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1.
Inorg Chem ; 49(5): 2173-81, 2010 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-20088549

RESUMO

The reactions of PbR(2)(OAc)(2) (R = Me, Ph) with 3-(2-thienyl)-2-sulfanylpropenoic acid (H(2)tspa) in methanol or ethanol afforded complexes [PbR(2)(tspa)] that electrospray ionization-mass spectrometry (ESI-MS) and IR data suggest are polymeric. X-ray studies showed that [PbPh(2)(tspa)(dmso)] x dmso, crystallized from a solution of [PbPh(2)(tspa)] in dmso, is dimeric, and that [HQ](2)[PbPh(2)(tspa)(2)] (Q = diisopropylamine), obtained after removal of [PbPh(2)(tspa)] from a reaction including Q, contains the monomeric anion [PbPh(2)(tspa)(2)](2-). In the solid state the lead atoms are O,S-chelated by the tspa(2-) ligands in all these products, and in the latter two have distorted octahedral coordination environments. NMR data suggest that tspa(2-) remains coordinated to PbR(2)(2+) in solution in dmso. Neither thiamine nor thiamine diphosphate reacted with PbMe(2)(NO(3))(2) in D(2)O. Prior addition of H(2)tspa protected LLC-PK1 renal proximal tubule cells against PbMe(2)(NO(3))(2); thiamine had no statistically significant effect by itself, but greatly potentiated the action of H(2)tspa. Administration of either H(2)tspa or thiamine to male albino Sprague-Dawley rats dosed 30 min previously with PbMe(2)(NO(3))(2) was associated with reduced inhibition of delta-ALAD by the organolead compound, and with lower lead levels in kidney and brain, but joint administration of both H(2)tspa and thiamine only lowered lead concentration in the kidney.


Assuntos
Acrilatos/química , Chumbo/química , Compostos Organometálicos/química , Compostos Organometálicos/toxicidade , Compostos de Sulfidrila/química , Tiamina/química , Animais , Linhagem Celular , Difosfatos/química , Espectroscopia de Ressonância Magnética , Masculino , Modelos Moleculares , Conformação Molecular , Compostos Organometálicos/sangue , Compostos Organometálicos/síntese química , Sintase do Porfobilinogênio/antagonistas & inibidores , Sintase do Porfobilinogênio/sangue , Propilaminas/química , Ratos , Ratos Sprague-Dawley
2.
Inorg Chem ; 47(14): 6262-72, 2008 Jul 21.
Artigo em Inglês | MEDLINE | ID: mdl-18563877

RESUMO

Gold complexes of the type [(AuPEt3)2xspa] were prepared by reacting AuPEt3Cl in basic media with the 3-(aryl)-2-sulfanylpropenoic acids H2xspa [x = p, Clp, -o-mp, -p-mp, -o-hp, -p-hp, diBr-o-hp, f, t, -o-py; p = 3-phenyl, Clp = 3-(2-chlorophenyl)-, -o-mp = 3-(2-methoxyphenyl)-, -p-mp = 3-(4-methoxyphenyl)-, -o-hp = 3-(2-hydroxyphenyl)-, -p-hp = 3-(4-hydroxyphenyl)-, diBr-o-hp = 3-(3,5- dibromo-2-hydroxyphenyl)-, f = 3-(2-furyl)-, t = 3-(2-thienyl)-, -o-py = 3-(2-pyridyl); spa = 2-sulfanylpropenoato], and 2-cyclopentylidene-2-sulfanylacetic acid (H2cpa). The complexes were characterized by spectroscopic methods (IR, (1)H, (13)C and (31)P NMR) and mass spectrometry, and the complexes [(AuPEt3)2pspa] x 3 H2O, [(AuPEt3)2-p-hpspa] x 3 H2O, [(AuPEt3)2tspa)] x 3 H2O, and [(AuPEt3)2-o-hpspa] by X-ray diffractometry. The crystals of the first three complexes contain (H2O)6 clusters hydrogen bonded to [(AuPEt3)2xspa]2 dimer units, whereas in the -o-hpspa derivative the hydrogen bonds are between the monomer [(AuPEt3)2-o-hpspa] units. The antiinflammatory activity of the complexes against plantar edema induced by carrageenan in rats is generally significant, with the values for the o-hpspa and tspa derivatives being particularly high.


