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1.
Chem Cent J ; 9: 69, 2015.
Artigo em Inglês | MEDLINE | ID: mdl-26715938

RESUMO

BACKGROUND: Hydrazones and their metal complexes were heavily studied due to their pharmacological applications such as antimicrobial, anticonvulsant analgesic, anti-inflammatory and anti-cancer agents. This work aims to synthesize and characterize novel complexes of VO(2+), Co(2+), Ni(2+), Cu(2+), Zn(2+), Zr(4+)and Pd(2+) ions with oxalo bis(2,3-butanedione-hydrazone). Single crystals of the ligand have been grown and analyzed. RESULTS: Oxalo bis(2,3-butanedionehydrazone) [OBH] has a monoclinic crystal with P 1 21/n 1 space group. The VO(2+), Co(2+), Ni(2+), Cu(2+), Zn(2+), Zr(4+) and Pd(2+) complexes have the formulas: [VO(OBH-H)2]·H2O, [Co(OBH)2Cl]Cl·½EtOH, [Ni2(OBH)Cl4]·H2O·EtOH, [Cu(OBH)2Cl2]·2H2O, [Zn(OBH-H)2], [Zr(OBH)Cl4]·2H2O, and [Pd2(OBH)(H2O)2Cl4]·2H2O. All complexes are nonelectrolytes except [Co(OBH)2Cl]Cl·½EtOH. OBH ligates as: neutral tetradentate (NNOO) in the Ni(2+) and Pd(2+) complexes; neutral bidentate (OO) in [Co(OBH)2Cl]Cl·½EtOH, [Zr(OBH)Cl4]·2H2O and [Cu(OBH)2Cl2]·2H2O and monobasic bidentate (OO) in the Zn(2+) and VO(2+) complexes. The NMR ((1)H and (13)C) spectra support these data. The results proved a tetrahedral for the Zn(2+) complex; square-planar for Pd(2+); mixed stereochemistry for Ni(2+); square-pyramid for Co(2+) and VO(2+) and octahedral for Cu(2+) and Zr(4+) complexes. The TGA revealed the outer and inner solvents as well as the residual part. The molecular modeling of [Ni2(OBH)Cl4]·H2O·EtOH and [Co(OBH)2Cl]Cl·½EtOH are drawn and their molecular parameters proved that the presence of two metals stabilized the complex more than the mono metal. The complexes have variable activities against some bacteria and fungi. [Zr(OBH)Cl4]·2H2O has the highest activity. [Co(OBH)2Cl]Cl·½EtOH has more activity against Fusarium. CONCLUSION: Oxalo bis(2,3-butanedionehydrazone) structure was proved by X-ray crystallography. It coordinates with some transition metal ions as neutral bidentate; mononegative bidentate and neutral tetradentate. The complexes have tetrahedral, square-planar and/or octahedral structures. The VO(2+) and Co(2+) complexes have square-pyramid structure. [Cu(OBH)2Cl2]·2H2O and [Ni2(OBH)Cl4]·H2O·EtOH decomposed to their oxides while [VO(OBH-H)2]·H2O to vanadium. The energies obtained from molecular modeling calculation for [Ni2(OBH)Cl4]·H2O·EtOH are less than those for [Co(OBH)2Cl]Cl·½EtOH indicating the two metals stabilized the complex more than mono metal. The Co(II) complex is polar molecule while the Ni(II) is non-polar.

2.
Artigo em Inglês | MEDLINE | ID: mdl-26073596

RESUMO

The reaction between 2,5-hexanedione and isonicotinic acid hydrazide in EtOH gave two products. The ethanol insoluble product was identified as 2,5-hexanedione bis(isonicotinylhydrazone) [HINH] and the soluble ethanol product as N-(2,5-dimethyl-1H-pyrrol-1-yl)isonicotinamide [DINA]. A series of Cr(3+), Fe(3+), Co(2+), Ni(2+), Cu(2+), Zn(2+), Cd(2+), Hg(2+) and Pd(2+) complexes of HINH and Co(2+), Cu(2+), Zn(2+) and Hg(2+) complexes of DINA have been synthesized and structurally characterized. Based on the elemental analysis, mass spectra and molar conductance, the complexes have assigned the proposed imperical formulae. The crystal structures of N-(2,5-dimethyl-1H-pyrrol-1-yl)isonicotinamide and its Zn(2+) and Hg(2+) complexes have been solved by X-ray diffraction having [Zn(DINA)2Cl2] and [Hg(DINA)2Cl2] in a tetrahedral structure. In the DINH complexes, the ligand coordinates as a monodentate through the pyridine nitrogen. On the other hand, HINH behaves as a tetradentate (neutral or binegative) manner with the two metal ions. The magnetic moments and electronic spectra of all complexes provide tetrahedral, square-planar, trigonal biyramid and/or octahedral structure. The thermal decomposition of the complexes revealed the outer and inner solvents as well as the end product. The steady part of [Zn(DINA)2Cl2] and [Hg(DINA)2Cl2] thermograms till 303 and 286 °C indicates the absence of any outside solvents. All compounds have activity against bacteria more than fungi. [Cd4(HINH)Cl8]·3H2O has the highest values.


