reducing agent) are under investigation.3

References: 1. Alves, R. J.; de Oliveira, R. B. Química Nova 2002, 25, 976. 2. Lippard, S. J.; Graf, N. Advanced Drug Delivery Reviews 2012, 64, 993. 3. Lanznaster, M.; Bustamante, F. L. S.; Miranda, F. S. et al. Journal of Inorganic Biochemistry 2014, 132, 37. 4. Ware, D. C.; Chang, J. Y.; Lu, G. et al. Inorganic Chemistry 2013, 52, 7688. CAPES, CNPQ, FAPERJ

47

P4

CRYSTAL AND MOLECULAR STRUCTURES OF THE FIVE COBALT COMPLEXES DERIVED FROM 1,2,4,5-BENZENETETRACARBOXYLIC ACID

Ana Maria Atria 1, José Parada 1, Gino Corsini 2, Ricardo Baggio 3

1 UCH - Facultad De Ciencias Químicas Y Farmacéuticas. Universidad, 2 CIBM - Centro De Investigación Biomédica, Universidad Autónoma De C, 3 CACCEA- Centro Atómico

Constituyentes, Comisión De Energía Atómica.

Keywords: Cobalt , Complexes , Structures

As part of our research project we have synthesized and structurally characterized systems formed with metal ions and 1,2,4,5-benzenetetracarboxylic acid, taking advantage of the ability of this ligand to coordinate metal centers generating structures of varying complexity. In this work we report the structures of five cobalt (II) complexes with benzenetetracarboxylic acid (H4btc) and nitrogen bases: 2,6-diaminopurine (dap); pyrazole (pyr); 1,2-bis(4-piridyl)ethane (bpethane); 1,2-bis(4-pyridyl)ethene (bpethene); 1,3-bis(4-pyridyl)propane (bppropane). The first complex ,[Co(Hdap)2(H2O)4] (btc)∙4H2O, (I) is an ionic structure comprising a [Co(Hdap)2(H2O)4]4+ cationic unit in a general position, charge-balanced by two btc4- anions straddling two different inversion centres such that two independent half-anions in the asymmetric unit provide the required -4 charge. The second complex {[Co2(btc)(pyr)8]∙4H2O}n, (II), correspond a two-dimensional array with a square grid motif presenting the btc4- ligands at the corners, interconnecting the two non-equivalent [Co(pyr)4]2+ units located at the edge centres, in a process which involves both atoms Co1 and Co2. The third and fourth compound {[Co(H2btc)(bpethene)(H2O)2]∙(bpethene)}n,(III),and {[Co(H2btc)(bpethane)(H2O)2]∙(bpethane)}n, (IV), are isomorphic species whose structures correspond to two- dimensional array, with an elemental unit in the shape of a parallelogram having the Co (II) cations at the corners, linked in one direction by bpethene or bpethane bridges and in the opposite direction by H2btc groups. The last compound {(H2btc)[Co(Hbtc)∙(bppropane)(H2O)2]2∙5H2O}n, (V) , is an ionic structure comprising an anionic two-dimensional mesh characterized by a {[Co(Hbtc)(bppropane)(H2O)2]}2 motif with interspersed (H2bppropane)2+ cations, and water molecules providing the charge balance and structure stabilization.

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P5

QUANTUM DOTS - NITROSYL RUTHENIUM COMPLEXES INTERACTIONS. NEW APPROACHES FOR THERANOSTIC APPLICATIONS

Leandro Nériton Cândido Máximo 1, Juliana Cristina Biazotto 2, Roberto Santana Da Silva3

1 FFCLRP/USP - Faculty Of Philosophy, Science And Letters Of Ribeirão Preto, 2 FCFRP/USP - Faculty Of Pharmaceutical Sciences Of Ribeirão Preto, 3 FCFRP/USP -

Faculty Of Pharmaceutical Sciences Of Ribeirão Preto

Keywords: Quantum Dots , Fluorescence, Photochemotherapy, Nitric Oxide, Nitrosyl Complex Of Ruthenium

The research about the nitric oxide (NO) has been increased expressively in last years and nowadays, this molecule is considered vital for many human physiological processes, such as vasodilatation, neurotransmission and cell death[1]. The role of NO in biological system seems to be dependent on its concentration. In this sense, the main goal of this work is to investigate the photoinduced electron transfer process between trans-[Ru(NH3)4(L)(NO)]3+ (RuNO) and cadmium telluride quantum dots (CdTe QDs), as mechanism of NO release by photochemical irradiation and imaging diagnostics[2]. The trans-RuNO complexes were synthesized as previously published procedure[3] and characterized by means of elemental analysis, electrochemistry techniques and electronic and vibrational spectroscopy. The CdTe QDs were synthesized using 3 mercaptopropionic acid (MPA) as capping agent and were characterized by means of fluorescence quantum yield, UV-Visible and fluorescence spectroscopy, resonance light scattering and size particle and lifetime measurements. The fluorescence quenching experiments showed that the ligands (L) have a greater effect on the photophysical properties of interactions RuNO-CdTe. The fluorescence quenching of CdTe by trans-[Ru(NH3)4(L)(NO)]3+ obeys the Stern-Volmer equation, which was described by a linear process for L = pyridine and acetilpyridine and quadratic process for L = 4-picoline and isonicotinamide, suggesting the occurrence of dynamic and static processes simultaneously. ΔG negative values (around - 35 kj.mol-1) shows the spontaneity of interaction. ΔH ˂ 0 and ΔS ˃ 0 values suggest the electrostatic interaction between ruthenium complexes and CdTe QDs. The Stern-Volmer constant (Ksv) were evaluated and the values, between 3,4.105 (L = isonicotinamide) and 1,8.106 (L = pyridine) are dependent on lifetime at excited state and slightly dependent of the ligand. The results suggest a promising system for use as theranostic agent.

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P6

SYNTHESIS AND STRUCTURAL STUDY OF COMPLEX HELICATE OF CU (I)

Dayra Escudero Pérez 1, Pedro Levin 1, Juan Guerrero 1, Luis Lemus 1, Allen Oliver 5, Guillero Ferraudi 5, Alexander Graham Lappin 5

1 USACH- Dayra Escudero, 2 USACH- Pedro Levin, 3 USACH - Juan Guerrero , 4 USACH - Luis Lemus, 5 U Of Notre Dame - Allen Oliver, 6 U Of Notre Dame - Graham Lappin, 7 U

Of Notre Dame - Guillermo Ferraudi

Keywords: Complex, Copper (I), Helicate

Copper (I) is a key cation for the construction of supramolecular structures based on the hierarchical organization of molecular entities.1 When the tetrahedral geometry of the metal is combined with information elements encoded into the ligands, it is possible the arising of different architectures supported on non-covalent interactions, which confer dynamic properties driving to the setting of equilibria in solution.2 This work presents the synthesis, characterization and spectroscopical studies of three bimetallic copper (I) complexes, derived from bis-bipyridine and bis-phenanthroline ligands, namely [CuI2(mphenpr)2](ClO4)2, [CuI2(mphenet)2](ClO4)2 and [CuI2(mbipypr)2](ClO4)2. Complexes were characterized in solution by NMR, UV-vis and X-Ray crystallography in solid phase. [CuI2(mphenpr)2](ClO4)2 and [CuI2(mbipypr)2](ClO4)2 resulted unstable in solution due to their odd alkyl-bridges,3 which is manifested in the establishment of dissociation equilibria with the formation of monometallic complexes. The overall dissociation constants (Kd) for both helicates were determined by 1H-NMR in a series of solvents with different Lewis basicity. Kinetic studies were performed using UV-vis, in order to determine the role of the solvent in the different stages involved in the dissociation reaction. Chiral resolution was performed through counterion exchange, with Δ-[AsV(Cat)3]- (cat=catecholate) as resolution agent for 1H-NMR studies.

50

P7

CHARGE EFFECT OF NEW RUTHENIUM PHYTALOCIANINESIN MODULATION OF NITRIC OXIDE AND SINGLET OXYGEN RELEASE. PHYSICAL CHEMISTRY

CHARACTERIZATIONS AND CYTOTOXICITY EVALUATION IN CANCER CELLS

Loyanne Carla Barbosa Ramos 1, Juliana Alves Uzuelli 1, Juliana Cristina Biazzotto 1, Francisco Batista Do Nascimento 2, Anderson Ribeiro Orzari 2, David Anderson Wink 3,

Roberto Santana Da Silva 1

1 FCFRP-Usp - Faculdade De Ciências Farmacêuticas De Ribeirão Preto , 2 UFABC - Universidade Federal Do ABC, 3 NCI - National Cancer Institute

Keywords: Ruthenium, Phthalocyanines, Photodynamic Therapy, Nitric Oxide

Nowadays metallodrugs have being used to treat several diseases including cancer. In this perspective, structural modifications associated to the use of alternative cancer therapies, as Photodynamic therapy (PDT), has been used to improve selectivity, effectiveness and minimize undesirable effects. PDT involves a photosensitizer, such as ruthenium phthalocyanines, which is activated by light to produce reactive oxygen species (ROS) that induces cytotoxicity. This work describe the physico-chemical characterization as well the influence of the charge in the subcellular localization and cytotoxicity properties of new ruthenium-phthalocyanines complexes – [RuNO(Pc-COOH)Cl] or [RuNO(Pc-(COOH)4)Cl]. The complexes were synthesized using microwave techniques and characterized by UV-visible, infrared, fluorescence spectroscopy and mass spectrometry. Cellular viability was achieved using MTT assays in tumor cells B16F10 and MDA-MB468 and healthy cells L929 and MCF10. The protein expression was evaluated by Western Blotting. The electronic spectrum of the ruthenium-phthalocyanine compounds in dimethylsulfoxide presents intense absorption in 660 nm region correspondent to band-Q. FTIR of the nitrosyl specie shows νNO stretching in 1887 cm-1.The singlet oxygen quantum yield and NO released evaluated using NO-meter shows the potential of these complexes as singlet oxygen and NO donors. The phthalocyanines were not cytotoxic in healthy cells and presented cytotoxity towards B16F10 and MDA-MB468 cancer cells with light irradiation. Fluorescent microscopy images showed that the complexes penetrated in B16F10 cell line after 30 minutes of incubation (10 µM). Western Blotting assay has been used to investigate the expression of different proteins as PARP cleaved and Phospho-PKB, which will direct our future tests to understand the cellular proliferation and the relationship between structure and death mechanisms.

FAPESP, CAPES, CNPq and NAP-photochem.

51

P8

SYNTHESIS AND CHARACTERIZATION OF FERROMAGNETIC IRON (0) NANOPARTICULES

Juan Bustamante 1,3, José Iván Chango Villacis 3, Martha Romero 2, Juan Roberto Anacona 3,1

1 EPN - Escuela Politécnica Nacional, 2 INPC - Instituto Nacional Patrimonio Cultural, 3 CIAP- Centro De Investigaciones Aplicadas A Polímeros

Keywords: Ferromagnetic, Iron (0), Nanoparticules

Synthesis and characterization of nanoparticles is presently an important area of research, as selection of size and shape of nanoparticles provides an efficient control over many of the physical and chemical properties. Processes used for nanoparticles synthesis are chemical, physical, and a recently developed biological method. The latter is an advance over chemical and physical methods of nanoparticle synthesis, as it is cost-effective and environmentally friendly. In the biological method, fungi, bacteria, and plants are used for the synthesis of nanomaterials.1,2 In this work, we present a systematic characterization of the iron nanoparticles prepared by metal ion reduction with cephalexin antibiotic. Particle size, size distribution and surface composition were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), UV-visible spectroscopy, Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), BET surface area and magnetic measurements.. Nanoscale zero-valent iron particles can be prepared in aqueous solutions via the reduction of ferric iron(III) or ferrous iron(II) with cephalexin. We have successfully demonstrated that size, shape and the magnetic activity iron nanoparticles largely depend on the nature of reducing agents, pH, concentration and time of mixing of the reactants. The effect of these experimental parameters were evaluated to optimize the synthesis route producing the metal nanoparticles. SEM images confirmed that metal nanoparticles are in nano range and they are approximately spherical in shape. The powder XRD shows that crystalline with peaks corresponding to Fe nanoparticles. The metallic nature of Fe nanoparticle, confirmed by characteristic peaks of Fe nanoparticles were on 2θ = 43.7° and 50.8°. Results of vibrating sample magnetometer (VSM) indicated that the prepared Fe nanoparticles exhibit ferromagnetic behavior and low saturation magnetization at room temperature.

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P9

SYNTHESIS AND CHARACTERIZATION OF SUPERPARAMAGNETIC IRON(0) NANOPARTICULES

Katherine Vanessa Pazmiño Viteri 1, José Iván Chango Villacís 1, Darío Niebieskikwiat 3, Juan Roberto Anacona Ramírez 1

1 E.P.N. - Escuela Politécnica Nacional, 3 U.S.F.Q. - Universidad San Francisco De Quito

Keywords: Superparamagnetism, Iron (0), Nanoparticles, Clindamicina

The iron nanoparticle technology has received considerable attention for its potential applications in groundwater treatment and site remediation. Recent studies have demonstrated the efficacy of zero-valent iron nanoparticles for the transformation of halogenated organic contaminants and heavy metals.1,2 In this work, we present a systematic characterization of the iron nanoparticles prepared by metal ion reduction using clindamicina. Particle size, size distribution and surface composition were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), UV-visible spectroscopy, Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), BET surface area and magnetic measurements. Nanoscale zero-valent iron particles can be prepared in aqueous solutions via the reduction of ferric iron(III) or ferrous iron(II) with clindamicina. A key advantage of this method is its simplicity. It can be safely done in most chemistry lab with simple chemical reagents. Experimental parameters such as pH, reactant concentrations, stirring speed, titration rate, reaction time and external temperature can, to some extent, influence the composition and surface properties of produced iron particles and hence need to be maintained constant in the experiments to produce consistent samples. SEM images confirmed that iron nanoparticles are in nano range and they are approximately spherical in shape. The powder XRD spectrum showed diffraction peaks at 2θ = 43.7° and 50.8° suggesting crystalline nature. Variable-field and variable-temperature magnetization studies were carried out. It can be seen that all magnetization curves appear s-shaped over the applied magnetic field and the samples exhibit typical superparamagnetic behavior, showing zero coercivity. The blocking temperature is TB = 83 K (B = 0.01 T).