Assuntos
Anti-Inflamatórios não Esteroides/síntese química , Anti-Inflamatórios não Esteroides/farmacologia , Compostos de Ouro/síntese química , Compostos de Ouro/farmacologia , Animais , Carragenina/toxicidade , Relação Dose-Resposta a Droga , Inflamação/induzido quimicamente , Inflamação/tratamento farmacológico , Modelos Moleculares , Estrutura Molecular , Ratos , Relação Estrutura-Atividade
3.
J Inorg Biochem ; 102(2): 184-92, 2008 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-17870173

RESUMO

The reaction of triphenylphosphinegold(I) chloride in ethanol in a 1:1 molar ratio with the 3-(aryl)-2-sulfanylpropenoic acids H(2)xspa [x: p=3-phenyl-, Clp=3-(2-chlorophenyl)-, -o-mp=3-(2-methoxyphenyl)-, -p-mp=3-(4-methoxyphenyl)-, -o-hp=3-(2-hydroxyphenyl)-, -p-hp=3-(4-hydroxyphenyl)-, diBr-o-hp=3-(3,5-dibromo-2-hydroxyphenyl)-, f=3-(2-furyl)-, t=3-(2-thienyl)-, -o-py=3-(2-pyridyl)-; spa=2-sulfanylpropenoato] gave compounds of the type [Au(PPh(3))(Hxspa)], which were isolated and characterized as solids by elemental analysis, IR spectroscopy and FAB mass spectrometry and in solution by (1)H, (13)C and (31)P NMR spectroscopy. The structures of the complexes [Au(PPh(3))(HClpspa)], [Au(PPh(3))(H-o-mpspa)] and [Au(PPh(3))(H-p-mpspa)].2/3C(3)H(6)O were determined by X-ray diffractometry. Hydrogen bonding was found along with Au-S and Au-P bonds in all cases and weak pi-pi stacking was found in the H-p-mpspa derivative. The in vitro antitumour activities against the HeLa-229, A2780 and A2780cis cell lines were determined for all complexes.


Assuntos
Antineoplásicos , Compostos Organoáuricos/síntese química , Acrilatos/síntese química , Acrilatos/química , Acrilatos/farmacologia , Antineoplásicos/síntese química , Antineoplásicos/química , Antineoplásicos/farmacologia , Linhagem Celular Tumoral , Proliferação de Células/efeitos dos fármacos , Cristalografia por Raios X , Células HeLa , Humanos , Espectroscopia de Ressonância Magnética , Compostos Organoáuricos/química , Compostos Organoáuricos/farmacologia , Fosfinas/síntese química , Fosfinas/química , Fosfinas/farmacologia
4.
Eur J Med Chem ; 43(11): 2489-97, 2008 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-18752868

RESUMO

We investigated the reactions of silver nitrate with 3-(substituted phenyl)-2-sulfanylpropenoic acids H(2)L [L=xspa, where spa=2-sulfanylpropenoato and xin{Clp=3-(2-chlorophenyl)-, -o-mp=3-(2-methoxyphenyl)-, -o-hp=3-(2-hydroxyphenyl)-, -p-hp=3-(4-hydroxyphenyl)-, diBr-o-hp=3-(3,5-dibromo-2-hydroxyphenyl)-}] in 1:1 and 2:1 molar ratios. The 1:1 reactions gave compounds of type [Ag(HL)], which reacted with NaOH to afford Na[Ag(L)].xH(2)O (x=1 or 2) and with diisopropylamine to afford [HQ][Ag(L)] (HQ=diisopropylammonium). The 2:1 reactions gave products of type [Ag(2)(L)]. All the new compounds were isolated and characterized by IR spectroscopy, and all except the 2:1 adducts (which were insoluble) were studied by (1)H and (13)C NMR spectroscopy; ESI-MS spectrometry was also used for [HQ][Ag(L)] and Na[Ag(L)].xH(2)O, and the crystal structures of H(2)Clpspa and [HQ][Ag(Clpspa)] were determined by X-ray diffractometry. The antimicrobial activities of the complexes against Escherichia coli, Staphylococcus aureus, Bacillus subtilis, Candida albicans, Pseudomonas aeruginosa and carbapenem-resistant P. aeruginosa were evaluated and compared with those of Ag(I) complexes with other aryl sulfanylpropenoates or related ligands.


