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ISI Articles of João Costa Pessoa in 2015 Publications – João Costa Pessoa - 2015 P. Adão, S. Barroso, M.F.N.N. Carvalho, C.M. Teixeira, M.L. Kuznetsov, J. Costa Pessoa, Amino acid derived Cu II compounds as catalysts for asymmetric oxidative coupling of 2-naphthol Dalton Trans., 2015, 44, 1612-1626 http://pubs.rsc.org/en/content/articlelanding/2015/dt/c4dt02731k Novel aminopyridine - L-amino acid derived Cu II -complexes are obtained. [Cu II (L)(CH 3 COO)] (HL = (S)-3-phenyl-2-(pyridin-2-ylmethylamino)propanoic acid) is the first ever reported aminopyridine-class Cu II complex bearing a tridentate N,N,O donor set and an monodentate acetato ligand. The complexes act as catalysts in the oxidative coupling of 2-naphthol in organic solvent/water mixtures using dioxygen as the terminal oxidant, to convert 2-naphthol to 1,1'-bi-2-naftol (BINOL) with moderate to low enantioselectivity. Basic additives are important to activity, but these also increase the formation of secondary oxidation products. Addition of peroxide scavengers such as KI resulted in an increase of conversion, yield of BINOL and enantioselectivity. OH OH + [Cu II (L)(X)] + X - B HB + + X - B HB + HOAr [Cu II (L)(OAr)] Cu I (L) O Cu I (L) O Cu I (L) O Cu I (L) 2 O 2 + 2 X - 2 HB + B H 2 O 2 [Cu II (L)(X)] 2 O 2 + X - HB + B O O [Cu II (L)(X)] 1 2 3 4 + H 2 O

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ISI Articles of João Costa Pessoa in 2015

Publications – João Costa Pessoa - 2015

P. Adão, S. Barroso, M.F.N.N. Carvalho, C.M. Teixeira, M.L. Kuznetsov, J. Costa

Pessoa, Amino acid derived CuII compounds as catalysts for asymmetric oxidative

coupling of 2-naphthol

Dalton Trans., 2015, 44, 1612-1626

http://pubs.rsc.org/en/content/articlelanding/2015/dt/c4dt02731k

Novel aminopyridine - L-amino acid derived CuII-complexes are obtained. [CuII(L)(CH3COO)] (HL = (S)-3-phenyl-2-(pyridin-2-ylmethylamino)propanoic acid) is the first ever reported aminopyridine-class CuII complex bearing a tridentate N,N,O donor set and an monodentate acetato ligand. The complexes act as catalysts in the oxidative coupling of 2-naphthol in organic solvent/water mixtures using dioxygen as the terminal oxidant, to convert 2-naphthol to 1,1'-bi-2-naftol (BINOL) with moderate to low enantioselectivity. Basic additives are important to activity, but these also increase the formation of secondary oxidation products. Addition of peroxide scavengers such as KI resulted in an increase of conversion, yield of BINOL and enantioselectivity.

OHOH

+[Cu II(L)(X)]

+ X-B HB+

+ X-B HB+

HOAr[Cu II(L)(OAr)]

CuI(L)

O

CuI(L)

O

CuI(L)

O

CuI(L)2

O2

+ 2 X-2 HB+B

H2O2

[Cu II(L)(X)]2

O2

+ X-HB+B

O

O

[Cu II(L)(X)]

1

2

3

4

+ H2O

ISI Articles of João Costa Pessoa in 2015

M.R. Maurya, N. Chaudhary, F. Avecilla, P. Adão, J. Costa Pessoa,

Oxidovanadium(IV) and dioxidovanadium(V) complexes of hydrazones of 2-

benzoylpyridine and their catalytic applications

Dalton Trans., 2015, 44, 1211-1232

http://pubs.rsc.org/en/content/articlelanding/2015/dt/c4dt02474e

Upon reaction of Hbzpy-tch and Hbzpy-inh with [VIVO(acac)2] yielded

[VIVO(acac)(bzpy-tch)] 1 and [VIVO(OMe)(bzpy-inh)] 2. Compound 2, containing coordinated MeO−, corresponds to a VIVO-compound, where MeO− is one of the ligands, probably equatorially bound to VIV. Upon oxidation in MeOH solution, dinuclear [{VVO(bzpy-tch)}2(µ-O2)] 3 and [{VVO(bzpy-inh)}2(µ-O2)] 4 were obtained and characterized by single-crystal XRD. Treatment of 1 or 2 in MeOH with H2O2 yielded [VVO(O2)(L)] complexes, which upon isolation in the solid state confirmed the formation of [{VVO(O2)(bzpy-tch)}2µ-O2] 5 and [VVO(O2)(bzpy-inh)(H2O)]·0.5MeOH 6a, compound 6a corresponding to a quite unusual structure for a VV-peroxido complex.