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P10

PREPARATION OF A HYBRID MESOPOROUS SILICA USING A VERSATILE COPPER COMPLEX AS A TEMPLATE

Tatiana Ribeiro-Santos 1, Walace Do Pim 1,2, Cynthia Pereira 1, Maria Araujo 1

1 UFMG - Universidade Federal De Minas Gerais, 2 CEFET-MG - Centro Federal De Educação Tecnológica De Minas Gerais

Keywords: Mesoporous Silica, Hybrid material, Copper Complex

The ordered mesoporous materials, especially those compounds of silica structures, have attracted considerable interest because they have high surface areas, regular sizes adjustable pores, large pore volumes and stable structures.1 The great advantage in the synthesis of mesoporous materials has been the use surfactants/templates. The characteristics of these materials vary according to the properties of this templates.2 In order to develop a hybrid material, we combined a bistable copper-metallacyclic complex that can be used as a molecular switch for the reversible formation of emulsions by simple change of pH.3 This complex was previously applied in a catalytic/separation process.3 In this work we used this copper(II) complex Cu2(H2L)2 [H2L = 2,2’-ethylenediphenylenebis(oxamic acid)] as template in the synthesis of mesoporous materials [Si_Cu2(H2L)2, 1]. The hybrid material and the pure complex were characterized by thermal analyses, FTIR and XRD. Additionally, 1 was characterized by TEM. In both, the weight loss was observed below 150°C due to their hydration water. The thermal analysis for the complex show two weight losses at 298°C and 338°C, probably due to the decomposition of the ligand leading to a residual mass of 16%. For 1 it was observed a weight loss at 306°C, characteristic of decomposition of the complex leading to a residual weight of 76%, must likely indicating the presence of 16% of the complex on silica. In the FTIR spectra were observed characteristic bands of the complex. Significant displacements of the stretch characteristic of C=O bands in 1 in comparison to the pure complex from 1680 and 1637 cm‒1 (Cu2(H2L)2) to 1623 and 1593 cm‒1 (1) suggest an interaction between the complex and the mesoporous silica. Our goal is to apply this new material in heterogeneous catalysis for oxidation / removal of nitrogen compounds from petroleum and apply it as selective catalyst in the oxidation of products of interest in fine chemistry.

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P11

PREPARATION OF SINGLE-WALLED CARBON NANOTUBE COMPOSITE USING COPPER-MANGANESE OXAMATE COMPLEX

Walace Do Pim 1,2, Ingrid Silva 1, Gustavo Do Nascimento 5, Wdeson Barros 3, Ivo Teixeira 4, Ana Teixeira 1, Cynthia Pereira 1, Humberto Stumpf 1

1 UFMG Universidade Federal De Minas Gerais, 2 CEFET-MG - Centro Federal De Educação Tecnológica De Minas Gerais, 3 UNICAMP- Universidade Estadual De

Campinas, 4 University Of Oxford - University Of Oxford, 5 UFABC - Universidade Federal Do ABC

Keywords: Carbon Nanotubes, Spintronics, Hybrid Materials

The development of new materials with technological applications is increasing specifically in the fields of spintronics and molecular magnetism. Thus, a promising strategy for constructing molecular spintronic devices, in the molecular scale-limit, is that of combining conducting materials with small magnetic molecules. A propitious class of compounds that can provide the required magnetism and dimensionality includes the composites prepared from carbon nanotubes (CNTs) and molecule-based magnets.1,2 In this work, selective interactions between the constituents of the composite SWCNT@MnCu (2) prepared using SWCNTs (1) and the heterobimetallic chain [MnCu(opba)]n (MnCu), opba = ortho-phenylenebis(oxamate), were studied mainly by Resonance Raman spectroscopy, Fourier Transform Infrared spectra (FTIR) thermogravimetric analyses (TG and DTA) and Transmission Electron Microscopy (TEM). An apparent interaction between carbon nonotubes (CNTs) and MnCu complex with the wrapping of the former by the heterobimetallic complex was observed in the microscopy images. The Resonance Raman data suggest that the interations between MnCu complex and the CNTs are selective, occurring mainly with metallic CNTs independently of the diameter and excitation energy, however, for semiconducting CNTs, this interactions solely occurs with tubes having diameter higher than ca. 1.47 nm.

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P12

SYNTHESIS OF Ta2O5 NANOPARTICLES FROM 1-N-ALKYL-3-METHYLIMIDAZOLIUM HEXACHLOROTANTALATE IONIC LIQUIDS

Virgínia Serra De Souza, Jackson Damiani Scholten, Jairton Dupont1

UFRGS - Federal University Of Rio Grande De Sul

Keywords: Ionic liquids , Nanoparticles , 1-n-alkyl-3-methylimidazolium hexachloro, Water splitting process

This resume describes the synthesis of Ta2O5 nanoparticles (NPs) from 1-n-alkyl-3-methylimidazolium hexachlorotantalate (alkyl = butyl: BMI.TaCl6, decyl: DMI.TaCl6) ionic liquids1 (ILs) and their application in the water splitting process.2 By this route it is desired the use of intrinsic properties of ILs to act as precursors and stabilizing agents in the formation of nanosized Ta2O5 particles. TEM analyses showed that NPs prepared from the hydrolysis of BMI.TaCl6 and DMI.TaCl6 have mean diameters of 8 and 2 nm, respectively, indicating a significant role of the IL cation on the formation and stabilization of the NPs. In the electron diffraction mode, TEM revealed that the as-prepared Ta2O5 NPs are crystalline. The optimization of the synthesis parameters and photocatalysis (sacrificial agent, catalyst amount) gives maximization in the hydrogen photoproduction. The sample DMI 1:0,5 showed an excellent photoactivity in the hydrogen generation using ethanol as sacrificial agent (apparent quantum efficiency of 17% and hydrogen production of 7,2 mmol H2.h-1.g-1). The photoactivities of the as-prepared Ta2O5 NPs were superior to those obtained for the thermal treated samples. These results can be related to the presence of remained IL in the samples, which provides hydrophilic regions helping in the water molecule approach to the catalyst active sites favoring the photocatalytic reaction, while in thermal treated samples there is a loss of IL after the treatment. In order to improve the hydrogen production, Pt NPs were deposited by sputtering3 technique onto the surface of Ta2O5 NPs. The sample DMI 1:0,5 Pt was capable to increase the hydrogen production up to 30% (9,2 mmol H .h-1.g-1) during the water splitting process.

(1) Dupont, J.; Consorti, C. S.; Suarez, P. A. Z.; de Souza, R. F. In Organic Syntheses; John Wiley & Sons, Inc.: 2003. (2) Kudo, A.; Miseki, Y. Chemical Society Reviews 2009, 38, 253-278. CNPQ

56

P13

ORGANOTIN(IV) LEVOFLOXACIN COMPLEXES: SYNTHESIS, BIOLOGICAL ACTIVITY AND INTERACTION WITH ALBUMIN

Lucius Flavius Ourives Bomfim Filho, Rafaela Sernagiotto Barbosa, Jacqueline Aparecida Takahashi, Letícia Regina De Souza Teixeira

UFMG - Universidade Federal De Minas Gerais

Keywords: Fluoroquinolone, Organotin, Complexes

The fluoroquinolones group of synthetic drugs are highly active against both Gram-positive and Gram-negative pathogens and present favorable pharmacokinetic properties for treating a wide array of infections.1 The tri-substituted organotin(IV) species, containing alkyl groups, have greater antimicrobial activity than the mono and di-substituted.2 Thus, in order to connect levofloxacin and organotin(IV) activities and in consideration of the fact that there are no reports in the literature on the organotin(IV) levofloxacin complexes, in this present work, four Sn(IV) complexes Sn(CH3)2(lfx) (1), Sn(C4H9)2(lfx) (2), Sn(CH3)3(lfx) (3) and Sn(C4H9)3(lfx) (4) where lfx = levofloxacin, were obtained and characterized by elemental analyses, IR, 1H, 13C and 119Sn NMR. The in vitro antimicrobial activity of the compounds was evaluated against two Gram-positive bacterial strains (Staphylococcus aureus and Bacillus cereus), Gram-negative bacterial strains (Escherichia coli and Salmonella enteritidis) and the fungi Candida albicans. The organotin(IV) levofloxacin complexes showed a significant increase in antibacterial activity when compared to free levofloxacin. Complexes 1 – 4 demonstrated that they can interact with human serum albumin (HSA) thus indicating that they could be carried by albumin in the blood.

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P14

METAL COMPLEXES WITH CHALCONE-DERIVED THIOSEMICARBAZONES: CYTOTOXIC ACTIVITY AND INTERACTION WITH TOPOISOMERASE AND

THIOREDOXIN REDUCTASE.

Luciana Sâmia 1, Jeferson Da Silva 2, Gabrieli Parrilha 1, Jonas Ramos 3, Elaine Souza-Fagundes 3, Silvia Castelli 4, Alessandro Desideri 4, Heloisa Beraldo 1

1 UFMG - Universidade Federal De Minas Gerais, 2 UFJF- Universidade Federal De Juíz De Fora, 3 UFMG - Universidade Federal De Minas Gerais, 4 University Of Rome -

University Of Rome "Tor Vergata"

Keywords: Metal Complexes, Thiosemicarbazone, Cytotoxic Activity, Topoisomerase, Thioredoxin Reductase

Thiosemicarbazones are class of compounds with a wide range of pharmacological applications.1 Chalcone-derived thiosemicarbazones and their metal complexes were shown to possess cytotoxic activity against human cancer cell lines.2 While the main biological target of thiosemicarbazones is believed to be ribonucleotide reductase (RR), the mode of action of their metal complexes may involve inhibition of other cellular targets such as thioredoxin reducatse (TrxR) and topoisomerase II (TopoII).3,4 In the present work we investigated the cytotoxic effects of Cu(II), Au(III) and Pt(II) complexes with 3-(4-bromophenyl)-1-pyridin-2-ylprop-2-en-1-one thiosemicarbazone (HL) against leukemia (Hl-60, Jurkat, THP-1) and solid (MCF-7, HCT-116) tumor cells as well as the interactions of the compounds under study with TopoII and TrxR. The free thiosemicarbazone exhibited potent cytotoxic activity. Upon coordination activity incread in [Cu(L)Cl], complex (1) and [Au(L)Cl]Cl, complex (2) whereas [Pt(L)Cl], complex (3) showed poor cytotoxic effects. While the thiosemicarbazone did not show any inhibitory effects in vitro on TrxR at 10µM, its Cu(II) and Au(III) complexes inhibited 60% and 91%, respectively of the enzyme activity. Assays on topoisomerase activity indicated that the Cu(II) complex (1) is able to inhibit relaxation cleavage and religation of DNA. 1 does not interact with DNA even at high concentration as monitored by gel electrophoresis. The Au(III) complex (2) clearly inhibits relaxation inhibition and shows a strong interaction with DNA at high concentrations.

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P15

SYNTHESIS, CHARACTERIZATION AND DIESTERASE ACTIVITY OF NEW BIOMIMETICS FOR PURPLE ACID PHOSFATASES (PAPS) WITH SECOND-

COORDINATION-SPHERE EFFECTS

Renata Heying, Ademir Neves

UFSC - Federal University Of Santa Catarina

Keywords: Purple Acid Phosphatases, Polydentate Ligands, Second-coordination-sphere

The development of model complexes mimicking the active site of metalloenzymes is one of the main focus of research in Bioinorganic Chemistry [1]. Currently, the development of new ligands and their complexes which besides the first-coordination-sphere of the active site, also takes into account the effects of the second-coordination-sphere to enhance catalysis, has increased significantly [2]. This work consists on the structural modification of the dinucleating H2L ligand already described in the literature [3], followed by the synthesis of its dinuclear FeIII(µ-OH)-ZnII (1) and FeIII(µ-OH)CuII (2) complexes. The ligand H2LHex was prepared by a reductive amination of H2L and 1,6-hexanediamine and was characterized by 1H NMR, IR and ESI-MS while the complexes were characterized by IR, ESI-MS, conductometry, UV-vis spectrophotometry and electrochemistry. Kinetic studies on the hydrolysis of the diester substrate bis(2,4-dinitrophenyl)phosphate in presence of 1 or 2 revealed that, while the catalytic constant kcat is decreased, the association constant of the substrate-complex intermediate is significantly favored when compared to the complexes without the second- coordination-sphere effects. Finally, it is concluded that the role of the second-coordination-sphere seems to be quite complex and that such studies should significantly contribute to the understanding of these effects in biomimetic catalysts.