Assuntos
Antibacterianos/síntese química , Antibacterianos/farmacologia , Propano/síntese química , Propano/farmacologia , Compostos de Prata/síntese química , Compostos de Prata/farmacologia , Compostos de Enxofre/síntese química , Antibacterianos/química , Cristalografia por Raios X , Ligação de Hidrogênio , Viabilidade Microbiana/efeitos dos fármacos , Modelos Moleculares , Estrutura Molecular , Propano/química , Compostos de Prata/química , Espectrofotometria Infravermelho , Compostos de Enxofre/química , Compostos de Enxofre/farmacologia
5.
J Inorg Biochem ; 180: 163-170, 2018 03.
Artigo em Inglês | MEDLINE | ID: mdl-29291491

RESUMO

The reaction of 3-(aryl)-2-sulfanylpropenoic acids [H2xspa; x: p=3-phenyl-, f=3-(2-furyl)-, t=3-(2-thienyl)-] with methanol or ethanol gave the corresponding methyl (Hxspme) or ethyl (Hxspee) esters. The reaction of these esters (HL) with triphenyltin(IV) hydroxide gave compounds of the type [SnPh3L], which were isolated and characterized as solids by elemental analysis, IR spectroscopy and mass spectrometry and in solution by multinuclear (1H, 13C and 119Sn) NMR spectroscopy. The structures of [SnPh3(pspme)], [SnPh3(fspme)] and [SnPh3(fspee)] were determined by X-ray diffractometry and the antimicrobial activity against E. coli, S. aureus, B. subtilis, P. aeruginosa, Resistant P. aeruginosa (a strain resistant to 'carbapenem'), and C. albicans was tested and the in vitro cytotoxic activity against the HeLa-229, A2780 and A2780cis cell lines was determined for all compounds.


Assuntos
Ácidos Carboxílicos/química , Ácidos Carboxílicos/farmacologia , Compostos Orgânicos de Estanho/química , Compostos Orgânicos de Estanho/farmacologia , Enxofre/química , Anti-Infecciosos/farmacologia , Candida albicans/efeitos dos fármacos , Ácidos Carboxílicos/síntese química , Linhagem Celular Tumoral , Cristalografia por Raios X , Ensaios de Seleção de Medicamentos Antitumorais , Esterificação , Bactérias Gram-Negativas/efeitos dos fármacos , Bactérias Gram-Positivas/efeitos dos fármacos , Humanos , Espectroscopia de Ressonância Magnética , Testes de Sensibilidade Microbiana , Compostos Orgânicos de Estanho/síntese química , Espectrometria de Massas por Ionização por Electrospray , Espectrofotometria Infravermelho
6.
J Inorg Biochem ; 100(11): 1858-60, 2006 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-16965818

RESUMO

Reaction of the vitamin K(3) derivative menadione sodium bisulfite thiosemicarbazone (NaK(3)TSC) with chloro(triethylphosphine)gold(I) afforded the complex [AuPEt(3)(K(3)TSC)]. This compound consists of discrete molecules in which the metal is almost linearly coordinated to P and S. Preliminary in vitro screening showed significant anti-cancer activity, notably against the cisplatin-resistant cell line A2780cis.


Assuntos
Compostos Organoáuricos/química , Vitamina K 3/química , Linhagem Celular Tumoral , Cisplatino/farmacologia , Resistencia a Medicamentos Antineoplásicos/efeitos dos fármacos , Ensaios de Seleção de Medicamentos Antitumorais , Humanos , Ligação de Hidrogênio , Concentração Inibidora 50 , Estrutura Molecular , Compostos Organoáuricos/farmacologia
7.
J Inorg Biochem ; 100(1): 124-32, 2006 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-16337684

RESUMO

The reaction of oxythiamine chloride hydrochloride (HOxTCl x HCl) with ZnCl2, CdCl2 and HgCl2 in ethanol yielded the complexes [ZnCl3(HOxT)], [CdCl3(HOxT)] and [HgCl3(HOxT)]. In water, the reaction with CdCl2 afforded [CdCl2(OxT)], but reaction with ZnCl2 or HgCl2 yielded unidentified products. The four new complexes were characterized by mass spectrometry and IR spectroscopy in the solid state and by 1H, 13C and 15N nuclear magnetic resonance (NMR) spectroscopy in hexadeuterated dimethylsulfoxide (DMSO-d6), and three were also studied by X-ray diffractometry. In [ZnCl3(HOxT)] and [HgCl3(HOxT)] the oxythiamine ligand is bound to the metal via N(1') and adopts the V conformation exhibited by thiamine in biological contexts. The infrared (IR) spectrum of [CdCl3(HOxT)] suggests a similar coordination mode. In [CdCl2(OxT)] each OxT zwitterion coordinates to one Cd(II) ion via its N(1') atom and to another via its N(3') and O atoms, giving rise to a polymeric chain along the x-axis. The coordination number of the metal is made up to six by Cdc...Cl interactions, two of which link the polymeric chains in pairs. This seems to be the first metal complex containing the oxythiamine ligand as a zwitterion, with the N(3')-H/O(4'alpha)-H group deprotonated. Neither HOxTCl nor its zinc(II) complex showed any significant activity in vitro against HeLa cells.


