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1.
Acta Crystallogr E Crystallogr Commun ; 72(Pt 4): 538-42, 2016 Apr 01.
Artigo em Inglês | MEDLINE | ID: mdl-27375884

RESUMO

A trinuclear nickel complex of phenanthrene-9,10-dione dioxime (H2pqd), namely bis-[µ2-9,10-bis-(oxido-imino)-phenanthrene]-bis-[µ2-10-(oxido-imino)phenanthrene-9-one oxime](phenanthrene-9,10-dione dioxime)trinickel(II) toluene disolvate, [Ni3(C14H8N2O2)2(C14H9N2O2)2(C14H10N2O2)]·2C7H8, has been isolated and its crystal structure determined. This complex features three independent Ni(II) atoms that are arranged in a triangular fashion along with five supporting ligands. There are two square-planar Ni(II) atoms and a third pseudo-octa-hedral Ni(II) atom. While the square-planar Ni(II) atoms are stacked, there are no ligand bridges between them. Each square-planar Ni(II) atom, however, bridges with the pseudo-octa--hedral Ni(II) atom through Ni-N-O-Ni and Ni-O-Ni bonds. A fluorido-bor-ation reaction of the proton-bridged species gave the analogous complex bis-(µ2-bis-{[10-(oxido-imino)-9,10-di-hydro-phenanthren-9-yl-idene]amino}di-fluorido-borato)(phenanthrene-9,10-dione dioxime)trinickel(II) dichloromethane trisolvate, [Ni3(C28H16BF2N4O2)4(C14H10N2O2)]·3CH2Cl2, which shows the same binding structure, but features a widened Ni-Ni inter-action between the square-planar Ni(II) atoms. The proton-bridged complex completes the macrocyclic coordination around the square-planar Ni(II) atoms by means of an O-H⋯O hydrogen bond. Both compounds feature O-H⋯N hydrogen bonds between the oxime and the N atoms attached to square-planar nickel atom. The nickel units show no direct inter-action with their nearest neighbors in the extended lattice. Two π-stacking inter-actions between adjacent mol-ecules are found: one with a centroid-centroid distance of 3.886 (2) Šand the other with a centroid-centroid distance of 4.256 (3) Å. In the latter case, although not aromatic, the distance to the centroid of the central phenanthrene ring is shorter, with a distance of 3.528 (3) Å. Toluene mol-ecules occupy the solvent channels that are oriented along the c axis. In the fluorido-boronate structure, the solvent (DCM) was too badly disordered to be modelled, so its contribution was removed using SQUEEZE [Spek (2015 ▸). Acta Cryst. C71, 9-18].

2.
Int J Mol Sci ; 17(3): 329, 2016 Mar 03.
Artigo em Inglês | MEDLINE | ID: mdl-26950118

RESUMO

Silver nanoparticles have been synthesized by subjecting a reaction medium to a Fusarium oxysporum biomass at 28 °C for 96 h. The biosynthesized Ag nanoparticles were characterized on the basis of their anticipated peak at 405 nm using UV-Vis-NIR spectroscopy. Structural confirmation was evident from the characteristic X-ray diffraction (XRD) pattern, high-resolution transmission electron Microscopy (HRTEM) and the particle size analyzer. The Ag nanoparticles were of dimension 40 ± 5 nm and spherical in shape. The study mainly focused on using the confocal laser scanning microscope (CLSM) to examine the cytotoxic activities of fungal synthesized Ag nanoparticles on a human breast carcinoma cell line MCF7 cell, which featured remarkable vacuolation, thus indicating a potent cytotoxic activity.