Reaction of 3 and 4 with PS-im in DMF gave PS–im[VVO2(bzpy-inh)(MeOH)] 7 and PS–im[VVO2(bzpy-tch)(MeOH)] 8, which were used for the catalytic oxidation of isoeugenol. The recycle ability of the grafted complexes gives 7 and 8 additional advantages over the corresponding neat ones for the catalytic oxidation of isoeugenol.

ISI Articles of João Costa Pessoa in 2015

M.R. Maurya, B. Uprety, F. Avecilla, P. Adão, and J. Costa Pessoa, Vanadium (V) complexes of a tripodal ligand, their characterisation and biological

implications

Dalton Trans., 2015, 44, 17736-17755.

http://pubs.rsc.org/en/content/articlelanding/2015/dt/c5dt02716k

The reaction of a tripodal tetradentate dibasic ligand H2L

1 with [VIVO(acac)2] in MeCN gave [VVO(acac)(L1)] 1. Crystallisation of 1 in MeCN at ~0 ºC, gave crystals of 1, but at RT afforded crystals of [{VVO(L1)}2µ–O] 3. Addition of MeOH to 1 yielded [VVO(OMe)(MeOH)(L1)] 2. All complexes are analyzed by single–crystal XRD. In the reaction of H2L

1 with VIVOSO4 partial hydrolysis of the tripodal ligand occurs resulting in elimination of the pyridyl fragment of L1 and the formation of 4, containing the ONO tridentate ligand 6,6'–azanediylbis(methylene)bis(2,4–di–tert–butylphenol), H2L

2. Compound 4 undergoes dimerization in acetone yielding the hydroxido–bridged dimer, [{VVO(L2)}2µ(HO)2] 5, having distorted octahedral geometry around each vanadium. In contrast, from a solution of 4 in acetonitrile, the dinuclear compound [{VVO(L2)}2µ–O] 6 is obtained, with trigonal bipyramidal geometry around each vanadium. Complex 2 is successfully employed as a catechol–oxidase mimic in the oxidation of catechol to o–quinone under air. Complex 2 is also used as catalyst precursor for the oxidative bromination of thymol in aqueous medium with very good selectivity

ISI Articles of João Costa Pessoa in 2015

T. Mukherjee, J. Costa Pessoa, A. Kumar, A.R. Sarkar, Formation of an unusual

pyridoxal derivative; characterization of Cu(II), Ni(II) and Zn(II) complexes and

evaluation of binding to DNA and to human serum albumin

Inorg. Chim. Acta, 2015, 426, 150-159

http://www.sciencedirect.com/science/article/pii/S0020169314007324

The in-situ reaction of pyridoxal (pyd) and N-methyl-1,3-diamino propane (mdp) with Cu(II)-, Ni(II)-or Zn(II)-acetate yielded complexes [CuII

2(pyd-mdp)(pyd-mmdp)Cl] (1), [NiII2(pyd-mdp)(pyd-mmdp)Cl] (2) and [ZnII

2(pyd-mdp)(pyd-mmdp)Cl] (3), respectively, where pyd-mdp− is the Schiff base ligand and H2pyd-mmdp is an unexpected compound, A plausible mechanism for the formation of the pyd-mmdp2− ligand is discussed. The molecular structure of 1 is determined by single-crystal X-ray diffraction. The binding of pyd-mmdp2− to the metal centers involves two phenolato-O, imine-N and amine-N atoms, and that of pyd-mdp− ligand one phenolato-O, the imine-N and the amine-N atoms; phenolato-O and chloro-Cl atoms bridge the metal centers. The competitive binding of 1-3 with DNA is studied, the apparent binding constants being K = 5.6×104, 3.9×104, and 5.8×104 M−1, respectively. Complex 3 shows insulin-enhancing activity with an IC50 value of 0.51 relative to zinc sulfate. In the presence of HSA, compounds 1-3 progressively decompose with time, forming monomeric M(Schiff base)-HSA adducts, probably involving the formation of bonds with imidazole- or amine-nitrogen atoms of the protein.