Assuntos
Antimetabólitos/química , Cloreto de Cádmio/química , Cloretos/química , Cloreto de Mercúrio/química , Oxitiamina/química , Tiamina/química , Compostos de Zinco/química , Antimetabólitos/farmacologia , Cloreto de Cádmio/farmacologia , Cloretos/farmacologia , Ensaios de Seleção de Medicamentos Antitumorais , Células HeLa , Humanos , Espectroscopia de Ressonância Magnética , Espectrometria de Massas , Cloreto de Mercúrio/farmacologia , Compostos Organometálicos/química , Compostos Organometálicos/farmacologia , Oxitiamina/farmacologia , Espectrofotometria Infravermelho , Tiamina/farmacologia , Difração de Raios X , Compostos de Zinco/farmacologia
8.
J Inorg Biochem ; 131: 68-75, 2014 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-24269769

RESUMO

Heteronuclear complexes of the type [AgAu(PPh3)2(xspa)] [H2xspa=3-(aryl)-2-sulfanylpropenoic acids; (x=3-phenyl-; 3-(2-chlorophenyl)-; 3-(o-methoxyphenyl)-; 3-(p-methoxyphenyl)-; 3-(p-hydroxyphenyl)-; 3-(2-furyl)-; 3-(2-thienyl)-; spa=2-sulfanylpropenoate)] were prepared by reacting the appropriate [Au(PPh3)(Hxspa)] precursor with Ag(PPh3)NO3. The compounds were characterized by spectroscopic methods, (IR; (1)H, (13)C and (31)P NMR) and mass spectrometry and the structures of the phenyl and p-methoxyphenyl derivatives were determined by X-ray diffraction. The in vitro antitumor activity against the HeLa-229, A2780 and A2780cis cell lines was determined and compared with that of cisplatin and the equivalent homonuclear gold(I) complexes.


Assuntos
Antineoplásicos/química , Antineoplásicos/farmacologia , Compostos Organoáuricos/química , Compostos Organoáuricos/farmacologia , Compostos de Prata/química , Compostos de Prata/farmacologia , Antineoplásicos/síntese química , Ácidos Carboxílicos/química , Técnicas de Química Sintética , Cristalografia por Raios X , Ensaios de Seleção de Medicamentos Antitumorais , Células HeLa/efeitos dos fármacos , Humanos , Espectroscopia de Ressonância Magnética , Estrutura Molecular , Compostos Organoáuricos/síntese química , Compostos de Prata/síntese química , Relação Estrutura-Atividade
9.
J Inorg Biochem ; 138: 89-98, 2014 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-24935091

RESUMO

Gold complexes of the type [Au(PEt3)(Hxspa)] were prepared by reacting triethylphosphinegold(I) chloride in ethanol/water (8:1) with the 3-(aryl)-2-sulfanylpropenoic acids H2xspa [x=p=3-phenyl-; f=3-(2-furyl)-; t=3-(2-thienyl)-; py=3-(2-pyridyl); Clp=3-(2-Chlorophenyl)-; -o-mp=3-(2-methoxyphenyl)-; -p-mp=3-(4-methoxyphenyl)-; -o-hp=3-(2-hydroxyphenyl)-; -p-hp=3-(4-hydroxyphenyl)-; -diBr-o-hp=3-(3,5-dibromo-2-hidroxyphenyl-); spa=2-sulfanylpropenoato] or 2-cyclopentylidene-2-sulfanylacetic acid (H2cpa) and KOH in a 1:1:1 mole ratio. The compounds were characterized by IR spectroscopy and FAB mass spectrometry and by (1)H, (13)C and (31)P NMR spectroscopy. The in vitro antitumor activity of these and of the previously described dinuclear [(AuPEt3)2(xspa)] complexes against the HeLa-229, A2780 and A2780cis cell lines was determined and compared with those of the analogous PPh3 complexes. The results show that the substitution of the PPh3 ligand by PEt3 is particularly effective in increasing the cytotoxicity of the dinuclear [(AuPR3)2(xspa)] complexes, giving rise to compounds that are significantly more active than cisplatin against the aforementioned cell lines. In addition, and as a preliminary test for nephrotoxicity, the cytotoxicity of the most active compounds against the normal renal LCC-PK1 cell line was evaluated and compared with that of cisplatin.