Assuntos
Antineoplásicos/química , Antineoplásicos/farmacologia , Nanopartículas Metálicas/química , Prata/química , Prata/farmacologia , Mama/efeitos dos fármacos , Mama/patologia , Neoplasias da Mama/tratamento farmacológico , Neoplasias da Mama/patologia , Sobrevivência Celular/efeitos dos fármacos , Feminino , Fusarium/química , Humanos , Células MCF-7 , Nanopartículas Metálicas/ultraestrutura , Microscopia Confocal , Nanotecnologia
3.
Int J Mol Sci ; 16(10): 24718-31, 2015 Oct 16.
Artigo em Inglês | MEDLINE | ID: mdl-26501273

RESUMO

N-Heterocyclic carbene (NHC) metal complexes possess diverse biological activities but have yet to be extensively explored as potential chemotherapeutic agents. We have previously reported the synthesis of a new class of NHC metal complexes N-heterocyclic with acetate [IPr(BIAN)AuOAc] and chloride [IPr(BIAN)AuCl] ligands. In the experiments reported herein, the zebrafish embryos were exposed to serial dilutions of each of these complexes for 10-12 h. One hundred percent mortality was observed at concentrations≥50 µM. At sub-lethal concentrations (10-30 µM), both compounds influenced zebrafish embryonic development. However, quite diverse categories of abnormalities were found in exposed embryos with each compound. Severe brain deformation and notochord degeneration were evident in the case of [IPr(BIAN)AuOAc]. The zebrafish embryos treated with [IPr(BIAN)AuCl] exhibited stunted growth and consequently had smaller body sizes. A depletion of 30%-40% glutathione was detected in the treated embryos, which could account for one of the possible mechanism of neurotoxicity. The fact that these compounds are capable of both affecting the growth and also compromising antioxidant systems by elevating intracellular ROS production implies that they could play an important role as a new breed of therapeutic molecules.


Assuntos
Ouro/química , Compostos Heterocíclicos/química , Metano/análogos & derivados , Animais , Embrião não Mamífero/efeitos dos fármacos , Ouro/farmacologia , Compostos Heterocíclicos/farmacologia , Metano/química , Metano/farmacologia , Estrutura Molecular , Estresse Oxidativo/efeitos dos fármacos , Peixe-Zebra/embriologia
4.
Asian Pac J Cancer Prev ; 16(16): 7003-6, 2015.
Artigo em Inglês | MEDLINE | ID: mdl-26514482

RESUMO

BACKGROUND: Nanoparticles of gold and silver are offering revolutionary changes in the field of cancer therapy. N-heterocyclic carbene (NHC) metal complexes possess diverse biological activities and are being investigated as potential chemotherapeutic agents. The purpose of this study was to examine the cytotoxicity and possible mechanisms of action of two types of newly synthesized nanofiber composites containing BIAN N-heterocyclic gold carbene complexes in two types of human cancer cells, namely breast cancer (MCF7) and liver cancer (HepG2) cells and also in normal human embryonic kidney cells (HEK 293). MATERIALS AND METHODS: Cytotoxicity was assessed by MTT cell viability assay and oxidative stress by checking the total glutathione level. RESULTS: Both compounds affected the cell survival of the tested cell lines at very low concentrations (IC50 values in the micro molar range) as compared to a well-known anti-cancer drug, 5 fluorouracil. A 60-80% depletion in total glutathione level was detected in treated cells. CONCLUSIONS: Reduction in total glutathione level is one of the biochemical pathways for the induction of oxidative stress which in turn could be a possible mechanism of action by which these compounds induce cytotoxicity in cancer cell lines. The in vitro toxicity towards cancer cells found here means that these molecules could be potential anticancer candidates.


Assuntos
Acenaftenos/farmacologia , Antineoplásicos/farmacologia , Ouro/farmacologia , Compostos Heterocíclicos/farmacologia , Metano/análogos & derivados , Estresse Oxidativo/efeitos dos fármacos , Sobrevivência Celular/efeitos dos fármacos , Complexos de Coordenação/farmacologia , Fluoruracila/farmacologia , Glutationa/metabolismo , Células HEK293 , Células Hep G2 , Humanos , Concentração Inibidora 50 , Células MCF-7 , Metano/farmacologia , Nanofibras
5.
Dalton Trans ; 44(26): 11984-96, 2015 Jul 14.
Artigo em Inglês | MEDLINE | ID: mdl-26074406

RESUMO

Bis(imino)acenaphthene (BIAN) zinc complexes with para-substituted aryl groups have been synthesized and investigated from the standpoint of their photophysical properties. Each complex was found to be nonemissive in solution. However, complexes 1-6 turned out to be emissive in the solid state, while complexes 7 and 8 remained nonemissive. The emissions for complexes 1-8 displayed color tunability ranging from red-yellow. A detailed crystallographic study of the "as-synthesized" structures revealed a distinct difference in the crystal packing environments of the emissive and nonemissive complexes. Furthermore, a solvatomorphic study provided further emission tunability via changes in the crystal packing environments of each solvatomorph. Lastly, TD-DFT calculations were performed in order to investigate the effect of different para-substituents on the flanking aryl rings of the BIAN ligand.