Assuntos
Antibacterianos , Complexos de Coordenação , Hidrazonas , Niacinamida/química , Antibacterianos/síntese química , Antibacterianos/química , Antibacterianos/farmacologia , Complexos de Coordenação/síntese química , Complexos de Coordenação/química , Complexos de Coordenação/farmacologia , Cristalografia por Raios X , Hidrazonas/síntese química , Hidrazonas/química , Hidrazonas/farmacologia , Ácidos Isonicotínicos/síntese química , Ácidos Isonicotínicos/química , Ácidos Isonicotínicos/farmacologia , Espectroscopia de Ressonância Magnética , Espectrometria de Massas , Testes de Sensibilidade Microbiana , Modelos Moleculares , Conformação Molecular , Difração de Raios X
3.
Spectrochim Acta A Mol Biomol Spectrosc ; 145: 295-301, 2015 Jun 15.
Artigo em Inglês | MEDLINE | ID: mdl-25791887

RESUMO

A single crystal of 3,4-dihydroxybenzylidene isonicotinylhydrazone, HBINH, has been grown and solved by X-ray crystallography. The VO(2+), Zr(4+), Co(2+), Ni(2+), Cu(2+), Zn(2+), Cd(2+), Hg(2+) and Pd(2+) complexes of HBINH have been prepared and spectroscopically characterized. The data confirmed the formulae [Co(HBINH)(H2O)Cl]Cl·H2O, [Pd(HBINH)Cl2], [Zn(HBINH)2Cl2], [Cd(HBINH)(H2O)2Cl2]·1½H2O, [(VO)2(HBINH-3H)(OH)(H2O)], [Ni2(HBINH)(H2O)6Cl2]Cl2, [Cu2(HBINH-3H)(H2O)2(OAc)]·3H2O, [Zr2(HBINH-3H)Cl4]Cl, [Hg2(HBINH)Cl4] and the dimer {[Cu(HBINH)Cl]Cl}2. Most of the complexes have intense colors and high melting points and some are electrolytes in DMSO solution. The ligand behaves as a neutral bidentate in the Co(II), Cu(II), Pd(II), Zn(II) and Cd(II) complexes; dibasic tetradentate in [Ni2(HBINH)(H2O)6Cl2]Cl2 and tribasic tetradentate in [Cu2(HBINH-3H)(OAc)]·5H2O, [(VO)2(HBINH-3H)(OH)(H2O)] and [Zr2(HBINH-3H)Cl4]Cl by the loss of 3H(+) due to the deprotonation of the two hydroxyl groups and the enolization of the amide (OCNH) group. A tetrahedral geometry was proposed for the Co(II), Cu(II), Zn(II) and Hg(II) complexes; square-planar for the Pd(II) complex; square-pyramid for the VO(2+) complex and octahedral for the Ni(II) and Cd(II) complexes. The complexes [Cd(HBINH)(H2O)2Cl2]·1½H2O, [(VO)2(HBINH-3H)(OH)(H2O)] and [Cu2(HBINH-3H)-(H2O)2(OAc)]·3H2O have activities against Bacillus sp. M3010, Candida albicans, Escherichia coli, Staphylococcus aureus and Slamonella sp. PA393.


Assuntos
Anti-Infecciosos/química , Anti-Infecciosos/farmacologia , Complexos de Coordenação/química , Complexos de Coordenação/farmacologia , Hidrazonas/química , Hidrazonas/farmacologia , Isoniazida/química , Isoniazida/farmacologia , Bactérias/efeitos dos fármacos , Espectroscopia de Ressonância Magnética Nuclear de Carbono-13 , Cor , Cristalografia por Raios X , Elétrons , Fungos/efeitos dos fármacos , Ligantes , Fenômenos Magnéticos , Espectrometria de Massas , Testes de Sensibilidade Microbiana , Conformação Molecular , Peso Molecular , Espectroscopia de Prótons por Ressonância Magnética , Espectrofotometria Infravermelho , Termogravimetria , