Book of Abstracts: Coordination / Bioinorganic Chemistry, and Inorganic Materials / Related Areas

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
GENERAL INFORMATION
Instructions to Authors
It is suggested that speakers turn in their CD, USB drive or slides, properly
Speakers 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.
i
SCIENTIFIC PROGRAM
TRACK 1
SUNDAY, OCTOBER 18
14:30 - 17:30 Registration
18:00 - 20:00 Opening Ceremony
The Catalytic Production of Chemicals from

IL11/2 David Cole-Hamilton
Waste Bio-Oils
The Role of Secondary Effects on the Catalytic

IL21/2 Ademir Neves
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
From Molecular to Nanostructured
9:45 - 10:30 IL31 Koiti Araki
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
Analysis of Magnetic Behavior of Composites

12:15 - 12:35 OC11 Pablo Fuentealba Based on the Layered Manganese(II)
Thiophosphate Phase
12:35 - 14:30 Lunch
Quantification of HNO in Real Time: NO/HNO

14:30 - 15:15 IL51 Fabio Doctorovich
Interconversion
Emerging Applications of Ruthenium Compounds

15:15 - 15:45 SL21 Roberto S. da Silva as Modulators of Nitric Oxide Singlet Oxygen by
Light Irradiation. Use Against Cancer Cells
Biomimetic Approach to PHM Monooxygenase

15:45 - 16:05 OC21 Brenda Eguía Active Site with Triplet Cupric-Superoxo
Complexes
Regulation of Oxidoreductase Activity by Cytotoxic

16:30 - 17:00 SL31 Ronan Le Lagadec
Ruthenium and Osmium Complexes
ii
On the Design of Mn(III) N-Pyridylporphyrin-
17:00 - 17:30 SL41 Julio S. Rebouças Based Biomimetic Models of Oxidoreductase
Enzymes
Poster session
17:30 - 19:00
(odd numbers)
IL = Invited Lecture (45 min); SL = Short Invited Lecture (30 min); OC = Oral Communication (20 min)
TUESDAY, OCTOBER 20
Schiff Base-Derived Ligands and Metal
9:00 - 9:45 IL61 Heloisa Beraldo Complexes: Relevance in Medicinal Inorganic
Chemistry
9:45 - 10:15 SL51 Maribel Navarro Metal-Based Agents Against Sporothrix schenckii
Reaction Mechanism for Methane Oxidation
10:15 - 10:35 OC31 Willian R. Rocha Reaction Promoted by a Structural Model of the
PMMO Enzyme
Conditional Surrender: Designing Molecules to
11:00 - 11:45 IL71 Katherine Franz
Put Biological Metals in Their Place
Facially Capping P-Macrocycles - The Control of
11:45 - 12:15 SL61 Peter G. Edwards Lability in Metal-Phosphine Complexes and
Applications in Reactivity
Niobium(V) as Bridge for Magnetic Coupling in a
12:15 - 12:35 OC41 Willian Xerxes
Cr(III)2Nb(V)2 Molecular Square
12:35 - 14:30 Lunch
Determinants of Electron Transfer Efficiency
14:30 - 15:15 IL81 Daniel H. Murgida and Gain of Alternative Functions in Redox
Metalloproteins
Potential Cancer Chemotherapeutics Based on
15:15 - 15:45 SL71 Maria Contel Heterometallic Titanium-Gold and Ruthenium-Gold
Scaffolds
The Electronic Structure of Molecular Uranium(V)
15:45 - 16:05 OC51 Nicholas Chilton
Nitrides
Mechanistic Insight Into Proton Coupled Mixed
16:30 - 16:50 OC61 Luke A. Wilkinson
Valency
Adsorption Process Induced by Supramolecular
16:50 - 17:10 OC71 Brenda Ruiz
Interactions
Stability in Aqueous Solution of Novel [(para-
17:10 - 17:30 OC81 Javier Gomez Cymene)Ru(II)(Aza-Chalcone)Cl]+ Complexes:
Unexpected Alkene Hydration Reaction
Poster session
17:30 - 19:00
(even numbers)
iii
WEDNESDAY, OCTOBER 21
Illuminating Metals: Fluorescent Tools for the
9:00 - 9:45 IL91 Daniela Buccella
Study of Magnesium Homeostasis
Metal Complexes Aiming Application as