6.
Dalton Trans ; 44(29): 13017-29, 2015 Aug 07.
Artigo em Inglês | MEDLINE | ID: mdl-25867174

RESUMO

Reported here are the syntheses and characterization of cobaloximes that feature a bis(imino)acenaphthene (BIAN) appended ligand. The X-ray crystal structures and spectroscopy ((1)H NMR or EPR) of the complexes within the series [Co(aqdBF2)2(MeCN)2] (), [Co(aqdBF2)(MeCN)2](-) () and [Co(aqdBF2)2(MeCN)2](2-) (, ) are reported and the 3-electron reduced complex [Co(aqdBF2)2(MeCN)2](3-) () has been prepared in situ and characterized by (1)H NMR spectroscopy. The X-ray crystal structures revealed the presence of a 6-coordinate Co(II) species (), a 5-coordinate Co(I) species (), and a 4-coordinate complex (, ). In the case of complex , evidence from single crystal EPR spectroscopy (g‖ = 2.017, g⊥ = 1.987; <10 G linewidths) in conjunction with DFT calculations indicate that the EPR signal originates from a delocalized ligand-based unpaired spin. The frontier orbitals obtained from DFT calculations on , , , & support the electronic assignments that were observed spectroscopically. The cathodic cyclic voltammogram (CV) of the solvato congener in DMF solution, namely [Co(aqdBF2)2(DMF)2], exhibits three reversible redox events near -1.0, -1.5 and -2.0 V vs. Fc/Fc(+). Catalytic proton reduction was observed by CV near the third redox peak. Compared with other cobaloximes (Ecat = -1.0 V), the delay of catalytic onset arises from the existence of a series of resonance-stabilized intermediates.

7.
Dalton Trans ; 43(48): 18117-22, 2014 Dec 28.
Artigo em Inglês | MEDLINE | ID: mdl-25355459

RESUMO

A new sterically shielded carbene with branched aromatic substituents (9a) and two palladium halogenide complexes (11a,b) have been prepared. The single crystal X-ray structures of free carbene 9a and palladium carbene complexes 10b and 11a were determined. Very high catalytic efficiencies were evident for the sterically shielded palladium carbene complexes 10b and 11a,b when the latter complexes were employed as catalysts for hydrodechlorination of the chloroarenes p-dichlorobenzene and hexachlorobenzene. When optimized, the foregoing approach is significantly more effective than those of currently known transition metal carbene complexes. The most active catalysts were found to be the monocarbene complexes of palladium chloride and iodide, both of which feature highly branched aromatic substituents (11a,b).

8.
Dalton Trans ; 43(43): 16227-37, 2014 Nov 21.
Artigo em Inglês | MEDLINE | ID: mdl-25030067

RESUMO

The new sterically shielded 1,3,4-trisubstituted 1,2,4-triazol-5-ylidenes 8b­d were synthesized by a three step method starting from 2-phenyl-1,3,4-oxadiazole. The syntheses of palladium complexes 9a­d and 10a­d (including the sterically shielded derivatives 9c,d and 10a­d) were carried out via the reactions of the stable carbenes 8a­d with palladium halogenide salts in THF or toluene solution. Complexes 9c,d and 10a­d were found to be excellent catalysts for the reductive dechlorination (hydrodechlorination) of p-dichlorobenzene. The structures of 8c, 9a,b, and 10a were determined by single-crystal X-ray diffraction.