Assuntos
Antineoplásicos/síntese química , Compostos Organoáuricos/síntese química , Fosfinas/síntese química , Ácidos Sulfanílicos/síntese química , Antineoplásicos/farmacologia , Linhagem Celular Tumoral , Resistencia a Medicamentos Antineoplásicos/efeitos dos fármacos , Feminino , Humanos , Compostos Organoáuricos/farmacologia , Fosfinas/farmacologia , Relação Estrutura-Atividade , Ácidos Sulfanílicos/farmacologia
10.
Dalton Trans ; 42(16): 5916-23, 2013 Apr 28.
Artigo em Inglês | MEDLINE | ID: mdl-23459791

RESUMO

The hexanuclear complex [HQ][Ag(p-mpspa)] (H2-p-mpspa = 3-(4-methoxyphenyl)-2-sulfanylpropenoic acid) was prepared by reacting the precursor [Ag(H-p-mpspa)] with diisopropylamine (Q). The complex was characterized by spectroscopic techniques and the structure was solved by a single crystal X-ray diffraction study. The crystal contains hydrogen-bonded diisopropylammonium cations and [Ag6(p-mpspa)6](6-) anions that are based on a regular Ag6 ring with each S-donor atom of the sulfanylcarboxylate ligand bridging two Ag atoms. The Ag-Ag bond distances, 2.8036(6) Å, are very short and suggest a closed shell d(10)···d(10) argentophilic interaction. To analyze the relative role of this interaction and that of the S-bridging atom the anionic [Ag6(p-mpspa)6](6-) moiety has been studied theoretically at the Hartree-Fock (HF) and 2(nd) order Møller-Plesset perturbation theory (MP2) levels on a very simple [Ag6(SH)6] A model system. A large model system [Ag6(p-mpspa)6](6-)B has also been studied by applying the ONIOM (QM/MM) approach using HF/UFF and MP2/UFF combinations as levels of theory. The six experimentally observed Ag(I)···Ag(I) supported interactions are reproduced when dispersion-type interactions are considered in the theory levels MP2 and ONIOM MP2/UFF for models A and B, respectively. The use of HF and ONIOM HF/UFF levels led to a similar hexanuclear structure but displayed a large hexagonal disposition without argentophilic contacts for both models A and B. The steric hindrance exerted by the ligands did not preclude the formation of argentophilic interactions, as observed experimentally.


Assuntos
Complexos de Coordenação/química , Prata/química , Ânions/química , Cristalografia por Raios X , Ligação de Hidrogênio , Modelos Moleculares , Conformação Molecular , Propilaminas/química
11.
J Inorg Biochem ; 104(5): 551-9, 2010 May.
Artigo em Inglês | MEDLINE | ID: mdl-20144847

RESUMO

Compounds of the type [(AuPPh(3))(2)(xspa)]; H(2)xspa [x:p=3-phenyl-, f=3-(2-furyl)-, t=3-(2-thienyl)-, -o-py=3-(2-pyridyl)-, Clp=3-(2-chlorophenyl)-, -o-mp=3-(2-methoxyphenyl)-, -p-mp=3-(4-methoxyphenyl)-, -o-hp=3-(2-hydroxyphenyl)-, -p-hp=3-(4-hydroxyphenyl)-, -diBr-o-hp=3-(3,5-dibromo-2-hydroxyphenyl)-; spa=2-sulfanyl propenoato] were synthesized and characterized by IR and NMR ((1)H, (13)C and (31)P) spectroscopy and by FAB mass spectrometry. The structures of [(AuPPh(3))(2)(Clpspa)], [(AuPPh(3))(2)(o-hpspa)], [(AuPPh(3))(2)(p-hpspa)].MeOH and [(AuPPh(3))(2)(diBr-o-hpspa)].2Me(2)CO show the dinuclear nature of the complexes with the two gold atoms, one of which is also O-bonded to an O atom of the carboxylate group, bonded to the S atom. The in vitro antitumor activities against the HeLa-229, A2780 and A2780cis cell lines were determined and the compounds were found to be highly effective, in particular against the A2780cis cell line, with eight of the nine compounds having IC(50) values better than that of cisplatin. This behavior is indicative of a high ability to circumvent the cellular resistance to this drug.


Assuntos
Ácidos Carboxílicos , Linhagem Celular Tumoral/efeitos dos fármacos , Compostos Organoáuricos , Ácidos Carboxílicos/síntese química , Ácidos Carboxílicos/química , Ácidos Carboxílicos/farmacologia , Cristalografia por Raios X , Ensaios de Seleção de Medicamentos Antitumorais , Humanos , Modelos Moleculares , Dados de Sequência Molecular , Estrutura Molecular , Ressonância Magnética Nuclear Biomolecular , Compostos Organoáuricos/síntese química , Compostos Organoáuricos/química , Compostos Organoáuricos/farmacologia
12.
J Inorg Biochem ; 104(5): 599-610, 2010 May.
Artigo em Inglês | MEDLINE | ID: mdl-20211491

RESUMO

We investigated the reaction of Pb(2+), PbMe(2)(2+) and PbPh(2)(2+) with 3-(phenyl)-2-sulfanylpropenoic acid (H(2)pspa) to give the complexes [Pb(pspa)], [PbMe(2)(pspa)], [PbPh(2)(pspa)], [HQ](2)[Pb(pspa)(2)] and [HQ[(2)[PbPh(2)(pspa)(2)] (HQ=diisopropylammonium), which were characterized by IR and NMR ((1)H, (13)C and (207)Pb) spectroscopy and by fast atom bombardment (FAB) spectrometry. The structures of [PbMe(2)(pspa)], [PbPh(2)(pspa)], [PbPh(2)(pspa)(dmso)].dmso and [HQ[(2)[PbPh(2)(pspa)(2)] are interesting examples of unexplored Pb coordination kernels and supramolecular association. Pig renal proximal tubule LLC-PK1 culture cells were used to determine in vitro the effect of the pretreatment with H(2)pspa (alone or combined with vitamin B(6)) and [HQ](2)[Zn(pspa)(2)] on the cytotoxicity of PbMe(2)(2+) and PbPh(2)(2+) by comparing the results with those of meso-2,3-dimercaptosuccinic acid (dmsa). The results show that the cell viability was scarcely affected by these agents. The ability of these reagents to decorporate lead was investigated in vivo by analysing the lead levels in the liver, kidney, brain and blood. In the case of the dimethyl derivative, and under certain protocols, undesirable effects such as an increase in brain and liver lead levels were detected. These increases were not detected when the diphenyl derivative was assayed but in this case a positive effect was not identified either. The blood lead levels also increased in the case of the dimethyl derivative and the activity of delta-ALAD was significantly recovered upon treatment with vitamin B(6) or H(2)pspa; neither the blood lead levels nor the delta-ALAD activity was modified in the case of the diphenyl derivative.


Assuntos
Ácidos/química , Chumbo/química , Animais , Linhagem Celular , Cristalografia por Raios X , Humanos , Chumbo/metabolismo , Intoxicação por Chumbo/metabolismo , Masculino , Dados de Sequência Molecular , Estrutura Molecular , Ressonância Magnética Nuclear Biomolecular , Ratos , Ratos Sprague-Dawley
13.
J Inorg Biochem ; 103(7): 1023-32, 2009 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-19501912

RESUMO

Compounds of the type [HQ][Au(PPh(3))(xspa)] and [HP][Au(PPh(3))(xspa)] {HQ=diisopropylammonium; HP=triethylammonium; H(2)xspa=3-aryl-2-sulfanylpropenoic acids [x: p=3-phenyl-, f=3-(2-furyl)-, t=3-(2-thienyl)-, -o-py=3-(2-pyridyl)-, Clp=3-(2-chlorophenyl)-, -o-mp=3-(2-methoxyphenyl)-, -p-mp=3-(4-methoxyphenyl)-, -o-hp=3-(2-hydroxyphenyl)-, -p-hp=3-(4-hydroxyphenyl)-, diBr-o-hp=3-(3,5-dibromo-2-hydroxyphenyl]} were synthesized and characterized by IR and NMR ((1)H, (13)C and (31)P) spectroscopy and by FAB mass spectrometry. The structures of [HQ][Au(PPh(3))(Clpspa)] and [HQ][Au(PPh(3))(-o-mpspa)] show that the crystal contains hydrogen-bonded diisopropylammonium cations and [Au(PPh(3))(xspa)](-) anions. The anions in the two compounds have different structures, with the carboxylate group either coordinated or not coordinated to the gold atom, respectively. The in vitro antitumour activities against the HeLa-229, A2780 and A2780cis cell lines were determined for all complexes. The diisopropylammonium derivatives were generally found to be more active, in particular against the A2780cis cell line, and showed a high ability to circumvent the cellular resistance to cisplatin.