Reference: 1. Karlin, K. D., Barton, J. K.; Curr. Opin. Chem. Biol. 2001, 5, 165. 2. Zhao, M.; Wang H. B.; Ji, L. N.; Mao, Z. W.; Chem Soc. Rev. 2013, 42, 8360. 3. Piovezan, C. et al.; Inorg. Chem. 2010, 49, 2580. CNPQ, CAPES, INCT- Catálise, UFSC

59

P16

ANALYSIS OF BIOREDUCTION AND CYTOTOXICITY OF CO3+ COMPLEXES CANDIDATES TO ANTITUMOR PRODRUGS

Rafaella Rebecchi Rios, Marcos D. Pereira, Marciela Scarpellini

UFRJ- Universidade Federal Do Rio De Janeiro

Keywords: Bioinorganic, Antitumor, Complexes, Cobalt, Cancer

Solid tumors present regions of low oxygen (hypoxia) controlled by the irregular growth of blood vessels, which usually become resistant to chemo and radiotherapies. This characteristic have been explored for the development of hypoxia target-specific prodrugs, since this region of the tumor is a reducing environment. Then, cobalt complexes have been exploited as drug delivery, specially because of two oxidation states with different lability, Co3+ that is inert, and Co2+ which is more labile. In order to evaluate a series of complexes to act as bioreductively activated prodrugs1,2, here is presented the potential of biomoleculesto reduce the following series, [Co(bhi-R)2]+ - with R= H, CH3, OCH3, Br and NO2, in addition to their cytotoxicity activity against the tumor cell line MCF-7, with and without previous reduction. Ligands were synthesized reacting histamine with 5-R-salicilaldehydes and treated with cobalt salts affording the desired complexes. After recristalization, single crystals were obtained, caracterizated,³ and then used for bioreduction and cytotoxicity analyses. Bioreductions were spectroscopically monitored using complexes solutions (1x10-4M). The LMCT bands were monitored before and after the addition of cysteine (or ascorbic acid) in two different concentrations (5x10-4M and 10-3M) during 1/2, 1, 3/2, 2, 20, 24, 44, 48 and 120h. The best results were achieved with ascorbic acid (10-3M), where the decrease of the LMCT band after 120h was: 9,3% for [Co(bhi-H)2]BF4; 14,2% for [Co(bhi-CH3)2]+; 10,5% for [Co(bhi-OCH3)2]BF4; 12% for [Co(bhi-NO2)2]ClO4.

The cytotoxicity analyses are under investigation, incubating the tumoral cell line MCF-7 with 100uM of the complexes, for 24h, and the cellular viability is being evaluated by MTT test. 1SOUZA, E. T.; Journal of Inorganic Biochemistry, 2009, 103, 1355-1365. 2SOUZA, E. T.; Journal of Inorganic Biochemistry, 2011, 105, 1767-1773. 3Personal information (data not published).

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P17

NOVEL ANTI-DEPRESSANT ACTIVITY IN ANIMAL MODEL OF ZN(II)-S-METHYL-CYSTEINE COMPLEX AND OTHER PHARMACOLOGICAL ACTIVITIES.

Evelina Ferrer 8, Graciela Escudero 4, Nancy Martini 1, Khalil Jori 2, Nadir Jori 3, Nahuel Maresca 5, Carlos Laino 6, Patricia Williams 7

1 N. Martini - Cequinor/Conicet, Unlp, C. C. 962, 1900 La Plata, Argentina, 2 K. Jori - Cequinor/Conicet, Unlp, C. C. 962, 1900 La Plata, Argentina, 3 N. Jori - Cequinor/Conicet, Unlp, C. C. 962, 1900 La Plata, Argentina, 4 G.E. Escudero - Ibyf-Ceniit-Unlar , Av Vernet Y Ap. Felipe (5300) La Rioja, 5 N.R. Maresca - Ibyf-Ceniit-Unlar , Av Vernet Y Ap. Felipe

(5300) La Rioja, 6 C.H. Laino - Biotec-Ceniit-Unlar, Av Vernet Y Ap Felipe (5300) La Rioja, 7 P.A.M. Williams - Cequinor/Conicet, Unlp, C. C. 962, 1900 La Plata, Argentina, 8 E.G.

Ferrer - Cequinor/Conicet, Unlp, C. C. 962, 1900 La Plata, Argentina

Keywords: Anti-Depressant Activity, Zn(II), S-Methyl-Cysteine

The antidepressant-like effect of simple Zn(II) salts has been proved in several animal models of depression1. In this study, a coordination metal complex of Zn(II) having a sulfur containing ligand is tested as antidepressant for the first time. Treatment of Zn(S-Met)2 (S-Met= S-methyl-L-cysteine) in the rat forced swimming test model of depression shows a decrease in the immobility and an increase in the swimming behavior being this action more effective and remarkable than ZnCl2 (synergic effect as a result of the coordination). There is a great scientific attention in new pharmacological compounds proficient in inhibiting phosphatases activities2 and also acting as antioxidant compounds. The interest in the determination of the antioxidant activity of S-methyl-L-cysteine was based on previous data that indicated the decrease in oxidative stress under the presence of cysteine-containing agents.3 In addition, this work includes the determination of the antioxidant activity and the inhibition studies on acid phosphatase enzyme (AcP). Both S-methyl-L-cysteine and the Zn(S-Met)2 complex have been tested against peroxyl and hydroxyl radicals. The results present evidence of attenuation of hydroxyl but not peroxyl activity. S-methyl-L-cysteine do not produces effect on AcP activity in contrast to the Zn(S-Met)2 complex that behaves as a good inhibitor agent. Finally, bioavailability studies have been performed using fluorescence spectroscopy and the ability of albumin to transport the complex can be determined.

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P18

ORGANOMETALLIC SULFONAMIDES CONTAINING FERROCENYL AND CYRHETRENYL MOIETIES: SYNTHESIS, CHARACTERIZATION, X-RAY AND ANTI-

MICROBACTERIUM TUBERCULOSIS EVALUATION

Rodrigo Arancibia 1,2, Cristobal Quintana 2, Hugo Klahn 2, Laurent Kremer 3

1 UDEC - Universidad De Concepción, 2 PUCV - Pontificia Universidad Catolica De Valparaiso, 3 UM1 - Université De Montpellier

Keywords: Bioorganometallics, Sulfonamides, Tuberculosis, Cyrhetrene, Ferrocene

Organic compounds containing sulfonamides fragments (Sfn) have been extensively investigated with regards to their biological properties.[1] Nevertheless, organometallic analogues have received considerably less attention, according to our acknowledge some cyrhetrenyl-Sfn and ferrocenyl-Sfn have been evaluated as carbonic anhydrase inhibitor agents.[2,3] With the aim to get more insights in this type of compounds, we would like to report the design, synthesis and characterization of new ferrocenyl and cyrhetrenyl sulfonamides and their biological evaluation against Mycobacterium tuberculosis strain. All compounds were isolated as pure samples and characterized by spectroscopic techniques (IR, NMR and MS) and the structures for two of them were confirmed by the X-ray crystallography. At present the biological studies against Mycobacterium tuberculosis are under investigation.

References: 1. Dai, H.; Stepan, A.; Plummer, M.; Zhang, Y.; Yu, J. J. Am. Chem. Soc. 2011, 133, 7222. 2. Can, D.; Spingler, B.; Schmutz, P.; Mendes, F.; Raposinho, P.; Fernandes, C.; Carta, F.; Innocenti, A.; Santos, I.; Supuran, C..T; Alberto,R. Angew. Chem. Int. Ed. 2012, 51, 3354. 3. Salmon, A.; Williams, M.; Wu, Q.; Morizzi, J.; D. Gregg, D.; Charman, S.; Vullo, D.; Supuran, C.; Poulson, S. J. Med. Chem., 2012, 55, 5506. FONDECYT-Chile (Project 11130443) D.I. Pontificia Universidad Católica de Valparaíso.

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P19

IN(III) COMPLEXES WITH 2-ACETYLPYRIDINE-DERIVED THIOSEMICARBAZONES: CYTOTOXIC ACTIVITY AGAINST LEUKEMIA AND SOLID TUMOR CELLS LINES

Alexandre Almeida Oliveira 1, Luana Escriche Rodrigues 1, Jeferson Gomes Da Silva 2, Gabriele Matos Cardoso Perdigão 3, Elaine Maria De Souza Fagundes 3, Heloisa De

Oliveira Beraldo 1

1 UFMG- Dept. Of Chemistry, 2 UFJF - Dept. Of Pharmacy, Campus Governador Valadares, 3 UFMG- Dept. Of Physiology And Biophysics

Keywords: Thiosemicarbazones, Indium(III), Cytotoxic Activity

111In radiopharmaceuticals are the main highlight of research and applications of In(III) complexes in medicine.1 However, the research on indium-based drug candidates remains practically unexplored. 2-acetylpyridine-derived thiosemicarbazones possess potent cytotoxic effect against human solid tumor and leukemia cell lines. Upon coordination their cytotoxic effects increased in several cases.2 Considering that there are not many reports in the literature on the cytotoxic activity of In(III) complexes and in view of the potential use of 111In in diagnostic and therapy, in the present work six novel [In(L)2]NO3 complexes with HL = 2-acetylpyridine-N(4)-phenyl thiosemicarbazone (H2Ac4Ph) (In1) and its N(4)-ortho-chlorophenyl- (In2), N(4)-meta-chlorophenyl- (In3), N(4)-para-chlorophenyl- (In4), N(4)-para-fluorphenyl- (In5) and N(4)-para-iodophenyl- (In6) derivatives were obtained. The in vitro cytotoxic activity was evaluated against human leukemia (HL60, Jurkat and THP-1) and solid tumor cell lineages (MDA-MB-231, MCF-7 and HCT- 116). Cytotoxicity against Vero cells as healthy cell model was also evaluated in order to determine the therapeutic indexes (TI). Upon coordination to In(III) cytotoxicity in the solid tumor cells increased in several cases, especially against HCT-116 cells (In1, TI = 201; In5, TI = 420). Complexation also resulted in higher cytotoxic effect against HL60 cells. In1 proved to be the most active compound with IC50 = 40 nM (TI = 80), 4-fold more active than the parent ligand and 12-fold more active than cisplatin. In(NO3)3 proved to be inactive against the cancer cells.

References: 1. Weiner, R. E.; Thakur, M. L. In Handbook of radiopharmaceuticals; Welch, M. J.; Redvanly, C. S., eds.; John Wiley & Sons: England, 2005, ch. 11. 2. Parrilha, G. L.; Ferraz, K. S. O.; Lessa, J. A.; Oliveira, K. N.; Rodrigues, B. L.; Ramos, J. P.; Souza-Fagundes, E. M.; Ott, I.; Beraldo, H. Eur. J. Med. Chem. 2014, 84, 537. CNPq, INCT-INOFAR, FAPEMIG and CAPES

63

P20

SYNTHESIS, CHARACTERIZATION AND IN VITRO CYTOTOXIC ACTIVITY OF THE PALLADIUM(II) COMPLEXES WITH PYRIDINE-3-CARBALDEHYDE AND QUINOLINE-3-CARBALDEHYDE THIOSEMICARBAZONE LIGANDS AGAINST VARIOUS HUMAN

TUMOR CELL LINES

Wilfredo Román Hernández Gorritti 2, Fernando Carrasco 3, Abraham Vaisberg 4, Jorge Manzur 5, Evgenia Spodine 6, Lothar Beyer 7

2 Wilfredo Hernández - Universidad De Lima, 3 Fernando Carrasco - Universidad De Lima, 4 Abraham Vaisberg - Universidad Peruana Cayetano Heredia, 5 Jorge Manzur -

Universidad De Chile, 6 Evgenia Spodine - Universidad De Chile, 7 Lothar Beyer - Universidad De Leipzig-Alemania

Keywords: Thiosemicarbazone, Antitumor activity, palladium(II) complexes

The present work describes the preparation, characterization and antitumor activity of palladium(II) bis-chelates, PdL2, of pyridine-3-carbaldehyde and quinoline-3-carbaldehyde thiosemicarbazones derivatives [1]. The ligands and their palladium complexes have been synthetized and characterized by elemental analysis and IR and NMR (1H, 13C) spectroscopy. Analytical and spectroscopy data are consistent with the proposed structural formulae for the ligands and their complexes. The spectroscopy data revealed that the deprotonated pyridine-3-carbaldehyde and quinolone-3-carbaldehyde thiosemicarbazone derivatives are coordinated to the Pd(II) ion through the nitrogen and sulphur atoms [2]. The in vitro antitumor activity of the ligands and their complexes was determined against six human tumor cell lines: H460, DU145, M14, HT29, K562 and MCF-7. The antitumor studies revealed that the palladium(II) complexes are more cytotoxic (IC50= 8.40 – 13.50 µΜ) than their ligands (IC50= 44.30 – >460.0 µΜ) . The palladium(II) complex with the 4-phenyl-1-(6´-methoxy-quinoline-3´-carbaldehyde) thiosemicarbazone ligand showed higher antiproliferative activity (CI50 = 8.40 μM) than the other tested palladium(II) complexes against H460, K562 and MCF-7 tumor cell lines. W. H. thanks the Universidad de Lima Scientific Research Institute for financial support to carry out the research work. E. S. and J. M. thank Basal Project FB0807 (CEDENNA).

References 1. Maia, P. I.; Graminha, A.; Pavan, F.R.; Leite, C.Q.; Batista, A.A; Back, D.F; Lang, E.S; Ellena, J; Lemos, S.S; Salistre-de-Araujo, H.S; Deflon, D.M. J. Braz. Chem. Soc., 2010, 21, 1177-1186. 2. Hernández, W.; Paz, J.; Carrasco, f., Vaisberg, A.; Spodine, E.; Manzur, J.; Hennig, L.; Sieler, J.; Blaurock, S.; Beyer, L. Bioinorg. Chem. Appl., Volume 2013, Article ID 524701, 12 pages.