9.
J Am Chem Soc ; 135(37): 13939-46, 2013 Sep 18.
Artigo em Inglês | MEDLINE | ID: mdl-24003941

RESUMO

The synthesis, characterization, and theoretical study of the sterically directed functionalization of the redox-active bis(imino)acenaphthene (BIAN) ligand class has been explored. With dependence on the steric congestion encompassing the N-C-C-N fragment of the Ar-BIAN ligand, functionalization can be directed to proceed either via a radical backbone dearomatization or a nucleophilic imine C-alkylation pathway. The structures of the Ar-BIAN derivatives 14-19 were determined by means of single-crystal X-ray diffraction. The reaction pathways involved in Ar-BIAN functionalization were monitored by means of EPR spectroscopy. The experimental results and observations were examined in conjunction with DFT-D calculations in order to explain the driving forces that direct the pathways leading to Ar-BIAN functionalization.

10.
Dalton Trans ; 41(48): 14671-82, 2012 Dec 28.
Artigo em Inglês | MEDLINE | ID: mdl-23060004

RESUMO

A new aromatic carboxylate ligand, 4-[4-(9H-carbazol-9-yl)butoxy]benzoic acid (HL), has been synthesized by the replacement of the hydroxyl hydrogen of 4-hydroxy benzoic acid with a 9-butyl-9H-carbazole moiety. The anion derived from HL has been used for the support of a series of lanthanide coordination compounds [Ln = Eu (1), Gd (2) and Tb (3)]. The new lanthanide complexes have been characterized by a variety of spectroscopic techniques. Complex 3 was structurally authenticated by single-crystal X-ray diffraction and found to exist as a solvent-free 1D coordination polymer with the formula [Tb(L)(3)](n). The structural data reveal that the terbium atoms in compound 3 reside in an octahedral ligand environment that is somewhat unusual for a lanthanide. It is interesting to note that each carboxylate group exhibits only a bridging-bidentate mode, with a complete lack of more complex connectivities that are commonly observed for extended lanthanide-containing solid-state structures. Examination of the packing diagram for revealed the existence of two-dimensional molecular arrays held together by means of CH-π interactions. Aromatic carboxylates of the lanthanides are known to exhibit highly efficient luminescence, thus offering the promise of applicability as optical devices. However, due to difficulties that arise on account of their polymeric nature, their practical application is somewhat limited. Accordingly, synthetic routes to discrete molecular species are highly desirable. For this purpose, a series of ternary lanthanide complexes was designed, synthesized and characterized, namely [Eu(L)(3)(phen)] (4), [Eu(L)(3)(tmphen)] (5), [Tb(L)(3)(phen)] (6) and [Tb(L)(3)(tmphen)] (7) (phen = 1,10-phenanthroline and tmphen = 3,4,7,8-tetramethyl-1,10-phenanthroline). The photophysical properties of the foregoing complexes in the solid state at room temperature have been investigated. The quantum yields of the ternary complexes 4 (9.65%), 5 (21.00%), 6 (14.07%) and 7 (32.42%), were found to be significantly enhanced in the presence of bidentate nitrogen donors when compared with those of the corresponding binary compounds 1 (0.11%) and 3 (1.45%). Presumably this is due to effective energy transfer from the ancillary ligands.

11.
J Am Chem Soc ; 134(38): 15672-5, 2012 Sep 26.
Artigo em Inglês | MEDLINE | ID: mdl-22974228

RESUMO

The syntheses and characterizations of [Li(4)][(1,2-di-(tert-butyl)-dpp-BIAN)(2)] (7), (1,2-di-(tert-butyl)-dpp-BIAN) (8), and (1-(tert-butyl)-2-OH-dpp-BIAN) (9) are described. Compound 7 was formed via a radical dearomatization, two-electron reduction pathway that was accompanied by vicinal di-tert-butylation of the BIAN ligand backbone. Oxidation of 7 afforded a dearomatized vicinal di-tert-butyl substituted BIAN ligand (8). An analogous dearomatized vicinal tert-butyl-hydroxy substituted BIAN ligand (9) was also isolated in the course of mechanistic studies related to the formation of 7.