9:45 - 10:15 SL81 Victor M. Deflon
Radiopharmaceuticals
New Antimony Complexes as Potential

10:15 - 10:35 OC91 Cynthia Demicheli Antileishmanial Agents Against Sb(III)-Sensitive
and -Resistant Parasites
High Valent Iron Oxo Complexes as

11:00 - 11:45 IL101 Ebbe Nordlander Catalysts for the Oxidation of Alkanes and
Alkenes
Biologically-Inspired Nickel and Iron Complexes

11:45 - 12:15 SL91 Ivan Castillo
with Chelating Aminodi- and Trithiophenolates
Photoinduced Cytotoxicity and DNA Cleavage by

12:15 - 12:35 OC101 Elene Maia
Novel Ru(II) Complexes
12:35 - 14:30 Lunch
14:30 - 19:00 Free afternoon
THURSDAY, OCTOBER 22
Kinases as Targets for Oxindolimine Metal
9:00 - 9:45 IL111 Ana Ferreira
Complexes with Antitumor Activity
Triazolic Cobalt(III) Compounds as Carrier
9:45 - 10:15 SL101 Marciela Scarpellini
Prototypes for Antitumor Prodrugs
Phosphatase-Like Activity in non Symmetrical FeZn
10:15 - 10:35 OC111 Tiago Pacheco Complexes: Tunning the Second Coordination
Sphere Effects in the Phosphate Ester Hydrolysis
Design of Manganese Porphyrin-Based SOD
11:00 - 11:45 IL121 Ines Batinic-Haberle Mimics as Powerful Anticancer Drugs and
Radioprotectors
Lanthanide Compounds Used in OLEDs
11:45 - 12:15 SL111 Flávia C. Machado
Construction
Macrocyclic Transition Metal Complexes for
12:15 - 12:35 OC121 James Pankhurst
Electrochemical Reduction of Carbon Dioxide
12:35 - 14:30 Lunch
Organometallic Preparation of Metal
14:30 - 15:15 IL131 Liane M. Rossi Nanoparticles for the Design of Supported
Catalysts
iv
Zwitterionic Surfactant Stabilized Palladium
15:15 - 16:00 IL141 Faruk Nome
Nanoparticles as Catalysts
Tuning the Luminescence of Tetracoordinated
16:30 - 17:15 IL151 Pedro T. Gomes Organoboron Complexes with Iminopyrrolyl
Bidentate Ligands
Recent Advances in Phosphorus Coordination
17:15 - 18:00 IL161 Maurizio Peruzzini
and Organometallic Chemistry
18:00 - 18:30 Closing Ceremony
21:00 - 23:00 Farewell party
v
1
INVITED LECTURES
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
b
University 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 Fig. 1 Chemicals from cashew nut shell liquid
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.
2
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.
3
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.
4
IL41
MOLECULAR CHAIN “MAGNETS”

Miguel A. Novak*1, Rafael A. Cassaro2, Maria G. F. Vaz3
1
Institute 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
5
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 O 2 the amount of HNO
detected diminishes due to the reaction of HNO with O 2, 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.
6
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.
7
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.
8
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.
9
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
10
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.
11
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.
12
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 H 2O2-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 H 2O2
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).
13
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
14
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), Université 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.
15
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).
16
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.
17
18
ORAL INVITED LECTURES
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
19
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 1O 2
may improve Photodynamic Therapy.
Acknowledgments: FAPESP, CNPq, CAPES and photochem NAP
20
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.
21
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
22
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
23
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
24
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)
25
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
26
SL91
BIOLOGICALLY-INSPIRED NICKEL AND IRON COMPLEXES WITH CHELATING

AMINODI- AND TRITHIOPHENOLATES
Alexander Mondragón 1, Elvis Robles Marín 2, Ivan Castillo 2

1UNIVALLE - 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.
27
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 Co 3+
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
28
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.
29
30
ORAL COMMUNICATION
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.
31
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 O 22. 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
32
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
33
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
34
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
35
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.
36
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.
37
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
38
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.
39
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
40
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
41
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.
42
43
POSTER SESSION
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
44
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
45
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
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)](ClO 4)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
46
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
1UCH - 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)(H 2O)2]}2 motif
with interspersed (H2bppropane)2+ cations, and water molecules providing the charge
balance and structure stabilization.
47
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
1FFCLRP/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.
48
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.
49
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.
50
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.
51
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).
52
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
1UFMG - 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.
53
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.
54
P12
SYNTHESIS OF Ta2O5 NANOPARTICLES FROM 1-N-ALKYL-3-METHYLIMIDAZOLIUM
HEXACHLOROTANTALATE IONIC LIQUIDS
Virgínia Serra De Souza, Jackson Damiani Scholten, Jairton Dupont 1
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
55
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.
56
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.
57
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 H 2L 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
58
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).
59
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.
60
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.
61
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
62
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.
63
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 Å 3 (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.
64
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
1C. 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.
65
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
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
66
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
67
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.
68
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
1UDELAR - 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
69
P27
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
70
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
71
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
1UNAL - 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.
72
P30
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)(PPh 3)]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 cisplatin 3. 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.
73
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 [Ru 3O(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.
74
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 NaBH 4. 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.
75
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
1UFSCAR- 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.
76
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.
77
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
78
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.
79
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
80
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 universal 1. 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
81
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.
82
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).
83
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.
84
P42
NEW COMPLEXES OF THE TYPE [RhCl(COD)L], L= PYRIDYL-CHALCONES OR
PYRIDYL-INDOLINONES
Esperanza Galarza1*, Gala de la Vega1, Fernando Cuenú2

1
Departamento 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
85
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
86
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 H 2edb
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
87
AUTHOR INDEX
TRACK 1
Afzal, M. IL9 Biazotto, J. C. P5