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P21

SYNTHESIS AND CHARACTERIZATION OF CYRHETRENE COMPLEXES FUNCTIONALIZED WITH ARYLPIPERAZINE LIGANDS AND THE POTENTIAL

AFFINITY OF GSK-3 PROTEIN

Michelle Muñoz-Osses 1, Fernando Godoy 1, Angélica Fierro-Huerta 2

1 USACH- Universidad De Santiago De Chile, 2 PUC – Pontificia Universidad Católica De Chile

Keywords: Synthesis, Cyrhetrene , Complexes, Affinity

GSK-3B Glycogen synthase kinase 3β (GSK-3β) is a serine-threonine protein is related to diseases such as diabetes, Parkinson’s, Alzheimer’s. Studies described in literature indicate that arylpiperazine ligands have affinity for GSK-3β protein with IC50 values of the micromolar order [1]. While the presence of a metal center in these novel compounds plays a structural role in the distribution and spatial orientation of the organic ligands in the binding sites of various biological targets, improving the affinity of organometallic complexes with IC50 nanomolar order for GSK-3β [2]. In this work we synthetized a family of cyrhetrene complexes functionalized with arylpiperazine ligands such as potential drugs for GSK-3β protein. Using theoretical studies was possible to determine the cavity volume of GSK-3β protein, which was about 600 Å3.For organometallic complexes (η5-C5H4X-1-(diphenylmethyl)piperazine)Re(CO)3 (3) they have a volume between 560 to 580 Å3 (X=-CONH (a); HC=N (b); 2HC-NH (c)), whereas for complexes (η5-C5H4X-1-(2-methoxyphenyl)piperazine)Re(CO)3] (5) (X= CONH (a); HC=N (b); 2HC-NH (c)) the volume is between 491 and 499 Å3. With these results it is possible to estimate that cyrhetrene complexes could interact with the amino acid residues which form the binding site of the protein without limiting the volume of the systems. In relation of the synthesis of complexes, the reaction of acyl chloride cyrhetrene (1) with 1 diphenylmethylpiperazine amine (2a) or 1-2-methoxyphenylpiperazine amine (2b) under nitrogen atmosphere, the solutions were stirred for 2 hours at 0ºC, giving the corresponding amide 3a and 5a. The reaction of aldehyde cyrhetrene (4) with 2a or 2b under nitrogen atmosphere, the solutions were refluxed during 9 hours, giving the imine respective 3b and 5b. The complexes were obtained as oily solids in moderate and high yield. All complexes were characterized by 1H, 13C, 31P NMR, IR and MS. Later, all complexes will be evaluated in GSK-3β protein.

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P22

SYNTHESIS AND CHARACTERIZATION OF A DINUCLEAR COPPER(II) COMPLEX AS NUCLEASE WITH AN INTERCALATING AGENT

Claudia Pereira 1, Alana Homrich 2, Tiago Camargo 3, Ademir Neves 4, Rosely Peralta 5

1 C. Pereira - Claudia Pereira, 2 A.M. Homrich - Alana M. Homrich, 3 T. P. Camargo - Tiago Pacheco Camargo, 4 A. Neves - Ademir Neves, 5 R. A. Peralta - Rosely Aparecida

Peralta

Keywords: Nucleases, Nucleic Acids

DNA-intercalating Design and synthesis of DNA-targeted compounds have important application in chemistry, biology and medicine fields. DNA-intercalating molecules are those which intercalate DNA base pairs via electron-deficient planar chromophores with flexible side chains. These specially designed groups confer DNA sequence selectivity and allow aromatic heterocycles to position at proper sites or interact with topoisomerases so as to interfere with DNA replication and transcription. In this context it was designed an unsymmetrical ligand containing the 1,8-naphthalimide group. Several studies based on naphthalimide molecules have shown a high affinity for DNA via intercalative mechanism.3 Thus a dinuclear copper(II) complex containing the unsymmetrical ligand containing 1,8- naphthalimide, tertiary amino groups, pyridine and piperazine as donor atoms and a phenol group as a endogenous bridge was synthesized by adding to an acenotrile solution containing 1 mmol of the ligand and 2 mmol of copper(II) acetate under stirring and mild heating. After 5 min, a green crystalline solid was formed, which was characterized via infrared, electronic spectroscopy and square wave voltammetry. The infrared spectrum showed the displacement of the main bands of the ligand, showing the complexation of the metal (N-Hamine) 3211;(C-Haliph) 2935; (C=Onaphtalimide) 1572-1476; (C-Ophenol) 1290; (C-Har) 767; (C-Hpy) 664. The electronic spectrum showed two bands: the first one, centred at 670 nm, is attributed to d-d copper(II) ion transition and the second, centred at 405 nm is attributed to an intraligand electronic transition. The SWV showed two wave reduction processes: CuIICuII/CuIICuI with Epc=-480 mV vs NHE and CuIICuI/CuICuI with Epc=-995 mV vs NHE. Experiments of interaction and cleavage of the DNA with the complex are underway to study the intercalating ability of the 1,8-naphtalimide group, present in the ligand, and will be the subject of future publications.

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P23

A NEW COBALT(III)-TPA PLATFORM TO DELIVER TRIAZOLE-BASED DRUGS

Letícia Faro, Daniel Gonzaga, Fernando Silva, Fabio Miranda, Jackson A.L.C. Resende, Mauricio Lanznaster

UFF - Universidade Federal Fluminense

Keywords: Cancer, PDAH, Cobalt, Triazole, Drug Delivery

Hypoxic cells, common in solid tumors, provide the selectivity that differentiates healthy and cancerous cells. Thus, a substance might be designed to circulate intact in the body with minimal interactions with normal cells, being selectively activated at hypoxic regions of a tumor.1 Based on this approach, Co(III) complexes have been developed and tested as potential prodrugs activated by hypoxia (PDAH). In this way, our group initiated an investigation on the synthesis, characterization and study of the properties, reactivity and biological activity of Co(III) complexes, aiming to develop new prototypes of PDAHs. 1,2,3-Triazoles are an important class of N-heterocycles with great relevance to medicinal chemistry including anticancer activity. Moreover, Co(III) complexes with 1,2,3-triazole ligands as potential PDAHs are still unexplored. Therefore, in this work, we describe the synthesis of two new complexes, [CoIII(HTZ1)(TPA)](BF4)2 (1) and [CoIII(HTZ2)(TPA)](BF4)2 (2), were TPA = tris-(pyridin-2-ylmethyl)amine, HTZ1 = (E)-1-phenyl-1H-1,2,3-triazole-4-carbaldehyde oxime and HTZ2 = (E)-1-(4-chlorophenyl-1H-1,2,3-triazole-4-carbaldehyde oxime. These complexes were obtained from one-pot reactions between Co(BF4)2.6H2O, TPA, HTZ1 or HTZ2 and Et3N, and characterized by IR, UV-Visible and 1H NMR spectroscopies, mass spectrometry and CHN elemental analysis. Cyclic voltammetry revealed a quasi-reversible process at -0.58 V and -0.52 V vs Fc/Fc+ for 1 and 2, respectively, assigned to the Co3+/Co2+ redox pair. These data indicate that reduction of the Co3+ center is accessible in biological conditions. Dissociation of the TZ1− and TZ2− ligands was observed from the reaction of 1 and 2 with ascorbic acid (AA). A dependence on the O2 concentration was found for the reaction kinetics, suggesting the occurrence of redox cycling – Co2+ being re-oxidized back to Co3+ by O2 after reduction by AA.

Acknowledgments: CAPES, CNPQ, FAPERJ

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P24

SYNTHESIS AND CHARACTERIZATION OF NOVEL COBALT(III) COMPLEXES WITH COUMARIN AND CATECHOLATE LIGANDS AS PROTOTYPES FOR BIOREDUCTIVE

PRODRUGS

Renata Crispin Batista, Marcos Vinicius Palmeira De Mello , Gerardo Cebrián-Torrejón, Mauricio Lanznaster

IQ-UFF - Instituto De Química, Universidade Federal Fluminense

Keywords: Bioinorganic, Cancer, Solid tumors, Bioreductive Prodrugs

Cobalt Resistence to chemo- and radio-therapy are a main concernt in cancer treatment. The disorganized grow of a tumor creates regions of poor vascularization and consequent low concentrations of oxygen (hypoxic regions), which reduces the eficacy of the conventional therapies.1 This diferenciation from normal tissue, however, is being exploited to develop new therapeutic strategies to target cancerous cells, such as prodrugs activated by hypoxia.2 In this context, cobalt complexes have been studied, due to the differences between their oxidation states: +3 (inert) and +2 (labile). Ideally, coordination with Co3+ deactivates a drug toxicity and allows the complex to circulate throught the organism with minimum damage to normal tissues. When the complex reachs the hypoxic environment of the tumor, the cobalt (+3) is reduced to its labile +2 form, releasing the drug to perform its pharmacologic effects.3 The present work describes the synthesis and characterization of two novel cobalt(III) complexes containing 6,7-dihydroxycoumarin (L1) and pyrocatecholate (L2), namely [CoIII(py2en)(L1)]ClO4 (1) and [CoIII(py2en)(L2)]ClO4 (2), where py2en is the ancillary ligand N,N’-bis(pyridin-2-ylmethyl)ethane-1,2-diamine. The electrochemical analysis revealed a quasi-reversible process for the couple Co3+/Co2+. X-ray diffraction of 1 confirmed the presence of the 6,7-dihydroxycoumarin in its deprotonated form, and the ancillary ligand, both coordinated to the cobalt in an octahedral fashion. The average bond distances are close to the expected values for a Co3+ ion (~1.90 Å).4 Stability of both complexes and reactivity studies mimicking bioreductive agents are being conducted and will be presented.

References:

1. Brow, M.J.Cancer Research. 1998, 58, 1408. 2. Graf, N. et al. Advanced Drug Delivery Reviews. 2012, 64, 993. 3. Lanznaster, M. et al. Journal of Inorganic Biochem. 2014, 132, 37. 4. Orpen, A.G. et al. J. Chem. Soc., Dalton Trans. 1989, 12, S1. CAPES, CNPQ, FAPERJ

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P25

SYNTHESIS AND CHARACTERIZATION OF A NEW SYNTHETIC METALLOHYDROLASE FOR CATALYSIS AND SIMULATION OF THE SECOND

COORDINATION SPHERE

Anderson Bastos Pires 1, Tiago Pacheco De Camargo 1, Sandro Mireski 2, Ademir Neves 1

1 UFSC - University Federal Of Santa Catarina, 2 FURB - Regional University Of

Keywords: Bioinorganic Chemistry, Heterodinuclear Complex

Catalyze Second coordination sphere effects are generated primarily from the presence of charged groups or molecules, which may participate in hydrogen bonds with ligands present in the first coordination sphere of metalloenzymes. These effects are of vital importance in catalysis so that residual amino acids that are not directly coordinated to the metal ions are crucial for stabilization of the transition state, lowering ΔG and increasing the speed of reaction. 1 These groups influence the enzymatic catalysis by means of connections Hydrogen bond, Van Der Waals forces and electrostatic interactions, acting synergistically with the metal center. The objective of this work is the interest in modifying an existing ligand to simulate second coordination sphere effects and verify its consequences in the hydrolysis reaction of the substrate 2,4-BDNPP model. The ligand was modified adding a side chain a group histamine. It was then synthesized a complex of Fe(III)Zn(II) H2L-his with the ligand that has a non-symmetrical structure, in order to guide the formation of the heterodinuclear mixed valence complex.2 The imidazole group may act on hydrogen bonding effects which simulate second coordination sphere present in metalloenzymes. The ligand was characterized by infrared spectroscopy and 1H NMR (2H, 2.87, 2H 3.04, 1H, 5.04, His). The complex was characterized by infrared spectroscopy, UV-Vis, mass spectroscopy, cyclic voltammetry (E1/2 = 0.018 Volts) and potentiometric titration (pK1= 11.23, pK2= 8.58, pK3 = 5.58 pK4= 3.87). Kinetic studies are being carried out and will be the subject of future publications.

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P26

AROMATIC AMINE N-OXIDE ORGANOMETALLIC COMPOUNDS: SEARCHING FOR PROSPECTIVE AGENTS AGAINST Trypanosoma Cruzi

Esteban Rodríguez Arce 1, Florencia Mosquillo 2, Leticia Pérez 2, Gustavo Echeverría 3, Oscar Piro 3, Alicia Merlino 4, Laura Coitiño 4, Lucia Otero 1, Dinorah Gambino 1

1 UDELAR - Cátedra De Química Inorgánica, Facultad De Química, Uruguay, 2 UDELAR - Interacciones Moleculares, Facultad De Ciencias, Uruguay, 3 UNLP - Departamento De

Física, Facultad De Cs. Exactas, Argentina, 4 UDELARr - Laboratorio De Química Teórica Y Computacional, Uruguay

Keywords: Trypanosoma cruzi, pyridine-2-thiol 1-oxide, Ferrocene Compounds, Palladium and Platinum

American Trypanosomiasis, caused by the protozoan parasite Trypanosoma cruzi, constitutes a major health concern in Latin America. Searching for prospective agents against T. cruzi, [M(mpo)(dppf)](PF6) compounds, where M = Pd(II) or Pt(II), dppf = 1,1''-bis (diphenylphosphino) ferrocene and mpo = pyridine-2-thiolato-1-oxide, were synthesized and fully characterized in the solid state and in solution. The compounds are isomorphous. M(II) ion is in a nearly planar trapezoidal coordination bound to mpo and dppf molecules acting as bidentate ligands. Both compounds showed IC50 values in the nanomolar range on T. cruzi with good to excellent selectivity index values. The inclusion of the ferrocene moiety improved the selectivity towards the parasite when compared to the previously reported [M(mpo)2] complexes.1 Related to the probable mechanism of action of the complexes, molecular docking studies on modeled T. cruzi NADH-fumarate reductase (TcFR) predicted that both should be very good inhibitors of the enzyme. The effect of the compounds on the enzyme activity was experimentally confirmed and studied in detail using T. cruzi protein extracts. According to all obtained results, both [M(mpo)(dppf)](PF6) compounds could be considered promising anti-trypanosomal agents and leaders for further efforts in the design of better and more selective inhibitors against T. cruzi.