12.
Int J Nanomedicine ; 7: 2829-32, 2012.
Artigo em Inglês | MEDLINE | ID: mdl-22745545

RESUMO

This report concerns nanofiber composites that incorporate N-heterocyclic carbenes and the use of such composites for testing antimicrobial and antifungal activities. The nanofiber composites were produced by electrospinning mixtures of the gold chloride or gold acetate complexes of a bis(imino)acenaphthene (BIAN)-supported NHC with aqueous solutions of polyvinyl alcohol (PVA). The products were characterized by scanning-electron microscopy, which revealed that nanofibers in the range of 250-300 nm had been produced. The biological activities of the nanofiber composites were tested against two Gram-positive bacteria, six Gram-negative bacteria, and two fungal strains. No activity was evident against the fungal strains. However, the gold chloride complex was found to be active against all the Gram-positive pathogens and one of the Gram-negative pathogens. It was also found that the activity of the produced nanofibers was localized and that no release of the bioactive compound from the nanofibers was evident. The demonstrated antimicrobial activities of these novel nanofiber composites render them potentially useful as wound dressings.


Assuntos
Antibacterianos/farmacologia , Metano/análogos & derivados , Nanocompostos/química , Nanofibras/química , Antibacterianos/química , Bactérias/efeitos dos fármacos , Técnicas Eletroquímicas/métodos , Fungos/efeitos dos fármacos , Compostos de Ouro/química , Compostos de Ouro/farmacologia , Metano/química , Testes de Sensibilidade Microbiana , Nanotecnologia/métodos , Tamanho da Partícula
13.
J Am Chem Soc ; 134(27): 11056-9, 2012 Jul 11.
Artigo em Inglês | MEDLINE | ID: mdl-22720867

RESUMO

A p-type boron arsenide photoelectrode was prepared from a material consisting of a thin layer of boron arsenide on a boron substrate. The structure of the material was identified using X-ray diffraction and scanning electron microscopy, and the surface composition was determined by means of X-ray photoelectron spectroscopy. The electrode was found to be photoactive under both visible light and UV-vis irradiation and displayed a photocurrent of ~0.1 mA/cm(2) under UV-vis irradiation at an applied potential of -0.25 V vs Ag/AgCl. Mott-Schottky plots for this boron arsenide electrode displayed an estimated flat-band potential near the onset photopotential. The estimated indirect band gap, as determined from incident photon-to-electron conversion efficiency plots, is 1.46 ± 0.02 eV.

14.
Dalton Trans ; 41(22): 6842-54, 2012 Jun 14.
Artigo em Inglês | MEDLINE | ID: mdl-22506273

RESUMO

Three new bivalent nickel hydrazone complexes have been synthesised from the reactions of [NiCl(2)(PPh(3))(2)] with H(2)L {L = dianion of the hydrazones derived from the condensation of o-hydroxynaphthaldehyde with furoic acid hydrazide (H(2)L(1)) (1)/thiophene-2-acid hydrazide (H(2)L(2)) (2)/isonicotinic acid hydrazide (H(2)L(3)) (3)} and formulated as [Ni(L(1))(PPh(3))] (4), [Ni(L(2))(PPh(3))] (5) and [Ni(L(3))(PPh(3))] (6). Structural characterization of these compounds 4-6 were accomplished by using various physico-chemical techniques. Single crystal X-ray diffraction data of complexes 4 and 5 proved their distorted square planar geometry. In order to ascertain the potential of the above synthesised compounds towards biomolecular interactions, additional experiments involving interaction with calf thymus DNA (CT DNA) and bovine serum albumin (BSA) were carried out. All the ligands and corresponding nickel(ii) chelates have been screened for their scavenging effect towards O(2)(-), OH and NO radicals. The efficiency of complexes 4-6 to arrest the growth of HeLa, HepG-2 and A431 tumour cell lines has been studied along with the cell viability test against the non-cancerous NIH 3T3 cells under in vitro conditions.


Assuntos
Compostos Heterocíclicos/química , Hidrazonas/química , Níquel/química , Compostos Organometálicos/química , Compostos Organometálicos/metabolismo , Animais , Antineoplásicos/síntese química , Antineoplásicos/química , Antineoplásicos/metabolismo , Antineoplásicos/farmacologia , Sítios de Ligação , Bovinos , Linhagem Celular Tumoral , DNA/metabolismo , Etídio/química , Sequestradores de Radicais Livres/síntese química , Sequestradores de Radicais Livres/química , Sequestradores de Radicais Livres/metabolismo , Sequestradores de Radicais Livres/farmacologia , Humanos , Concentração Inibidora 50 , Modelos Moleculares , Conformação Molecular , Compostos Organometálicos/síntese química , Compostos Organometálicos/farmacologia , Soroalbumina Bovina/metabolismo , Análise Espectral , Relação Estrutura-Atividade
15.
Metallomics ; 4(5): 498-511, 2012 May.
Artigo em Inglês | MEDLINE | ID: mdl-22487989

RESUMO

Two new copper(I) hydrazone complexes have been synthesised from bivalent copper precursor [CuCl(2)(PPh(3))(2)] and ferrocene containing bidentate hydrazone ligands HL(1) (1) or HL(2) (2). Based on the elemental analyses and spectroscopic data, the complexes are best formulated as [CuL(1)(PPh(3))(2)] (3) and [CuL(2)(PPh(3))(2)] (4) of the monovalent copper ion. Solid state structures of ligand 2 and its corresponding complex 4 were also determined. The DNA/albumin interactions of all the synthesised compounds were investigated using absorption, emission and synchronous fluorescence studies. Further, antioxidant properties of all the compounds have also been checked against ABTS, O(2)(-) and OH radicals. Additionally, the in vitro cytotoxic activity of compounds 1-4 was assessed using tumour (HeLa, A431) and non-tumour (NIH 3T3) cell lines.


Assuntos
Antioxidantes/química , Antioxidantes/farmacologia , Cobre/química , Hidrazonas/química , Bases de Schiff/química , Bases de Schiff/farmacologia , Animais , Antioxidantes/síntese química , Antioxidantes/metabolismo , Ligação Competitiva , Bovinos , Sobrevivência Celular/efeitos dos fármacos , Cristalografia por Raios X , DNA/química , DNA/metabolismo , Etídio/química , Etídio/metabolismo , Compostos Ferrosos/química , Células HeLa , Humanos , Metalocenos , Camundongos , Modelos Moleculares , Células NIH 3T3 , Ligação Proteica , Bases de Schiff/síntese química , Bases de Schiff/metabolismo , Soroalbumina Bovina/química , Soroalbumina Bovina/metabolismo , Análise Espectral
16.
Dalton Trans ; 41(15): 4423-36, 2012 Apr 21.
Artigo em Inglês | MEDLINE | ID: mdl-22344370

RESUMO

A new series of geometrically different complexes containing ferrocenyl hydrazone ligands were synthesised by reacting suitable precursor complex [MCl(2)(PPh(3))(2)] with the ligands HL(1) or HL(2) (where M = Cu(II) or Ni(II); HL(1) = [Cp(2)Fe(CH=N-NH-CO-C(6)H(5))] (1) and HL(2) = [Cp(2)Fe(CH=N-NH-CO-C(5)H(4)N)]) (2). The new complexes of the composition [Cu(L(1))(PPh(3))(2)], (3) [Cu(L(2))(PPh(3))(2)] (4), [Ni(L(1))(2)] (5) and [Ni(L(2))(2)] (6) were characterised by various spectral studies. Among them, complexes 3 and 5 characterised by single crystal X-ray diffraction showed a distorted tetrahedral structure for the former with 1:1 metal-ligand stoichiometry, but a distorted square planar geometry with 1:2 metal-ligand stoichiometry in the case of the latter. Systematic biological investigations like DNA binding, DNA cleavage, protein binding, free radical scavenging and cytotoxicity activities were carried out using all the synthesised compounds and the results obtained were explained on the basis of structure-activity relationships. The binding constant (K(b)) values of the synthesised compounds are found to be in the order of magnitude 10(3)-10(5) M(-1) and also they exhibit significant cleavage of supercoiled (SC) pUC19 DNA in the presence of H(2)O(2) as co-oxidant. The conformational changes of bovine serum albumin (BSA) upon binding with the above complexes were also studied. In addition, concentration dependent free radical scavenging potential of all the synthesised compounds (1-6) was also carried out under in vitro conditions. Assays on the cytotoxicity of the above complexes against HeLa and A431 tumor cells and NIH 3T3 normal cells were also carried out.


Assuntos
Antineoplásicos/farmacologia , Antioxidantes/farmacologia , Cobre/farmacologia , DNA/metabolismo , Hidrazonas/farmacologia , Níquel/farmacologia , Animais , Antineoplásicos/química , Antioxidantes/química , Bovinos , Linhagem Celular Tumoral , Complexos de Coordenação/química , Complexos de Coordenação/farmacologia , Cobre/química , Clivagem do DNA/efeitos dos fármacos , Compostos Ferrosos/química , Compostos Ferrosos/farmacologia , Humanos , Hidrazonas/química , Camundongos , Modelos Moleculares , Células NIH 3T3 , Neoplasias/tratamento farmacológico , Níquel/química , Conformação Proteica/efeitos dos fármacos , Soroalbumina Bovina/química
17.
J Am Chem Soc ; 134(1): 176-8, 2012 Jan 11.
Artigo em Inglês | MEDLINE | ID: mdl-22129234

RESUMO

The differences in redox behavior of the monofunctional bis(imino)acenaphthene (BIAN) and bifunctional tetrakis(imino)pyracene (TIP) ligands have been explored by treatment of the latter with PI(3), TeI(4), or BI(3). These reactions result in the formation of products involving the transfer of three or four electrons. Accompanying DFT calculations reveal that in each case the extent of electron transfer from each p-block element into the TIP ligand is dependent upon the element-TIP bonding interactions.

18.
Dalton Trans ; 40(38): 9690-702, 2011 Oct 14.
Artigo em Inglês | MEDLINE | ID: mdl-21858314

RESUMO

Four new bivalent nickel hydrazone complexes have been synthesised from the reactions of [NiCl(2)(PPh(3))(2)] with H(2)L {L = dianion of the hydrazones derived from the condensation of salicylaldehyde or o-hydroxy acetophenone with p-toluic acid hydrazide (H(2)L(1)) (1), (H(2)L(2)) (2) and o-hydroxy acetophenone or o-hydroxy naphthaldehyde with benzhydrazide (H(2)L(3)) (3) and (H(2)L(4)) (4)} and formulated as [Ni(L(1))(PPh(3))] (5), [Ni(L(2))(PPh(3))] (6), [Ni(L(3))(PPh(3))] (7) and [Ni(L(4))(PPh(3))] (8). Structural characterization of complexes 5-8 were accomplished by using various physico-chemical techniques. In order to study the influence of substitution in the ligand and its planarity on the biological activity of complexes 5-8 containing them, suitable hydrazone ligands 1-4 have been selected in this study. Single crystal diffraction data of complexes 5, 7 and 8 proved the geometry of the complexes to be distorted square planar with a 1 : 1 ratio between the metal ion and the coordinated hydrazones. To provide more insight on the mode of action of complexes 5-8 under biological conditions, additional experiments involving their interaction with calf thymus DNA (CT DNA) and bovine serum albumin (BSA) were monitored by UV-visible and fluorescence titrations respectively. Further, the ligands 1-4 and corresponding nickel(ii) chelates 5-8 have been tested for their scavenging effect towards OH and O(2)(-) radicals. The effect of complexes 5-8 to arrest the growth of HeLa and Hep-2 tumour cell lines has been studied along with the cell viability against the non-cancerous NIH 3T3 cells under in vitro conditions.


Assuntos
Antineoplásicos/farmacologia , DNA/química , Sequestradores de Radicais Livres/química , Níquel/química , Compostos Organometálicos/farmacologia , Soroalbumina Bovina/química , Animais , Antineoplásicos/síntese química , Antineoplásicos/química , Sítios de Ligação/efeitos dos fármacos , Bovinos , Linhagem Celular Tumoral , Proliferação de Células/efeitos dos fármacos , Sobrevivência Celular/efeitos dos fármacos , Cristalografia por Raios X , Relação Dose-Resposta a Droga , Ensaios de Seleção de Medicamentos Antitumorais , Células HeLa , Humanos , Ligantes , Magnetismo , Camundongos , Modelos Moleculares , Estrutura Molecular , Células NIH 3T3 , Compostos Organometálicos/síntese química , Compostos Organometálicos/química , Estereoisomerismo , Relação Estrutura-Atividade
19.
Inorg Chem ; 50(11): 4882-91, 2011 Jun 06.
Artigo em Inglês | MEDLINE | ID: mdl-21534615