Alamo, M. F. OC7 P7
Amado, R. P32 Bombazar, C. C. P27
Anacona, J. R. P8 Borba-Santos, L. P. SL5
Araki, K. IL3 Brito, H. A. P1
Arancibia, R. P18 Broicher, C. IL14
Araujo, M. P10 Buccella, D. IL9
Arce, E. R. P26 Bueno-Janice, J.C. SL4
Atria, A. M. P4 Burgos, A.E. P29
Baader, S. IL1 Bustamante, J. P8
Baggio, R. P4 Cadenbach, T. OC12
Barbosa, R. S. P13 Camargo, T. P22
Barolli, J. P40 OC11
Barros, W. P11 Cano, J. OC4
Bartlett, S. IL1 Carlos, I. P30
Batinic-Haberle, I. IL12 Carneiro, Z. P31
SL4 Carrasco, F. P20
Batista, A. SL5 Cassaro, R. A. IL4
P33 Castelli, S. P14
P36 Castillo, I. SL9
P37 Cebrián-Torrejón, G. P3
P39 P24
P40 Chaves, C. OC11
P41 Chilton, N.F. OC5
. P34 Clavijo, J. P39
P35 Coitiño, L. P26
P38 Cole-Hamilton, D. J IL1
Batista, R. C. P24 Colina, L. SL5
Beraldo, H. IL6 Colina-Vegas, L. P37
P14 Cominetti, M. P33
P19 P35
Beyer, L. P20 Contel, M. SL7
Bhat, S. IL10 Correa, R. P33
88
P36 do Pim, W. P10
Corsini, G. P4 P11
Costa, N. J. S. IL14 do Prado, B. H. R. OC9
Costas, M. IL10 Doctorovich, F. IL5
Cuenú, F. P42 Dupont, J. P12
da Cruz, A. G. B. P1 Echeverría, G. P26
da Fonseca, M.G. SL4 Edwards, P. SL6
da Silva, C. P. P1 Eguía, B. N. S. OC2
da Silva, F. C. SL10 Ellena, J. P39
da Silva, J. P14 Escudero, G. P17
da Silva, J. G. P19 Escudero, R. OC7
da Silva, R. S. P5 Fagundes, E. M. S. P19
P7 Falcão, N.K.S.M. SL4
SL2 Faria, R. B. SL10
Das, B. IL10 Faro, L. P23
Dávila-Rodríguez, M. J. P40 Ferraudi, G. P6
de Albuquerque, S. P31 Ferreira, A. M. C IL11
de Camargo, T. P. P25 Ferrer, E. P17
de Fatima, G. D. P29 Fiedler, H. D. IL13
de la Vega, G. P42 Fierro-Huerta, A. P21
de Mello, M. V. P. P3 Filho, L. F. O. B. P13
P24 Fragoso, W.D. SL4
de Oliveira, K. P40 Franz, K.J. IL7
de Santana, R. C. OC1 Frézard, F. OC9
de Souza, I. C. A. P2 Fuentealba, P. OC1
de Souza, V. S. P12 Furst, M. IL1
de Souza, W. SL5 Gabriel, P. OC10
Deflon, V. M. P36 Gagini, T. SL5
P34 Galarza, E. P42
SL8 Gambino, D. P26
Demicheli, C. OC9 Garcia, R. D. IL1
Desideri, A. P14 Garrido, S. P30
do Nascimento, F. B. P7 Godinho, J. P37
P34 Godoy, F. P21
do Nascimento, G. P11 Gomes, P.T. IL15
89
Gomez, J. A. G. OC8 le Goff, R. IL1
Gonzaga, D. P23 le Lagadec, R. SL3
SL10 Leite, C. P41
González, R. A. P28 Lemus, L. P6
Gorritti, W. R. H. P20 Levin, P. P6
Graminha, A. P33 Liddle, S.T. OC5
Grawe, G. P36 Lin, Q. IL9
P39 Lloret, F. OC4
P40 Lopes, N. P. OC8
P34 Love, J. B. OC12
Gruskos, J. IL9 Luke, W. OC6
Guedes, A. P36 Macedo, T. S. P38
Guedes, G. P. P1 Machado, F. C. SL11
Guerrero, J. P6 Magon, C. J. OC1
Guimarães, M. P32 Maia, C.G.C. SL4
Herrera, B. L. R. OC7 Malinkin, S. IL10
Heying, R. P15 Manente, F. P30
Higuera, A. SL5 Manzur, J. OC1
Homrich, A. P22 P20
Honorato, J. P33 Maresca, N. P17
Idemori, Y.M. SL4 Marín, E.R. SL9
Islam, A. OC9 Martini, N. P17
Jori, K. P17 Martins, V. P44
Jori, N. P17 Matos, C. R. M. O. P44
Julis, J. IL1 Matos, R. R. SL10
Julve, M. OC4 Máximo, L. N. C. P5
Klahn, H. P18 McInnes, E.J.L. OC5
Kremer, L. P18 Melo, A.C.C. OC10
Laino, C. P17 Menezes, A. P33
Lanza, J. S. OC9 Merlino, A. P26
Lanznaster, M. P2 Mgani, Q. IL1
P3 Mgaya, J. IL1
P23 Miranda, F. P23
P24 P40
Lappin, A. G. P6 OC8
90
Mireski, S. P25 Orio, M. OC2
Mitra, M. IL10 Orzari, A. R. P7
Mmongoyo, J. IL1 Ospina, K. G. P29
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P22 Pereira, L. R. P34
P25 Pereira, M. D. P16
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5º SIMPOSIO LATINOAMERICANO DE QUÍMICA