ISI Articles of João Costa Pessoa in 2015

J. Costa Pessoa, S. Etcheverry, D. Gambino, Vanadium Compounds in Medicine

Coord. Chem. Rev., 2015, 301-302, 24-48.

http://dx.doi.org/10.1016/j.ccr.2014.12.002

Vanadium being relevant in several biological processes, many of its complexes with organic derivatives have been proposed for the treatment of several types of diseases, although no compound is presently used in the clinic. The mode of action of vanadium compounds is not well-established, but many of the reported therapeutic effects are related to the similarity of vanadate and phosphate, the ability to generate ROS probably being also be relevant.

Vanadium compounds activate numerous signaling pathways and transcription factors, this simultaneously potentiating application of vanadium compounds in therapeutics, but also exerting nonspecific opposite effects on different cell structures. The use of VCs to treat type 2 diabetes as well as cancer and parasitic-related diseases such as Amoebiasis or Chagas’, is still an open question and appears promising. The ability to overcome the balance existing between the therapeutic action and adverse effects exerted by vanadium compounds, by shifting this balance towards the beneficial side, is the crucial issue for the future use of vanadium compounds in Medicine.

Vanadate –phosphate analogy

Relevant for biological action

ISI Articles of João Costa Pessoa in 2015

J. Costa Pessoa, E. Garribba, M. F. A. Santos, T. Santos-Silva, Vanadium and

proteins: uptake, transport, structure, activity and function, Coord. Chem. Rev., 2015, 301-302, 49-86.

http://www.sciencedirect.com/science/article/pii/S001085451400335X

Vanadium is an element ubiquitously present in our planet’s crust and thus there are several organisms that use vanadium for activity or function of proteins. Examples are the vanadium-dependent haloperoxidases, the vanadium-containing nitrogenases; Vanabins are also a unique family of vanadium binding proteins found in ascidians. For all of the systems a discussion regarding the role of the V-containing proteins is made, mostly centered on structural aspects of the vanadium site and, when possible or relevant, relating this to the mechanisms operating. Phosphate is very important in biological systems and is involved in an extensive number of biological recognition and bio-catalytic systems. The ability of vanadium to interfere with the metabolic processes involving Ca2+ and Mg2+, connected with its versatility to undergo changes in coordination geometry, allow V to influence the function of a large variety of phosphate-metabolizing enzymes and vanadate(V) salts and compounds have been frequently used either as inhibitors of these enzymes, or as probes to study the mechanisms of their reactions and catalytic cycle. In this review an overview of the many examples so far reported is given. The prospective application of vanadium compounds as therapeutics is also discussed, namely how vanadium may be transported in blood and up-taken by cells are particularly relevant issues, this being mainly dependent on transferrin (and albumin) present in blood plasma.

There are thousands of studies reporting on the effects of vanadium compounds, reflecting the complexity of the interactions occurring, and it is anticipated that vanadium ions may interfere with many metabolic processes at many distinct levels. The additional knowledge that the presence of vanadium can change the action of a protein, other than simply inhibiting it, may also be important to understand how vanadium affects biological systems. This possibility, together with the vanadate-phosphate analogy, further potentiates the belief that vanadium probably has relevant functions in living beings, which may involve interaction or incorporation of the metal ion and/or its compounds with several proteins.

Structural representation of the adduct formed between the CiVCPO and the vanadate moiety, in the absence (left) and in the presence (right) of H2O2. A change is observed around the vanadium center due to the binding of peroxide.

ISI Articles of João Costa Pessoa in 2015

I. Correia, S. Roy, C.P. Matos, S. Borovic, N. Butenko, I. Cavaco, F. Marques, J. Lorenzo, A. Rodríguez, V. Moreno, J. Costa Pessoa, Vanadium(IV) and copper(II) complexes of salicylaldimines and aromatic heterocycles: cytotoxicity, DNA binding

and DNA cleavage properties

J. Inorg. Biochem., 2015, 147, 134-146

http://www.sciencedirect.com/science/article/pii/S0162013415000641

VIVO and CuII Schiff base complexes derived from salicylaldehyde and amino acids, containing H2O, phen or bipy as co-ligands were prepared. The VIVO-complexes do not exhibit relevant nuclease activity, but [Cu(sal-Gly)(phen)] 2 and [Cu(sal-L-Phe)(phen)] 5 are consistently the most active ones and are capable of double strand cleavage. Studies of binding affinity towards CT-DNA demonstrated that all complexes are able to induce conformational changes in DNA, some forming adducts, others by groove binding and/or by intercalating phen co-ligands between the DNA base pairs. [Cu(sal-L-Phe)(phen)] 5 depicts higher DNA binding ability of when compared to [Cu(sal-Gly)(phen)] 2, and the co-existence of more than one type of binding mode.