RESUMO

Two new aromatic carboxylic acids, namely, 3,5-bis(benzyloxy)benzoic acid (HL1) and 3,5-bis(pyridine-2-ylmethoxy)benzoic acid (HL2), have been prepared by replacing the hydroxyl hydrogens of 3,5-dihydroxy benzoic acid with benzyl and pyridyl moieties, respectively. The anions derived from HL1 and HL2 have been used for the support of a series of lanthanide coordination compounds [Eu(3+) = 1-2; Tb(3+) = 3-4; Gd(3+) = 5-6]. The new lanthanide complexes have been characterized on the basis of a variety of spectroscopic techniques in conjunction with an assessment of their photophysical properties. Lanthanide complexes 2, 4, and 6, which were synthesized from 3,5-bis(pyridine-2-ylmethoxy)benzoic acid, were structurally authenticated by single-crystal X-ray diffraction. All three complexes were found to exist as infinite one-dimensional (1-D) coordination polymers with the general formula {[Ln(L2)(3)(H(2)O)(2)]·xH(2)O}(n). Scrutiny of the packing diagrams for 2, 4, and 6 revealed the existence of interesting two-dimensional molecular arrays held together by intermolecular hydrogen-bonding interactions. Furthermore, the coordinated benzoate ligands serve as efficient light harvesting chromophores. In the cases of 1-4, the lowest energy maxima fall in the range 280-340 nm [molar absorption coefficient (ε) = (0.39-1.01) × 10(4) M(-1) cm(-1)]. Moreover, the Tb(3+) complexes 3 and 4 exhibit bright green luminescence efficiencies in the solid state (Φ(overall) = 60% for 3; 27% for 4) and possess longer excited state lifetimes than the other complexes (τ = 1.16 ms for 3; 1.38 ms for 4). In contrast to the foregoing, the Eu(3+) complexes 1 and 2 feature poor luminescence efficiencies.

20.
Eur J Med Chem ; 46(8): 3376-87, 2011 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-21600679

RESUMO

Divalent Co, Ni and Cu hydrazone complexes containing [N'-(phenyl(pyridine-2-yl)methylidene) benzohydrazide] ligand were synthesised and characterised. Interactions of these complexes with DNA revealed an intercalative mode of binding between them. Further, all the hydrazone chelates showed moderate ability to cleave pUC19 DNA. Synchronous fluorescence spectra proved that the interaction of metal complexes with bovine serum albumin (BSA) resulted in a conformational change of the latter. Assay on the cytotoxicity of the above complexes against HeLa tumor cells and NIH 3T3 normal cells revealed that the complexes are toxic only against tumor cells but not to normal cells. In all the biological assays, the complex with copper ion as the metal center showed enhanced activities than the other two.


Assuntos
Antineoplásicos/síntese química , Complexos de Coordenação/síntese química , Cobre/química , Hidrazonas/síntese química , Substâncias Intercalantes/síntese química , Soroalbumina Bovina/química , Animais , Antineoplásicos/farmacologia , Neoplasias da Mama/tratamento farmacológico , Neoplasias da Mama/patologia , Bovinos , Cobalto/química , Cobalto/metabolismo , Complexos de Coordenação/farmacologia , Cobre/metabolismo , Cristalografia por Raios X , DNA/metabolismo , Clivagem do DNA/efeitos dos fármacos , Feminino , Células HeLa , Humanos , Hidrazonas/farmacologia , Substâncias Intercalantes/farmacologia , Camundongos , Modelos Moleculares , Células NIH 3T3 , Níquel/química , Níquel/metabolismo , Plasmídeos/metabolismo , Ligação Proteica/efeitos dos fármacos , Conformação Proteica/efeitos dos fármacos , Piridinas/química , Soroalbumina Bovina/metabolismo , Espectrometria de Fluorescência
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