Organizing Committee of SILQCOM

Prof. Dalmo Mandeli - Federal University of ABC - Brazil

Organizing Committee of Brazil-France Bilateral Workshop

Prof. Dalmo Mandeli - Federal University of ABC - Brazil

Scientific Committee of SILQCOM

Prof. Anellise Casellato - Federal University of Rio de Janeiro - Brazil

Prof. Fabio Doctorovich - University of Buenos Aires – Argentina

Abstracts of Invited Lectures 1

Abstracts of Oral Invited Lectures 18

Abstracts of Oral Communications 30

18:00 - 20:00 Opening Ceremony

The Catalytic Production of Chemicals from

The Role of Secondary Effects on the Catalytic

21:00 - 22:30 Welcome mixer

10:35 - 11:00 Coffee-break

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

Analysis of Magnetic Behavior of Composites

12:35 - 14:30 Lunch

Quantification of HNO in Real Time: NO/HNO

Emerging Applications of Ruthenium Compounds

Biomimetic Approach to PHM Monooxygenase

16:05 - 16:30 Coffee-break

Regulation of Oxidoreductase Activity by Cytotoxic

Metal Complexes Aiming Application as

New Antimony Complexes as Potential

10:35 - 11:00 Coffee-break

High Valent Iron Oxo Complexes as

Biologically-Inspired Nickel and Iron Complexes

Photoinduced Cytotoxicity and DNA Cleavage by

12:35 - 14:30 Lunch

14:30 - 19:00 Free afternoon

THE CATALYTIC PRODUCTION OF CHEMICALS FROM WASTE BIO - OILS

THE ROLE OF SECONDARY EFFECTS ON THE CATALYTIC ACTIVITY OF

Keywords: Metalloydrolases, Biomimetics, DNA intercalation

From Molecular to Nanostructured Electrocatalysts

MOLECULAR CHAIN “MAGNETS”

CAPES, CNPQ, FAPERJ

QUANTIFICATION OF HNO IN REAL TIME: NO/HNO INTERCONVERSION

CONDITIONAL SURRENDER: DESIGNING MOLECULES TO PUT BIOLOGICAL

Keywords: electron transfer, CuA, cytochrome

conducted with support from New York University

HIGH VALENT IRON OXO COMPLEXES AS CATALYSTS FOR THE OXIDATION OF

CAPES, CNPQ, FAPESC

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

HYBRID MATERIALS: SYNTHESIS AND APPLICATIONS

CAPES, CNPQ, FAPERJ

EMERGING APPLICATIONS OF RUTHENIUM COMPOUNDS AS MODULATORS OF

Roberto Santana da Silva

University of Sao Paulo, Brazil

Acknowledgments: FAPESP, CNPq, CAPES and photochem NAP

REGULATION OF OXIDOREDUCTASE ACTIVITY BY CYTOTOXIC RUTHENIUM AND

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

Mn porphyhrins (MnPs) are long-known chemical models for oxidoreductase enzymes,

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

METAL-BASED AGENTS AGAINST SPOROTHRIX SCHENCKII

M. Navarro*1, G. Visbal1, L. Colina2, W. Villarreal2, A. Higuera3, W. de Souza4, A. Batista2,

Sporotrichosis is a subcutaneous mycosis of humans and mammals that has a worldwide

FAPERJ, CAPES, CNPQ

FACIALLY CAPPING P-MACROCYCLES - THE CONTROL OF LABILITY IN METAL-

POTENTIAL CANCER CHEMOTHERAPEUTICS BASED ON HETEROMETALLIC

Funded by NCI (grant 1SC1CA182844)

METAL COMPLEXES AIMING APPLICATION AS RADIOPHARMACEUTICALS