Most of the complexes also show cytotoxicity against different human tumor cell lines. The measured cytotoxicity and DNA cleavage ability show that [Cu(sal-L-Phe)(phen)] 5 is the most active one. In general, the CuII-complexes showed much higher cytotoxic activity than the corresponding vanadium complexes and the reference drug cisplatin (except [Cu(sal-Gly)(bipy)]). Moreover, the phenanthroline containing compounds are more cytotoxic than their bipyridine analogues.

DNA cleavage activity of [Cu(sal-Gly)(phen)] 2 and [Cu(sal-L-Phe)(phen)] 5 at 5, 10, 25, 50 and 100 µM (ri = 0.33, 0.67, 1.7, 3.3 and 6.7, respectively) in 10 mM PBS buffer. “Phen” is a control for 1,10-phenanthroline. The incubations were done for 5 h at 37 ºC.

ISI Articles of João Costa Pessoa in 2015

G. Scalese, J. Benítez, S. Rostán, I. Correia, L. Bradford, M. Vieites, L. Minini, A. Merlino, E. L. Coitiño, E. Birriel, J. Varela, H. Cerecetto, M. González, J. Costa Pessoa, D. Gambino, Expanding the family of heteroleptic oxidovanadium(IV)

compounds with salicylaldehyde semicarbazones and polypyridyl ligands showing anti-Trypanosoma cruzi activity,

J. Inorg. Biochem., 2015, 147, 116-125.

http://www.sciencedirect.com/science/article/pii/S0162013415000665

Searching for prospective vanadium-based drugs for the treatment of Chagas disease, in this work a series of [VIVO(L-2H)(NN)] compounds was expanded by including the more lipophilic 3,4,7,8-tetramethyl-1,10-phenanthroline (tmp) as NN ligand and seven tridentate salicylaldehyde semicarbazone derivatives (L1-L7). The complexes were evaluated in vitro for their activity against Trypanosoma cruzi (T. cruzi), and their selectivity was evaluated using J-774 murine macrophages as mammalian cells model. The seven new complexes are more active than the reference drug Nifurtimox and most of them are more active than the previously studied [VIVO(L-2H)(NN)] complexes containing other NN co-ligands. Due to both, high activity and selectivity, the L2, L4, L5 and L7 complexes could be considered new hits for further drug development. Lipophilicity probably plays a relevant role in the bioactivity of the compounds, and some of the most active compounds show lipophilicity that fit well with the optimal lipophilicity value obtained in a previous QSAR series. The reported [VIVO(L-2H)(NN)] compounds were designed aiming DNA as a molecular target and the whole family of compounds, as well as the heads of a different series were screened by computational modeling. Results showed that all complexes display ability to interact with DNA and suggest that the binding mode and strength depend on the NN co-ligand.

B-DNA 20-mer with a

preformed

intercalation site at CG

ISI Articles of João Costa Pessoa in 2015

J. Costa Pessoa, Thirty years of vanadium chemistry,

J. Inorg. Biochem., 2015, 147, 4-24.

http://www.sciencedirect.com/science/article/pii/S0162013415000689

The relevance of vanadium in biological systems is known for many years and vanadium-based catalysts have important industrial applications. The understanding of the broad bioinorganic implications resulting from the similarities between phosphate and vanadate(V) and the discovery of vanadium dependent enzymes gave rise to an enormous increase in interest in the chemistry and biological relevance of vanadium. Thereupon the last 30 years corresponded to a period of enormous research effort in these fields, as well as in medicinal applications of vanadium and in the development of catalysts for use in fine-chemicals synthesis, some of these inspired by enzymatic active sites. Since the 80s my group in collaboration with others made contributions, described throughout this text, namely in the understanding of the speciation of vanadium compounds in aqueous solution and in biological fluids, and to the transport of vanadium compounds in blood plasma and their uptake by cells. Several new types of vanadium compounds were also synthesized and characterized, with applications either as prospective therapeutic drugs or as homogeneous or heterogenized catalysts for the production of fine chemicals. The developments made are described also considering the international context of the evolution of the knowledge in the chemistry and bioinorganic chemistry of vanadium compounds during the last 30 years. This article was compiled based on the Vanadis Award presentation at the 9th International Vanadium Symposium.