References: 1. Vieites, M; Gambino D. et alJ.Biol. Inorg. Chem.,2008, 723. ANII (POS_NAC_2013_1_11436 and INI_X_2013_1_101093), CSIC-UdelaR, CONICET, ANPCyT

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DEVELOPMENT OF NEW COMPLEXES AND THEIR PHOSPHATASES ACTIVITIES

Graciela Aparecida Dos Santos Silva, Carolina Croceta Bombazar, Ademir Neves, Rosely Aparecida Peralta

UFSC - University Federal Of Santa Catarina

Keywords: Biomimetic, Acid Purple Phosphatase, Complexes Heterobinuclear

The use of inorganic bioinspired models capable of catalytically hydrolyze nucleic acids is extremely important due to their potential uses in biotechnology. Several studies of the first coordination sphere of PAPs are already proposed and now attention has been focused to understand the fate of the second sphere of coordination in the catalysis.1-3 Two ligands (H2L1) H2pmeapymff and (H2L2) H2pmeapycbut were synthesized and characterized by IR, NMR 1H and by mass spectrometry that proved the obtaining and purity. Two heterodinuclear complexes with the [FeIII(μ-OH)ZnII] core were synthesized with each ligand. The complexes were characterized by IR (KBr), (in cm-1): ([FeIII(μ-OH)ZnII]L1) υ (OH) 3443; υ (C=N and C=C) 1604-1419; υ (C-O) 1264 and ([FeIII(μ-OH)ZnII]L2) υ (O-H) 3560; υ (N-H) 3480-3412; υ (C=N e C=C) 1642-1417; υ (C-N) 1226; υ (Cl-O) 1094. The electronic spectrum of the complex ([FeIII(μ-OH)ZnII]L1) shows two absorption bands at λmax = 513 nm (ε = 1971 L mol-1 cm-1) and at λmax = 363 nm (ε = 7636 L mol-1 cm-1), both attributed with a ligand to metal charge transfer band (LMCT)

phenolate→iron(III) pπ-dπ∗ and pπ-dσ∗ and ([FeIII(μ-OH)ZnII]L2) in λmax = 534 nm (ε = 2397 L mol-1 cm-1). The square wave of the complexes were analyzed at pH 6 showing a single process for ([FeIII(μ-OH)ZnII]L1) with E1/2 = -18.5 mV vs NHE and for ([FeIII(μ-OH)ZnII]L2) with E1/2 = -16 mV vs NHE, which can be attributed to the FeIIIZnII/FeIIZnII process. Kinetic studies of the hydrolysis of the substrate 2,4-BDNPP catalyzed by ([FeIII(μ-OH)ZnII]L1) showed the following kinetic parameters: Vmax 1.20x10-8 mol L s-1, kcat 2.5x10-4 s-1, KM 2.7x10-4 mol L-1, Kass = 366.30 L mol-1 and E = kcat/KM 0.0915 L mol-1 s-1.

References: 1. Muxel, A. et al, Inorganic Chemistry, v.53, 2014, 2943. 2. Piovezan, C. et al, Inorganic Chemistry, v.51, 2012, 6104. 3. Souza, B. et al, Inorganic Chemistry, v.52, 2013, 3594. CAPES, CNPQ, FAPERJ, USFC, CAPES-STINT, LABINC and INCT-CATÁLISE

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P28

NEW ORGANOMETALLIC IMINES DERIVED FROM 4-NITROTHIOPHENE WITH POTENTIAL ANTICHAGASIC ACTIVITY

Patricia Toro Sánchez 1, Rodrigo Arancibia González 2, Adalberto Hugo Klahn Oliva 1

1 PUCV - Patricia Toro, 2 UDEC - Rodrigo Arancibia, 3 PUCV - A. Hugo Klahn

Keywords: Cyrhretrenylimines, Ferrocenylimines, 4-nitro-thiophene, Crystallography, Antitrypanosomal activity

Chagas disease is still considered a neglected disease in Central and South America.1 Accordingly there is an urgent need for the development of new antichagasic compound.2,3 In the last few years, our research group have reported a series of organometallic imines compounds containig 5-nitroheterocyclic scaffold, as potential trypanocidal agents.4,5 Studies have demonstrated the existence of a relationship between electronic effects of the organometallic fragments, the potential reduction of the nitro group (E1/2) and the trypanocidal activities. Most of the literature related to nitroheterocyclic compounds deals with derivatives of 5-nitrofurane and in less proportion with 5-nitrothiophene counterpart. According to our literature search, we could not find any studies involving the modification of the heterocyclic moiety with regard to: i) the position of the nitro group in the pentagonal ring and/or ii) the functional group located at the position 2. In this context, our laboratory has developed a rational design of organometallic Schiff bases formed through condensanción reactions between nitrothiophene precursors substituted in position 4 (4-nitro-thiophene-2-carboxaldehyde and 4-nitro-thiophene-2-acetyl) and organometallic amines. In the present work, we would like to report the synthesis and characterization of cyrhetrenyl and ferrocenyl imines derived of 4-nitrothiophene. The characterization of all compounds were performed using spectroscopic techniques and two of them by X-ray crystallography. Studies on the trypanocidal evaluation of these compounds, are presently, under investigation.

REFERENCES 1. http://www.who.int/chagas/en/, June 2015. 2. Bot, C., et. al.; Antimicrob. Agents Chemother. 2013, 57, 1638. 3. Scalese, G., et. al.; J. Inorg. Biochem. 2015, 147, 116. 4. Arancibia, R., et. al.; J. Organomet. Chem. 2011, 696, 3238. 5. Arancibia, R., et. al.; J. Organomet. Chem. 2013, 743, 49. FONDECYT 1150601, CONICYT 21130293, D.I. PUCV

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P29

IN SILICO BIOLOGICAL PROPERTIES EVALUATIONS AND ANTIMICROBIAL ACTIVITY OF CU(II) COMPLEX WITH SCHIFF BASES

K. G Ospina 1, M.L.G. Oliveira 2, G.D. De Fatima 2, C.J. Viasus 4, A.E. Burgos 1

1 UNAL - Universidad Nacional De Colombia, Sede Bogotá, 2 UFMG - Universidade Federal De Minas Gerais, Belo Horizonte, Brazil, 4 U.D.C.A - Facultad De Ciencia Y

Tecnología, Universidad De Ciencias Ap

Keywords: Aryl-S-benzyldithiocarbazate, Cu(II) complexes, PASSonline, Antimicrobial activity, ChemMapper

In the present work is described the synthesis and characterization of the three new ligands, 3,4-methylenedioxybenzyl-S-benzyldithiocarbazate (L1), p-chloro-benzyl-S-benzyldithiocarbazate (L2) and 2,6-dichlorobenzyl-S-benzyldithiocarbazate (L3). These Schiff base type ligands were obtained by means of the reaction of 3,4-methylenedioxybenzaldehyde, p-chlorobenzaldehyde and 2,6-dichlorobenzaldehyde with S-benzyldithiocarbazate, at molar ratio 1:1. The respective Cu(II) complex obtained C1, C2 and C3 were synthesized reacting L1, L2 or L3, with CuCl2.2H2O, at molar ratio 1:1. The chemical characterization of ligands and complexes was performed through its FT-IR, UV-Vis, 1H NMR and EPR spectroscopic data. Through the spectral data was established that both in solid as in solution, ligands is in thione tautomer form.1,2. The ligand L1, L2 and L3 and their correspondent complexes C1, C2 and C3 were subjected to in vitro radial diffusion assays against the Gram-negative bacteria Escherichia coli and Gram-positive Staphylococcus aureus and the fungus Candida albicans and Saccharomyces cerevisiae, with good results found for some of these compounds. To complex C1 was attributed the major in vitro antimicrobial activity, with inhibition effect observed for all microorganism subjected to assays. Due to its promising antimicrobial property, the complex C1 was subjected to EPR analyses aiming to establish its conformational structure.3 The prediction of biological activities of ligands and complexes was evaluated through the in silico simulation using the PASSonline and ChemMapper web tools. The data were in accordance with experimental results. The activity was attributed mainly to the metal-ligand interaction and probably by the presence of two oxygen atoms in the structure of C1, commonly found in active compounds. The present results contribute to future studies involving correlation structure-activity relationship (QSAR) related to similar complexes.

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STRUCTURE ACTIVITY RELATIONSHIP OF PALLADIUM(II) COMPLEXES BEARING THIOSEMICARBAZONES

Fillipe Rocha 1, Nathália Thomazella 1, Matheus Zytkuewisz 1, Adriano Oliveira 2, Saulo Garrido 1, Iracilda Carlos 3, Francine Manente 3, Adelino Netto 1

1 IQ-ARAR/UNESP - Institute Of Chemistry, UNESP, Araraquara, 2 UFS - Federal University Of Sergipe, 3 FCFAR - Faculty Of Pharmaceutical Sciences, UNESP,

Araraquara

Keywords: Palladiu(II), Thiosemicarbazone, Cytotoxicity

Type II topoisomerases are a class of ubiquitous enzymes that alter DNA topology by catalyzing the passing of an intact DNA double helix through a transient double-stranded break made in a second helix1. Topoisomerase II is one of the targets of thiosemicarbazones (TSC) and their complexes and the presence of a metal ion, in general, increases the activity2. Therefore, in this work we presents the synthesis, characterization, cytotoxicity and topoisomerase II inhibition of four palladium complexes bearing thiosemicarbazones as ligand. Complexes of general formulae [PdCl(L)(PPh3)]Cl {L = (2E) -2 - [(2E)-3-phenyl-1-ylidene] hydrazinecarbothioamide [TSC_HH (1)]; N-Methyl-(2E) -2 - [(2E)-3-phenyl-1-ylidene] hydrazinecarbothioamide [TSC_HC (2)]; N-Methyl-2-(1-methyl-3-phenylprop-2- en-1-ylidene)hydrazinecarbothioamide [TSC_CC (3)]; N-Methyl-(E)-2-[4-(4-hydroxyphenyl)butan-2-ylidene]hydrazine-1- carbothioamide [TSC_OH (4)]} were synthesized and fully characterized by elemental analysis, conductivity, mass spectrometry, IR and NMR spectroscopies. The characterization data showed the coordination of TSC by a bidentade anionic mode through azomethinic nitrogen and sulfur atoms. Cytotoxicity of free TSC and their complexes were tested against MCF-7 cell line (human mammary adenocarcinoma). The results were compared with cisplatin3. Ligands were considered to be inactive, since they showed no drug response at concentrations 1-4 were more cytotoxic than cisplatin, highlighting 3 and 4 which are 13 and 26 times more effective than cisplatin, respectively. Agarose gel electrophoresis experiments were performed to verify the topoisomerese II inhibition activity of 1-4. Circular pBR322 plasmid DNA was incubated with topo II in the presence of different concentrations of compounds. Depending on the TSC bound to the metal, distinct potential to inhibit topo II was observed.

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P31

IN VITRO TRIPANOCIDAL ACTIVITY POTENTIAL OF CARBONYL TRINUCLEAR RUTHENIUM CARBOXILATES

Mariete Moreira, Zumira Carneiro, Sérgio De Albuquerque, Sofia Nikolaou

USP - Universidade De São Paulo

Keywords: Trinuclear Ruthenium Carboxilates, Carbon Monoxide , Tripanocidal Activity

Chagas disease is endemic in Latin America and it’s is caused by the parasite T. cruzi. According to the World Health Organization 1, 12 million people are infected with the T. cruzi. Clusters of general formula [Ru3O(CH3COO)6(CO)(L)2] (L = N-heterocyclic ligands) constitute an important class of compounds to be investigated.2,3. This study shows the synthesis, characterization and study of tripanicidal activity of the complex [Ru3O(CH3COO)6(CO)(dmap)2] (dmap = 2,6-dimethylaminopyridine). Compound was obtained by agitation of a solution containing [Ru3O(CH3COO)6(CO)(CH3OH)2] and dmap ligand in estequiometric ratio for 6 hours in methanol. In vibrational spectrum it has observed a strong band CO stretch characteristic, observed stretching of CO in 1927 cm-1. Electronic spectrum shows three bands at 589 nm (ε=6753 cm-1mol-1L), 394 nm (ε=7657 cm-1mol-1L) and 263 nm (ε=39989 cm-1mol-1L). Three quasi-reversible waves were observed at -1.12, + 0.50, and +1.10 V, which were tentatively assigned to the RuIIIRuIIIRuII/ RuIIIRuIIIRuIII, RuIIIRuIIIRuIII/ RuIVRuIIIRuIII and RuIVRuIIIRuIII/ RuIVRuIVRuIII redox couples, characteristic of the cluster. 1H NMR signals of hydrogens of the coordinated ligand exhibit a shift towards higher frequencies compared to the free ligand due deshielded effect that remove of the electron density of the ligand to the [Ru3O] unit. While the signals relative to methyl protons of the bridges acetate exhibit a shift towards lower frequencies compared to the free ligand, because shielding effect is consistent with an increase in the electron density of cluster. Studied complex trypanocidal effect similar to benzonidazole and devoid of cytotoxicity. Compound showed an IC50 at 62 µM. Data obtained for the complex confirm its structure and the biological testes suggests it is a promising candidate as tripanocidal agent. More studies are underway in order to improve the understanding of the biological activity of this complex.

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P32

SINTHESIS AND CHARACTERIZATION OF THE NOVEL COMPLEX [Cu2(μ-Cl)2(BENZEPA)2Cl4] AS A POSSIBLE FUNCTIONAL BIOMIMETIC OF CATECHOL

OXIDASE

Marcus Guimarães 1, Marciela Scarpellini 1, Roberto Amado 1, Jackson Resende 2

1 UFRJ - Universidade Federal Do Rio De Janeiro , 2 UFF - Universidade Federal Fluminense

Keywords: Copper complexes , Functional Biomimetic, Catechol Oxidase

Copper complexes have been used as structural and functional models for the active site of several enzymes, among them, catechol oxidase. This work reports on the synthesis and characterization of a new CuII complex with the ligand N-benzyl(2-ethylpyrid-2-yl)amine(benzepa). The ligand benzepa was synthesized reacting 2-(2-aminoethyl) pyridine with benzaldehyde in methanol, followed by reduction with NaBH4. After characterized by IR and 1H and 13C NMR, the ligand was treated with CuCl2●4H2O in ethanol yielding a precipitate that was successively recrystallized to obtain green single crystals of the complex[Cu2(μ-Cl)2(benzepa)2Cl2]. These crystals were characterized by single crystal X-ray diffraction,IR,UV-Vis and molar conductivity analysis. X-ray diffraction reveals that complex [Cu2(μ2-Cl)2(benzepa)2Cl4] is a binuclear with two copper centers connected by two µ-chloro bridges. Each copper is also coordinated to a benzepa molecule and a chloride ion. A tau(τ) value of 0.56 suggests distorted bipyramidal trigonal geometries for each one. Molar conductivity(µScm-1) analysis of [Cu2(μ2-Cl)2(benzepa)2Cl4] in methanol solution(10-3 mol L-1) was measured for 7 days in the following time intervals: 1h(78,5), 4h(82,5), 24h(86,9), 48h(93,5), 72h(96,7), 144h(240),168h(247). For the first three days, the measured values were in the 1:1 electrolyte range, suggesting that one of the chloride ions dissociated. After five days, an increase on measured values was observed (2:1 electrolyte range) accompanied by a change on the color of solution from green to yellow, suggesting the release of the second chloride ion. After seven days the electronic spectra of this solution was recorded, and a band at λmax 255 nm(ε = 20005L mol-1 cm-1) was observed. This band is assigned as an intraligand charge transfer process, and was also observed in a freshly prepared solution at λmax 258 nm(ε =18849 L mol-1 cm-1). The catecholase activity of the complex is under investigation and will be presented.

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P33

CYTOTOXICITY AND ANTIOXIDANT ACTIVITY OF RUTHENIUM COMPLEXES CONJUGATED WITH GALLIC ACID AND DERIVATIVES

Angelica Graminha 1, Marcia Cominetti 1, Alzir Batista 1, Rodrigo Correa 1,5, João Honorato 1, Antônio Menezes 3

1 UFSCAR- Dept. Of Gerontology, Federal University Of São Carlos , 2 UFSCAR - Dept. Of Chemistry Federal University Of São Carlos, 3 UNIANA - Dept. Of Chemistry - State

University Of Anápolis.

Keywords: Ruthenium Complexes , Gallic Acid, Cancer

It has been demonstrated in the literature that gallic acid has high cytotoxic activity against different tumor cell lines, but low cytotoxicity against normal cells. Moreover, ruthenium compounds have attracted increasing interest over the last years as potential antitumor drugs. Therefore, in this context we evaluated the biological properties of ruthenium complexes conjugated with phosphine/ bipyridine ligands, which showed promising results as potential antitumor agents. Here the complexes were synthesized from the cis-[RuCl2(bipy)(dppb)] or from the cis-[RuCl2(dppe)2] [dppb = 1,4-bis(diphenylphosphine) butane; dppe = 1,2-bis(diphenylphosphine)ethane], with benzoic acid (A), gallic acid (B) and modified gallic acid (C). The complexes were characterized by elementar analysis, 31P{1H} NMR, molar conductivity, absorption spectroscopy in the infrared and UV-Visible regions and cyclic voltammetry. The characterization showed the formation of complexes of type [Ru(O-O)(bipy)(dppb)]PF6 (1) and [Ru(O-O)(dppe)2]PF6 (2). Furthermore, MTT cell viability assays were carried out using three different cell lines, MDA-MB-231 and MCF-7 (breast cancer) and L929 (healthy cells from mice). Assays to measure the interaction of the complexes with bovine soroalbumine (BSA) protein were performed by spectroscopic titration fluorescence.Clonogenic assays were performed with MDA-MB-231 and L929 cells. It was observed that compounds 2A , 2B and 2C showed less interaction with BSA compared to compounds 1A , 1B and 1C with constant- interaction (Kb) of 107 and 105 (37.5 °C), respectively. Regarding the antioxidant activity only compounds containing gallic acid (1B and 2B) showed activity with values close the free ligand ones. Cytotoxicity assays showed that the complexes of the (2) series had IC50 values less than (1) series at different times (24, 48 and 72 hours) in both cell lines.

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P34

SYNTHESIS, CRYSTAL STRUCTURE, DNA AND BSA BINDING STUDIES AND ANTICANCER ACTIVITY OF BIPHOSPHINE RUTHENIUM(II) COMPLEXES WITH 2-

MERCAPTOPYRIMIDINE

Luciano Rodrigues Pereira 1, Fábio Batista Do Nascimento 1, Kátia Mara Oliveira 1, Gregory Ferreira Grawe 1, Victor Marcelo Deflon 2, Alzir Azevedo Batista 1

1 UFSCAR - Universidade Federal De São Carlos, 2 USP - Universidade De São Paulo

Keywords: Ruthenium(II) Complexes, Anticancer Activity , 2-Mercaptopyrimidine

In vitro study is the first step in potential metallodrugs development. The interaction of drugs with DNA is a significant feature in pharmacology and plays a vital role in the determination of the mechanism of drug action. Likewise, the binding of a drug to a carrier proteins, like albumin, is a major determinant of its pharmacokinetic and pharmacodynamic profile. In this work we synthetized three new ruthenium complexes, [Ru(dppm)2(N-S)]PF6 (1), [Ru(dppe)2(N-S)]PF6 (2) and [Ru(dppp)(N-S)2] (3) [dppm = 1,1-bis(diphenylphosphino)methane, dppe = 1,2-bis(diphenylphosphino)ethane, dppp = 1,3-bis(diphenylphosphino)propane and N-S = 2-mercaptopyrimidine] aiming the evaluation of the influence of the diphenylphosphine in cytotoxic activity of the complexes against cancer cells. The complexes were characterized by spectroscopic techniques, molar conductance, elemental analysis, electrochemical techniques and X-ray diffraction. The DNA binding studies has been investigated using voltammetric and spectroscopic techniques. The results show that all complexes exhibits a weak interaction with DNA. The BSA interaction with all complexes were studied using fluorescence emission spectroscopy, where the results indicate a spontaneous interaction by static quenching mechanism. The cytotoxicity of the complexes has been evaluated against A549, MDA-MB-231 and V79 cells by MTT colorimetric assay. The IC50 values were from 0.055 to 0.24 µmolL-1 for complexes (1) and (2), showing better results comparing with cisplatin (2,43 to 11.54 µmolL-1). For the complex (3) at the maximum concentration investigated, 6.0 µmolL-1, no activity was observed. The diphosphines show an important role, as auxiliary ligands, in the cytotoxic activity of the complexes. The number of phosphine coordinate to the metal center is decisive to the cytotoxicity of the new compounds.

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P35

RUTHENIUM COMPLEXES CONTAINING LAPACHOL AND LAWSONE, AS CYTOTOXIC AGENTS

Katia Mara Oliveira 1, Márcia Regina Cominetti 2, Alzir Azevedo Batista 1

1 UFSCAR - Dept Of Chemistry, Federal University Of São Carlos, 2 UFSCAR - Dept Of Gerontology, Federal University Of São Carlos

Keywords: Ruthenium Complexes, Lapachol, Lawsone, Cancer

Complexes containing ligands of biological interest have relevance in the field of development of new metal-based drugs. Lapachol (2-hydroxy-3-(3-methyl-2-butenyl)-1,4-naphthoquinone) and lawsone (2-hydroxy-1,4-naphthoquinone) are two natural products of interest, because they exhibit a large range of biological activities, such as antitumor, antimalarial and antiprotozoal1,2. New lapachol and lawsone ruthenium complexes, with formula [Ru(lap)(P-P)(bipy)]PF6 and [Ru(law)(P-P)(bipy)]PF6 (lap = lapachol; law = lawsone; P-P = dppf = 1,1’-bis(diphenylphosphino)ferrocene or = dppb = 1,4-bis(diphenylphosphino)butane; bipy = 2,2’-bipyridine), were synthesized, and characterized by various spectroscopy techniques. The in vitro cytotoxicity of the ligands lap, law and of the complexes on two human tumor cells lines (DU-145 and MDA-MB-231) demonstrated lower IC50 values (ranging from 0.045 to 0.56 µM), in than for the reference metallodrug, cisplatin (2.00 and 2.43 µM, respectively).The complexes containing lap and law showed more efficiency for colony formation inhibition and migration of MDA-MB-231 tumor cells, than the free lap and law. The interaction of the complexes with ct-DNA (calf-thymus) was studied by UV-Vis absorption and circular dichroism (CD), and it was possible to verify that the ruthenium complexes interact weakly with calf-thymus ct-DNA, resulting in binding constants of 102-103 M-1.The interaction of the complexes with bovine serum albumin (BSA) protein was investigated at different temperatures. The binding constants (Kb) of the complexes with BSA presented magnitude of 105 M-1. Furthermore, negative values of ΔH° and positive values of ΔS° were obtained, indicating that the interaction between the complexes and BSA was mainly of electrostatic character.

References:

1. Fonseca, S. G. C.; Braga, R. M. C.; Santana, D. P. Rev. Bras. Farm., 2003, 84, 9. FAPESP (Proc. Nº 2014/04147-9), CNPQ,CAPES

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P36

RUTHENIUM COMPLEXES ENDOWING POTENT ANTICANCER AND ANTITUBERCULOSIS ACTIVITIES

Adriana Guedes 1, Gregory Grawe 1, Rodrigo Corrêa 1, Victor Deflon 2, Fernando Pavan 3, Alzir Batista 1

1 UFSCAR - Federal University Of São Carlos, 2 USP - University Of São Paulo, 3 UNESP - University State São Paulo

Keywords: Ruthenium Complexes, Biological Activity, Biomolecule Interactions

Ruthenium complexes attract considerable interest from researchers because some of them present good activity against various types of cancer. Moreover, the interactions of ruthenium (II) complexes with various biological systems have also been studied to understand their potential antitumor behavior. It is known that several complexes containing imidazoline and thiazoline-thione show antibacterial, antifungal and anticancer activity. Thus, our work involves ruthenium(II) complexes containing thio-derivatives ligands associated with the NH-C=S coordined moiety, aiming the evaluation of their antitumor and antimycobacterial properties. In this study, the complexes [Ru(L)(bipy)(dppf)]PF6 (dppf=1,1''-bis(diphenylphosphino)ferrocene, L=2-mercaptothiazoline, 2-mercapto-1-methyl-imidazole, imidazole or 6-methyl-2-thiouracil, were obtained and characterized by phisical and spectoscopic techniques. The interaction of the complexes with calf thymus DNA (CT-DNA) has been explored by using electronic absorption titration, viscosity measurements and square-wave voltammetry technique. The experimental results show that the binding of the complexes with CT-DNA is non-covalent, with weak electrostatic interactions. The interaction of complexes with HSA (human serum albumin) has also been studied using fluorescent quenching method. The experimental results show that the complexes exert high affinity with HSA, with Kb values of the order of magnitude 106 at 37ºC. In vitro evaluation of the complexes, using the MTT assay against prostate cancer (DU-145) and breast cancer (MCF-7) tumour cells, revealed their cytotoxic activities in a range of 2.5–6.1µM and 4.7–7.1µM, respectively. The antimycobacterial activities of the complexes for MTB cell, by the REMA method. The MIC for these complexes were found to be between 0.74 and 2.0 µg/mL.

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P37

ANTIPARASITIC AND ANTITUMOR ACTIVITY OF CLOTRIMAZOLE AND KETOCONAZOLE-TRIPHENYLPHOSPHINE-η6-P-CYMENE RU(II) COMPLEXES

Legna Colina-Vegas 1, Maribel Navarro 2, Joseane Godinho 3, C Scapin 3, Juliany Rodrigues 3, Phercyles Veiga-Santos 3, Wanderley Souza 3, Alzir Batista 1

1 UFSCAR - Chemistry Departament, Federal University Of São Carlos, 2 INMETRO - Nacional Institute Of Metereology, Quality And Tecnology, 3 UFRJ - Universidade Federal

Do Rio De Janeiro

Keywords: Ruthenium complexes, Cetoconazole, Clotrimazole, T.Cruzi, L. amazonensis

The development of efficacious agents against cancer and parasities diseases is critical, since these illnesses afflict millions of people in the world1. Two complexes with general formula [Ru(η6-p-cymene)(PPh3)(X)Cl]PF6, where X: clotrimazole (1) or ketoconazole (2) were synthesized and characterized by physical and spectroscopics tecnhiques. The activity of both metal complexes were evaluated against proliferative and infective stages of T. cruzi, L. amazonensis and tumor cells lines: MDA-MB-231 and DU-145, cultured in vitro. The compounds 1 and 2 inhibited the proliferation of epimastigote forms with IC50 values of 0.3 μM and 0.8 μM, respectively. The compounds also inhibited the proliferation of intracellular amastigotes in cultured LLC-MK2 cell lines , with IC50 values (96 h of exposure) <0.50μM, however compound 2 was more potent reducing the cell viability in 100% in concentrations >0.50 μM.The compounds exhibt growth inhibition on the human tumor cells lines with IC50 values of 0.60 μM, where its activity is bigger than those shown by the free ligands and reference drugs (cisplatin and doxorubicin), under the same experimental conditions.Taken together, our observations show that these organometallics complexes are promising selective inhibitors of T. cruzi and Leishmania proliferation, however new and profound studies are necessary to understand the mechanisms of action and the in vivo efficacy.

References:

1. http://www.who.int/gho/neglected_diseases/en

CAPES, CNPQ, FAPESP

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P38

CHIRAL PHOSPHINE-CHLOROQUINE PLATINUM(II) COMPLEXES AS ANTIMALARIAL AGENTS

Wilmer Villarreal 1, Taís Soares Macedo 2, Diogo Magalhaes Moreira 2, Milena Pereira Soares 2, Maribel Navarro 3, Alzir Azevedo Batista 1

1 UFSCAR - Universidade Federal De Sao Carlos, 2 FIOCRUZ - Gonçalo Moniz Research Center, 3 INMETRO - Nacional Institute Of Metereology, Quality And Tecnology

Keywords: Platinum complexes, Chloroquine complexes, Antimalarial agents, Fe(III)PPIX interactions, Chiral complexes

Malaria is a tropical disease with high rates of morbidity and mortality, affecting more than 500 million people worldwide, resulting in 1-3 million deaths each year. The reasons for the current severity of the malaria problem are multifaceted, the most notable in this regard is parasite resistance to chloroquine, which is now almost universal1. The most widely accepted mechanism of action of the successful antimalarial drugs e.g. chloroquine is the inhibition of the formation of hemozoin crystal. In view of this, we have developed strategies based on the structural modification of chloroquine, through the incorporation of transition metals into its molecular structure2. We present here the antimalarial activity and Fe(III)PPIX interaction studies of four phosphine chloroquine platinum (II) complexes with general formula [PtCl(CQ)(P2)]PF6, where CQ= Chloroquine and (P)2= triphenylphosphine (PPh3)(1),1,3-bis(diphenylphosphine)propane(dppp)(2), 1,4-bis(diphenylphosphine)butane (dppb) (3) and 1,1'-bis(diphenylphosphine)ferrocene (dppf) (4). The transformation of hemin to β-hematin in acidic acetate solutions was studied using IR spectroscopy, where all the platinum complexes inhibited the formation of β-hematin, showing the same behavior of the chloroquine, indicating that the mechanism of action was not modified after the coordination of CQ to Pt(II) center. The spectronic titrations with Fe(III)PPIX showed that the compounds exhibited interaction constant similar or greater than that one displayed by chloroquine and other antimalaric metal complexes2. The antimalarial activity of the complexes was determinated in the erythrocytic form of W2 and 3D7 strains of P. falciparum, while host cell cytotoxicity was examined in HepG2 cell. Except complex 3, the compounds were 2 to 3 more potent and selective than metal-free chloroquine. In addition, it was examined the complex 2 on the parasite cell cycle development, resulting arrested and exhibited parasiticidal effects

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P39

CYTOTOXIC ACTIVITY OF RU(II)/PHOSPHINE/2,2’-DIPYRIDILAMINE/DIIMINES COMPLEXES

Gabriel Ribeiro 1, Gregory Grawe 1, Legna Vegas 1, Juan Clavijo 2, Javier Ellena 2, Alzir Batista 1

1 UFSCAR - Dept. Of Chemistry, Federal University Of São Carlos, 2 USP - Institute Of Physics, University Of São Paulo

Keywords: Ruthenium, Cytotoxicity, Metal Complexes, Diimines

A series of mixed ligand ruthenium(II) complexes with general formula [RuCl(PPh3)(Hdpa)(diimine)]Cl 1-5 (PPh3 = triphenyphosphine, Hdpa = 2,2’-dipyridylamine and diimine = Hdpa (1), 2,2’-bipyridine (bipy, 2), 5,5’-dimethyl-2,2’-bipyridine (dmbipy, 3), 1,10-phenanthroline (phen, 4), 4,7- diphenyl-1,10-phenantholine (diphen, 5) have been synthesized and characterized by analytical and spectroscopic techniques. The complexes have been structurally characterized and the coordination geometry around Ru(II) is described as distorted octahedral. The interaction of the complexes with calf thymus (CT) DNA has been investigated by absorption and emission spectroscopy and viscosity measurement. The binding mode of the complexes (1-4) with ct-DNA is reversible, predominating electrostatic interactions, probably between the negative DNA phosphate groups and the positively charged complexes. However, the complex (5) showed a different mode of interaction compared to the other complexes. Circular dichroism spectroscopy studies reveal that the complex 5 causes significant change in the secondary conformation of ct-DNA and in the DNA superhelicity upon binding with supercoiled ptz57RT DNA. Further, the cytotoxicity of the complexes against breast adenocarcinoma cell line (MDA-MB-231) has been investigated. All the complexes showed good cytotoxicity, with IC50 values in the range of 5.65-1.65 μmolL-1. Interestingly, complex (5) exhibits values IC50 lower than the other complexes (1.65 ± 0.05 μmolL-1) and approximately 2 times less than cisplatin (2.4 ± 0.2 μmolL-1). The low IC50 values for all complexes shows that the –NH– group in the primary Hdpa ligand and in the diimines ligands contributes significantly to the cytotoxicity of the complexes and to the ct-DNA binding.

83

P40

CYTOTOXYCITY OF CARBONYL-HETEROBIMETALLIC RU(II)/FE(II) COMPLEXES

María-José Dávila-Rodríguez 1, João Barolli 1, Gregory Grawe 1, Katia De Oliveira 1, Fabio Miranda 2, Alzir Batista 1

1 UFSCAR - Federal University Of São Carlos, 2 UFF - Fluminense Federal University

Keywords: Ruthenium, 1,1'-Bis(diphenylphosphino)ferrocene, Cytotoxic activity , Intercalator agent, DNA

Chemotherapy is a regular and accessible cancer treatment. Although there over 100 chemotherapeutic agents available, their side-effects and acquired resistance drive the development of better drugs. Metal-based drugs offer one of the more plausible options.1 This study examines the in-vitro interaction with calf thymus DNA (ctDNA) and bovine serum albumin (BSA), and determined the cytotoxic activity (IC50) of the synthesized carbonyl-heterobimetallic Ru(II)/Fe(II) complexes ct-[RuCl(CO)(dpq)(dppf)] (1), ct-[RuCl(CO)(dppz)(dppf)]PF6 (2) and ct-[RuCl(CO)(dpqQX)(dppf)]PF6 (3) [dpq = dipyrido[3,2-f:2′,3′-h]-quinoxaline; dppz = dipyrido[3,2-a:2',3'-c] phenazine; dpqQX = quinoxalino[2',3':5,6] pyrazino[2,3-f][1,10] phenanthroline and dppf = 1,1’-bis(diphenylphosphino)ferrocene)]. The complexes were designed as DNA intercalators agents. UV-Vis absorption spectroscopy, squarewave voltammetry and viscosity measurements validated the intercalation ability of 1 and 2 with DNA.2 Fluorescence shows strong and spontaneous interactions of 1, 2 and 3 with BSA,3 resulting in binding constants in the order of 105 - 106 M-1. MTT assays in cell line MDA-MB-231 revealed IC50 values at range of 800 – 1110 nM. After these results, future trials will be necessary to explore in-vitro interactions of the complexes with other biomolecules like topoisomerases and evaluate cytotoxicity activity of the complexes against other cell lines and to test them in-vivo.

References: 1. Beraldo, H. Ciência E Cultura. 2011, 63, 29. 2. Sirajuddin, M.; Ali, S.; Badshah, A. J Photoch Photobio B. 2013, 124, 1. 3. Xue, F.; Xie, C.Z.; Zhang, Y.W.; Qiao, Z.; Qiao, X.; Xu, J. Y.; Yan. S.P. Inorg. Biochem. 2012, 115, 78. CAPES/PROEX, FAPERJ, FAPESP. J.P. Barolli acknowledges to FAPESP (Process: 2013/21611-8).

84

P41

CYTOTOXICITY OF RU (II)/ AMINO ACIDS COMPLEXES AND THEIR INTERACTIONS WITH BIOMOLECULES

Celisnolia Leite, Legna Vegas, Alzir Batista

UFSCAR - Federal University Of São Carlos

Keywords: Ruthenium (II) Complexes, Amino Acids, Cytotoxicity, BSA, DNA

The complexes new, [Ru(L-Cysteine)(dppb)(bipy)](PF6) (1), [Ru(D-Penicillamine)(dppb)(bipy)](PF6) (2) and [Ru(L-Deoxyalliin)(dppb)(bipy)](PF6) (3) were synthesized and characterized by elemental analysis, 31P and 13C NMR, UV-visible and IR spectroscopy, cyclic and differential pulse voltammetry and molar conductivity. The cytotoxicity of the complexes, against tumor cells were evaluated. All three complexes form two different conformational isomers, showed by 31P{1H} NMR analysis1. The cytotoxicity of the complexes, against tumor cells MCF-7 showed values between 10 and 30 µM. The interaction ability of the complexes with the biomolecules BSA and DNA were investigated. The binding constants (Kb) obtained by UV-visible spectroscopy are in the order 104, suggesting weak interactions of the complexes with DNA. Measurements of the viscosity of solutions DNA incubated with different concentrations of the compounds confirmed this interaction. In the study of the interaction of the complexes with BSA, at different temperatures, was observed decrease in the intrinsic fluorescence of BSA, with increasing concentration of the compounds, showing that the binding complex-BSA may change the protein conformation, subunit association or denaturation, leading to changes in the tryptophan environment of BSA. The Kq (L mol-1 s-1) values are in the order 1012 for all three compounds, indicating the existence of static quenching mechanism. Increasing the temperature, the bond strength complex-BSA increases as shown the Kb (mol L-1), with exception of compound (3), values (1): 1,60 x 104 (25°C); 1,90 x 104 (37°C), (2): 4,42 x 104 (25°C); 5,45 x 104 (37°C) and (3): 5,05 x 104 (25°C); 4,71 x 104 (37°C). The thermodynamic parameters suggest that hydrophobic forces played a major role in the binding of the ruthenium complexes and BSA. The processes of binding are spontaneous, in which Gibbs free energy is negative2.

85

P42

NEW COMPLEXES OF THE TYPE [RhCl(COD)L], L= PYRIDYL-CHALCONES OR PYRIDYL-INDOLINONES

Esperanza Galarza1*, Gala de la Vega1, Fernando Cuenú2

1Departamento de Química, Universidad del Valle, Cali - Colombia; 2 Laboratory of Inorganic Chemistry and Catalysis, Chemistry Program, Faculty of Basic Sciences

and Technologies, University of Quindio, Armenia - Colombia

In this work we report the synthesis of pyridyl-chalcones, pyridyl indolinones and the corresponding complexes of type [RhCl(ƞ4-1,5-COD)(N-het)], where N-Het are the pyridyl-chalcones (E)-1-(2-aminophenyl)-3-(pyridin-4-yl)prop-2-en-1-one (1); ((E)-1-(6-amino-1,3-benzodioxole-5-yl)-3-pyridin-4-yl)prop-2-en-1-one (2); (E)-1-(2-aminophenyl)-3-(pyridin-2-yl)prop-2-en-1-one (3); (E)-1-(6-amino-1,3-benzodioxol-5-yl)-3-pyridin-2-ylprop-2-en-1-one (4); or pyridyl-indolinones: (Z)-2-((pyridin-4-yl) methylene)-[1,3]dioxolo[4,5-f]-indolin-3-one (5); (Z)-2-((pyridin-2-yl)methylene)-[1,3] dioxolo[4,5-f]-indolin-3-one (6) and 4-terbutilpiridine (7). The spectroscopic data and elemental analyzes are consistent with the coordination of one ligand (pyridyl-chalcones or pyridyl-indolinones) through the pyridine nitrogen, which is corroborated by single crystal X-ray analysis. These complexes have been tested as precatalysts for the hydroformylation of naturally occuring arylpropenes. References:

1. A. Cruz, A. Sánchez, A. García, F. Cuenú, C. Rozo .J. Mol. Struct., 98, 2015,216-218.

Vicerrectoria de Investigaciones de la Universidad del Quindio -project 608

86

P43

SYNTHESIS, CHARACTERIZATION AND LEISHMANICIDAL ACTIVITY OF AN AMINOMETHYLNAPHTHOQUINONE (ANQ-PY-DEC) AND ITS COBALT(III) COMPLEX

Maria Oliveira 1,2, Marciela Scarpellini 1, Maria Vargas 4, Jackson Resende 4, Carolina Teles 3, Ana Santos 3

1 UFRJ - Universidade Federal Do Rio De Janeiro, 2 IFRO - Instituto Federal De Rondônia, 3 FIOCRUZ - RO - Fundação Oswaldo Cruz - Rondônia, 4 UFF - Universidade Federal

Fluminense

Keywords: Naphthoquinones, Co(III) complexes , leishmanicidal activity

Naphthoquinones are known to present a wide range of biological activities, such as anti-cancer, leishmanicidal and antimalarial.1-4 Our aim is the investigation of Co(III) complexes of tridentate aminomethylnaphthoquinones (ANQHs), which may act as leishmanicidal agents. The synthesis and characterization of one proligand (ANQH-py-Dec = [N-(n-decyl)aminopyridyl]-2-hydroxy-1,4-naphthoquinone) and of its cobalt complex, [Co(ANQ-py-Dec)2]Cl, are presented herein. The complex was obtained from the reaction of ANQH-Py-Dec and CoCl2•6H2O, and isolated as brown single crystals. 1H NMR and IV spectroscopies were used to characterize both the proligand and the complex. Elemental analysis indicated a Co:ANQ ratio of 1:2, confirmed by an X-ray diffraction study. In dimethylformamide (DMF), the complex presented a 1:1 electrolyte type behaviour (140 ohm-1cm2mol-1). The UV-Vis spectrum (DMF) of the complex shows bands attributed to LMCT (λmax 445, ε= 5890 mol-1Lcm-1) and ILCT (λmax 275, ε= 55708 mol-1Lcm-1). The proligand exhibited better leishmanicidal activity against promastigotes of L. amazonensis (0.038 μmol.mL-1) than the complex (0.067 μmol.mL-1). Cytotoxicity assays on macrophage cell line J774 revealed less toxicity of the proligand (MLD50 = 0.038 μmol.mL-1) than the complex (MLD50 = 0.019 μmol mL-1) after 72 hours. The proligand also provided satisfactory results on the antileishmanial activity test and results will be presented.