Assuntos
Antineoplásicos/química , Antineoplásicos/farmacologia , Compostos Organoáuricos/química , Compostos Organoáuricos/farmacologia , Compostos de Amônio Quaternário/química , Antineoplásicos/síntese química , Linhagem Celular Tumoral , Cristalografia por Raios X , Ensaios de Seleção de Medicamentos Antitumorais , Células HeLa , Humanos , Estrutura Molecular , Compostos Organoáuricos/síntese química
14.
Inorg Chem ; 46(16): 6236-8, 2007 Aug 06.
Artigo em Inglês | MEDLINE | ID: mdl-17602616

RESUMO

A mixture of pyridoxalrhodanine, triethylphosphinegold(I) chloride, and sodium methoxide in methanol unexpectedly afforded the azacoumarin complex [Au(TS)(PEt3)] [HTS = 5-(hydroxymethyl)-8-methyl-3-thiol-7-azacoumarin], which was characterized by X-ray diffractometry. Its crystals consist of independent molecules in which the metal atom is bound to the azacoumarin [Au-S = 2.9458(18) A] and the phosphine [Au-P = 2.262(2) A] in an almost linear arrangement [P1-Au1-S1 = 176.93(7) degrees]. The complex showed better in vitro antitumor activity than cisplatin against the cisplatin-resistant cell line A2780cis.


Assuntos
Cumarínicos/química , Ouro/química , Compostos Organoáuricos/química , Química Inorgânica/métodos , Concentração Inibidora 50 , Ligantes , Metanol/química , Modelos Químicos , Conformação Molecular , Temperatura , Termodinâmica
15.
Dalton Trans ; (28): 3074-85, 2007 Jul 28.
Artigo em Inglês | MEDLINE | ID: mdl-17622425

RESUMO

We have investigated the reactions of silver nitrate and 3-(aryl)-2-sulfanylpropenoic acids [H(2)xspa, x: p = 3-phenyl-, f = 3-(2-furyl)-, t = 3-(2-thienyl)-, py = 3-(2-pyridyl)-] and 2-cyclopentylidene-2-sulfanylacetic acid (H(2)L) in 1 : 1 and 2 : 1 molar ratios. The 1 : 1 molar ratio gave compounds of type [Ag(HL)]; reaction of these compounds with diisopropylamine and NaOH gave [HQ][Ag(L)] (HQ = diisopropylammonium) and Na[Ag(L)] x H(2)O, respectively. These compounds, as well as those of type [Ag(2)(L)] obtained with the 1 : 2 molar ratio, were isolated and characterized by IR and NMR ((1)H and (13)C) spectroscopy. (109)Ag NMR spectroscopy and ESI-MS spectrometry were also used in some cases. The crystal structures of [HQ][Ag(pspa)] (11), in which the presence of structural isomers was detected, and [HQ][Ag(cpa)] (15) were determined by X-ray diffractometry. The antimicrobial activity of the complexes against E. coli, S. aureus, B. subtilis, P. aeruginosa/Resistant P. aeruginosa, and C. albicans was tested.


Assuntos
Antibacterianos/síntese química , Antibacterianos/farmacologia , Ácidos Carboxílicos/química , Compostos de Prata/síntese química , Compostos de Prata/farmacologia , Prata/química , Enxofre/química , Ânions/química , Antibacterianos/química , Cristalografia por Raios X , Ligação de Hidrogênio , Isomerismo , Espectroscopia de Ressonância Magnética , Modelos Moleculares , Estrutura Molecular , Compostos de Prata/química , Espectrometria de Massas por Ionização por Electrospray , Espectrofotometria Infravermelho
16.
Dalton Trans ; (9): 1707-15, 2005 May 05.
Artigo em Inglês | MEDLINE | ID: mdl-15852122