4,0 5,0 6,0 7,0 8,0 9,0pH

0

20

40

60

80

100

% for

mat

ion

rela

tive

to (

VO

)

VIVO-hydrolysis - 100 nM

(VIVO)2(OH5)− Speciation of VIVO species in

water at 100 nM. At physiological

pH VIVO(OH)3− is relevant, thus it

might also be important in vivo.

ISI Articles of João Costa Pessoa in 2015

N. Butenko, J. P. Pinheiro, J. Paulo da Silva, A. I. Tomaz, I. Correia, V. Ribeiro, J.

Costa Pessoa, I. Cavaco, The effect of phosphate on the nuclease activity of

vanadium compounds,

J. Inorg. Biochem., 2015, 147, 165-176

http://www.sciencedirect.com/science/article/pii/S016201341500104X

The nuclease activity of VIVO(acac)2 (1) and its derivatives VO(hd)2 (2, hd = 3,5-

heptanedione), VO(Cl-acac)2, (3, Cl-acac = 3-chloro-2,4-pentanedione), VO(Et-acac)2 (4, Et-

acac = 3-ethyl- 2,4-pentanedione) and VO(Me-acac)2 (5, Me-acac = 3-methyl-2,4-

pentanedione), was studied by agarose gel electrophoresis, UV-vis spectroscopy, cyclic and

square wave voltammetry and 51V NMR. The mechanism is shown to be oxidative and

associated with the formation of reactive oxygen species (ROS). Hydrolytic cleavage of the

phosphodiester bond is also promoted by 1, but at much slower rate which cannot compete

with the oxidative mechanism. The generation of ROS is much higher in the presence of

phosphate buffer when compared with organic buffers and this was attributed to the

formation of a mixed-ligand complex containing phosphate, (VIVO)(VVO)(acac)2(HnPO4n-3),

presenting a quasi-reversible voltammetric behaviour. The formation of this species was

further observed by ESI-MS. Phosphate being an important species in most biological

media, the importance of the formation of mixed-ligand species in other vanadium systems

is emphasized.

ISI Articles of João Costa Pessoa in 2015

A.P.S. Roseiro, P. Adão, A.M. Galvão, J. Costa Pessoa, A.M. Botelho do Rego,

M.F.N.N. Carvalho, Activation of oxygen from air by copper camphor complexes,

Inorg. Chem. Front., 2015, 2, 1019-1028

http://pubs.rsc.org/en/content/articlelanding/2015/qi/c5qi00064e

Cleavage of the carboximide CN bond promoted by reaction of camphor carboximide hydrochlorides (OC10H15CONHCH2COOLi(H2O)2·2HCl (2) or OC10H15CONHCH(CH2Ph) COOLi(H2O)·HCl (3)) with CuCl2 leads to the corresponding amino acid complexes ([Cu(H2NCH2COO)2] (I) and [Cu{H2NCH(CH2Ph)COO}2]·(H2O) (II)), and the camphor carboxylate residue (OC10H15COO-), which is catalytically oxidized to camphorquinone by oxygen from air. The process is mediated by coordination of the camphor carboxylate to copper. The reaction of the camphor carboximide hydrochloride (OC10H15CONH(CH2)2COOLi(H2O)·HCl) (4) with CuCl2 follows a different trend. In this case the CN camphor carboximide bond remains intact and the complexes [CuCl{OC10H15CONH(CH2)2COOLi(H2O)}] (III) and [{CuCl2}2{OC10H15CONH(CH2)2COO Li(H2O)}] (IV) form. However, a redox process also occurs, since formation of III requires Cu(II)�Cu(I) reduction as confirmed by X-ray Photoelectron Spectroscopy and cyclic voltammetry. A related reduction process was identified in formation of [CuCl(OC10H15COOLi)] (V) from CuCl2 upon reaction with lithium camphor carboxylate (OC10H15COOLi) under nitrogen. The results show that electron transfer is highly facilitated in the Cu camphor carboximide/carboxylate system. Such ability was used to activate oxygen from air and promote the oxidation of ethylacetoacetate to pyruvate using the Cu-complex V as catalyst.

[Cu]

1´ 6O

O

O-

O

O+ 1/2 O2 + CO2