References:

1. NEVES, A. et al. J. Braz. Chem. Soc., Vol. 20, No. 4, 712-727, 2009. 2. BENITES, J. et al. European Journal of Medicinal Chemistry 45 (2010) 6052-6057. 3. SILVA, M. et al. J. Braz. Chem. Soc., Vol. 24, No. 9, 1420-1426, 2013. 4. BUSTAMANTE, F. L. S. et al. Journal of Inorganic Biochemistry 132 (2014) 37–44. CNPq, CAPES, FAPERJ, PRONEX2010, PGQu

87

P44

THE EFFECT OF RIGID AND FLEXIBLE LIGANDS ON THE CONSTRUCTION OF COORDINATION NETWORKS

C. R. M. O. Matos, V. Martins and C.M. Ronconi*

Supramolecular Chemistry and Nanotechnology Laboratory, Department of Inorganic Chemistry Fluminense Federal University, Outeiro São João Batista, s/n, Campus do

Valonguinho, Niterói, 24020-141, RJ, Brazil Coordination Networks (CNs) are obtained by the rational choice of building blocks (ligands and metals).1 Rigid ligands facilitate the control of structures and properties in CNs. However, flexible ligands have conformational freedom, which leads to unique architectures. To study the effect of ligands, we synthesized CNs based on the rigid 4,4'-ethynylenedibenzoic acid (H2edb) ligand and Cd2+, Co2+, Er3+, Gd3+. We also synthesized CNs based on Ag+ and flexible dicyanomethylene ligands, containing variable spacer lengths and types.2 Structural analyses showed a variety of structures for Ag+ CNs. Most of the dicyanomethylene ligands had their flexible spacer conformation changed due to the coordination to the Ag+ center. Topological studies showed that the connectivity of the networks is strongly affected by the coordination modes of Ag+ ions. Because of the flexibility of the Ag+ coordination sphere, a variety of geometries around the Ag+ were observed, resulting in multinuclear networks. The reaction between the rigid ligand H2edb and Co2+, Cd2+, Er3+, and Gd3+ resulted, respectively, in 1D, 2D and 3D CNs, based on secondary units with intrinsic geometries. Because of the rigidity of the ligand, the dimensionality and topology of the networks were affected mainly by the secondary units, which dictated the extensions and growth of the frameworks. In conclusion, flexible ligands can adopt unpredictable conformations and coordination geometries that influence the topologies and frameworks as well as the coordination metal sphere leading to particular structures. In contrast, the rigid ligand limits the growth of the framework mainly due to the secondary units formed.

1. Kitagawa, S.; Kitaura, R.; Noro, S.-I. Angew. Chem. Int. 2004, 43, 2334. 2. Matos, C. R. M. O.; Miranda, F. S.; Carneiro, J. W. M.; Pinheiro, C. B.; Ronconi C. M. Phys. Chem.

Chem. Phys. 2013, 15, 13013.

CAPES, CNPQ, FAPERJ

88

AUTHOR INDEX TRACK 1

Afzal, M. IL9

Alamo, M. F. OC7

Amado, R. P32

Anacona, J. R. P8

Araki, K. IL3

Arancibia, R. P18

Araujo, M. P10

Arce, E. R. P26

Atria, A. M. P4

Baader, S. IL1

Baggio, R. P4

Barbosa, R. S. P13

Barolli, J. P40

Barros, W. P11

Bartlett, S. IL1

Batinic-Haberle, I. IL12

SL4

Batista, A. SL5

P33

P36

P37

P39

P40

P41

. P34

P35

P38

Batista, R. C. P24

Beraldo, H. IL6

P14

P19

Beyer, L. P20

Bhat, S. IL10

Biazotto, J. C. P5

P7

Bombazar, C. C. P27

Borba-Santos, L. P. SL5

Brito, H. A. P1

Broicher, C. IL14

Buccella, D. IL9

Bueno-Janice, J.C. SL4

Burgos, A.E. P29

Bustamante, J. P8

Cadenbach, T. OC12

Camargo, T. P22

OC11

Cano, J. OC4

Carlos, I. P30

Carneiro, Z. P31

Carrasco, F. P20

Cassaro, R. A. IL4

Castelli, S. P14

Castillo, I. SL9

Cebrián-Torrejón, G. P3

P24

Chaves, C. OC11

Chilton, N.F. OC5

Clavijo, J. P39

Coitiño, L. P26

Cole-Hamilton, D. J IL1

Colina, L. SL5

Colina-Vegas, L. P37

Cominetti, M. P33

P35

Contel, M. SL7

Correa, R. P33

89

P36

Corsini, G. P4

Costa, N. J. S. IL14

Costas, M. IL10

Cuenú, F. P42

da Cruz, A. G. B. P1

da Fonseca, M.G. SL4

da Silva, C. P. P1

da Silva, F. C. SL10

da Silva, J. P14

da Silva, J. G. P19

da Silva, R. S. P5

P7

SL2

Das, B. IL10

Dávila-Rodríguez, M. J. P40

de Albuquerque, S. P31

de Camargo, T. P. P25

de Fatima, G. D. P29

de la Vega, G. P42

de Mello, M. V. P. P3

P24

de Oliveira, K. P40

de Santana, R. C. OC1

de Souza, I. C. A. P2

de Souza, V. S. P12

de Souza, W. SL5

Deflon, V. M. P36

P34

SL8

Demicheli, C. OC9

Desideri, A. P14

do Nascimento, F. B. P7

P34

do Nascimento, G. P11

do Pim, W. P10

P11

do Prado, B. H. R. OC9

Doctorovich, F. IL5

Dupont, J. P12

Echeverría, G. P26

Edwards, P. SL6

Eguía, B. N. S. OC2

Ellena, J. P39

Escudero, G. P17

Escudero, R. OC7

Fagundes, E. M. S. P19

Falcão, N.K.S.M. SL4

Faria, R. B. SL10

Faro, L. P23

Ferraudi, G. P6

Ferreira, A. M. C IL11

Ferrer, E. P17

Fiedler, H. D. IL13

Fierro-Huerta, A. P21

Filho, L. F. O. B. P13

Fragoso, W.D. SL4

Franz, K.J. IL7

Frézard, F. OC9

Fuentealba, P. OC1

Furst, M. IL1

Gabriel, P. OC10

Gagini, T. SL5

Galarza, E. P42

Gambino, D. P26

Garcia, R. D. IL1

Garrido, S. P30

Godinho, J. P37

Godoy, F. P21

Gomes, P.T. IL15

90

Gomez, J. A. G. OC8

Gonzaga, D. P23

SL10

González, R. A. P28

Gorritti, W. R. H. P20

Graminha, A. P33

Grawe, G. P36

P39

P40

P34

Gruskos, J. IL9

Guedes, A. P36

Guedes, G. P. P1

Guerrero, J. P6

Guimarães, M. P32

Herrera, B. L. R. OC7

Heying, R. P15

Higuera, A. SL5

Homrich, A. P22

Honorato, J. P33

Idemori, Y.M. SL4

Islam, A. OC9

Jori, K. P17

Jori, N. P17

Julis, J. IL1

Julve, M. OC4

Klahn, H. P18

Kremer, L. P18

Laino, C. P17

Lanza, J. S. OC9

Lanznaster, M. P2

P3

P23

P24

Lappin, A. G. P6

le Goff, R. IL1

le Lagadec, R. SL3

Leite, C. P41

Lemus, L. P6

Levin, P. P6

Liddle, S.T. OC5

Lin, Q. IL9

Lloret, F. OC4

Lopes, N. P. OC8

Love, J. B. OC12

Luke, W. OC6

Macedo, T. S. P38

Machado, F. C. SL11

Magon, C. J. OC1

Maia, C.G.C. SL4

Malinkin, S. IL10

Manente, F. P30

Manzur, J. OC1

P20

Maresca, N. P17

Marín, E.R. SL9

Martini, N. P17

Martins, V. P44

Matos, C. R. M. O. P44

Matos, R. R. SL10

Máximo, L. N. C. P5

McInnes, E.J.L. OC5

Melo, A.C.C. OC10

Menezes, A. P33

Merlino, A. P26

Mgani, Q. IL1

Mgaya, J. IL1

Miranda, F. P23

P40

OC8

91

Mireski, S. P25

Mitra, M. IL10

Mmongoyo, J. IL1

Mondragón, A. SL9

Moreira, D. M. P38

Moreira, M. P31

Mosquillo, F. P26

Muñoz-Osses, M. P21

Murgida, D. IL8

Nathan, P. OC6

Navarro, M. SL5

P37

P38

Netto, A. P30

Neves, A IL2

OC11

P15

P22

P25

P27

Niebieskikwiat, D. P9

Nikolaou, S. P31

Nome, F. IL13

Nordlander, E. IL10

Novak, M. A. IL4

Nunes, K.J.R.C. OC10

Oliva, A. H. K. P28

Oliveira, A. P30

Oliveira, A. A. P19

Oliveira, K. M. P34

P35

Oliveira, M. P43

Oliveira, M. L. G. P29

Oliveira, W. X. C. OC4

Oliver, A. P6

Orio, M. OC2

Orzari, A. R. P7

Ospina, K. G. P29

Otero, L. P26

Pankhurst, J. R. OC12

Parada, J. P4

Paredes-Garcia, V. OC1

Parrilha, G. P14

Pavan, F. P36

Peralta, R. OC11

P22

. P27

Perdigão, G. M. C. P19

Pereira, C. P10

P11

P22

Pereira, C. I. M. OC4

Pereira, L. R. P34

Pereira, M. D. P16

Pereira-Maia E.C. OC10

Pérez, D. E. P6

Pérez, I. C. OC2

Pérez, L. P26

Peruzzini, M. IL16

Philippot, K. IL14

Pinheiro, C. B. OC4

Pinto, V.H.A. SL4

Pinto-Pacheco, B. IL9

Pires, A. B. P25

Pires, B. M. SL10

Piro, O. P26

Pitteloud, J. IL9

Quintana, C. P18

Ramírez, J. R. A. P9

Ramos, J. P14

92

Ramos, L. C. B. P7

Rebouças, J.S. SL4

Resende, J. P32

P43

Resende, J. A. L. C. SL10

P2

P23

Ribeiro, G. P39

Ribeiro-Santos, T. P10

Rico, H. SL3

Rios, R. R. P16

Rocha, F. P30

Rocha, W. R. OC3

Rodrigues, B. L. OC9

OC10

Rodrigues, J. P37

Rodrigues, L. E. P19

Romero, M. P8

Ronconi, C.M. SL1

P44

Rossi, L. M. IL14

Rozental, S. SL5

Rubim, V. OC9

Sâmia, L P14

Sánchez, P. T. P28

Santana, J.M.S.V.P. OC10

Santos, A. P43

Sarmento-Neto, J.F. SL4

Scapin, C. P37

Scarpellini, M. SL10

P16

P32

P43

Scholten, J. D. P12

Silva Jr, H. C. P1

Silva, F. P23

Silva, G. A. S. P27

Silva, I. P11

Silva, I. D. A. OC1

Soares, M. P. P38

Souza, F. D. IL13

Souza, W. P37

Souza-Fagundes, E. P14

Spasojevic, I. IL12

SL4

Spodine, E. OC1

P20

Stumpf, H. P11

Takahashi, J. A. P13

Teixeira, A. P11

Teixeira, I. P11

Teixeira, L. R. S. P13

Teles, C. P43

Terenzi, H. OC10

Thomazella, N. P30

Torres, M. E. S OC7

Toscano, R. A. OC7

Tovmasyan, A. IL12

SL4

Tuna, F. OC5

Uzuelli, J. A. P7

Vaisberg, A. P20

Vargas, M. P43

Vargas, M. D. OC8

Vaz, M. G. F. IL4

Vegas, L. P39

P41

Veiga-Santos, P. P37

Venegas-Yazigi, D. OC1

Viasus, C.J. P29

93

Villacis, J. I. C. P8

P9

Villarreal, W. SL5

P38

Visbal, G. SL5

Viteri, K. V. P. P9

Vono, L. L. R. IL14

Williams, P. P17

Wink, D. A. P7

Zhang, G. IL9

Zytkuewisz, M. P30