RESUMO

We investigated the reactions of 1.5 : 1 : 1 mole ratio mixtures of triphenylphosphine, silver nitrate and 3-(aryl)-2-sulfanylpropenoic acids H(2)xspa in chloroform/water, where in the acid nomenclature, spa = 2-sulfanylpropenoato and x = p, Clp, mp, diBr-o-hp or f with p = 3-phenyl-, Clp = 3-(2-chlorophenyl)-, mp = 3-methoxyphenyl-, diBr-o-hp = 3-(3,5-dibromo-2-hydroxyphenyl)- and f = 3-(2-furyl)-. The compounds [Ag(PPh(3))(Hpspa)](1), [(AgPPh3)2(xspa)][x = Clp (2), o-mp (3), p-mp (4), diBr-o-hp (5) and f (6)] and [Ag(PPh3)3(Hfspa)](7) were isolated and all except 7 were characterized by IR, Raman and FAB mass spectrometry and by 1H, 13C and 31P NMR spectroscopy. Compound 6 was also characterized by (13)C CP/MAS, and compounds 1 and 6 by (109)Ag NMR spectroscopy. The crystal structures of 1, 2, 3, 4.(CH3)2CO, 5, 6.(CH3)2CO and 7 were determined by X-ray diffraction. has a supramolecular structure based on hydrogen bonding between dinuclear units, and all the other complexes adopt discrete structures. 2, 3, 4.(CH3)2CO, 5, and 6.(CH3)2CO are tetranuclear, and 7 mononuclear. The tetranuclear complexes contain the eight-membered coordination ring Ag4S2O2 (2, 3, 4.(CH3)2CO, 6.(CH3)2CO) or the twelve-membered ring Ag4(CO2)2S2 (5).


Assuntos
Compostos Organometálicos/química , Compostos de Enxofre/química , Ligação de Hidrogênio , Modelos Moleculares , Estrutura Molecular
17.
Inorg Chem ; 43(6): 1957-63, 2004 Mar 22.
Artigo em Inglês | MEDLINE | ID: mdl-15018516

RESUMO

The complex [SnMe(2)(HTDP)(H(2)O)]Cl.H(2)O, synthesized by reaction between dimethyltin(IV) dichloride and thiamine diphosphate hydrochloride (H(3)TDPCl) in water, was characterized by X-ray diffractometry and IR and Raman spectroscopy in the solid state, and by electrospray mass spectrometry (ESMS) and NMR spectroscopy ((1)H, (13)C, (31)P, (119)Sn and inverse-detection (1)H,(15)N HMBC) in aqueous solution. In the solid state the HTDP(-) anion chelates the metal via one oxygen atom of each phosphate group [Sn-O = 2.062(3), 2.292(3) A], and another oxygen atom belonging to the terminal phosphate links the SnMe(2)(2+) cations into chains. The tin atom has distorted octahedral coordination involving the trans methyl groups, the above-mentioned diphosphate oxygen atoms, and the oxygen atom of the coordinated water molecule. The thiamine moiety has F conformation. NMR studies suggest that the interaction between the organometallic cation and the HTDP(-) ligand persists in D(2)O solution, which is in keeping with the ESMS spectrum showing a peak corresponding to [SnMe(2)(HTDP)]. Both in the solid state and in solution, the acidic HTDP(-) proton in the complex is located on the N(1') atom of the pyrimidine ring. The enzymatic behavior of native pyruvate decarboxylase (EC 4.1.1.1, PDC), obtained from baker's yeast, was compared in a coupled assay with that shown by the "SnMe(2)-holoenzyme" created by incubation of apoPDC with [SnMe(2)(HTDP)(H(2)O)]Cl.H(2)O. The SnMe(2)-holoenzyme exhibited about 34% of the activity of the native enzyme (with a Michaelis-Menten constant of 2.7 microM, as against 6.4 microM for native PDC), so confirming the very low specificity of PDC regarding the identity of its metal ion cofactor. In view of the observed protonation of N(1'), it is suggested that the role of divalent cations in the mechanism of thiamine-diphosphate-dependent enzymes may be not only to anchor the cofactor in its binding site but also to shift the acidic proton of HTDP(-) from the diphosphate group to N(1'); protonation of N(1') is widely believed to be important for enzyme function, but the origin of the proton has never been clarified.


Assuntos
Compostos Orgânicos de Estanho/química , Tiamina Pirofosfato/química , Tiamina/química , Estanho/química , Catálise , Magnésio/química , Espectroscopia de Ressonância Magnética , Modelos Moleculares , Estrutura Molecular , Piruvato Descarboxilase/química , Saccharomyces cerevisiae/enzimologia , Espectrometria de Massas por Ionização por Electrospray , Espectrofotometria Infravermelho , Análise Espectral Raman , Tiamina Pirofosfato/síntese química , Água/química , Difração de Raios X
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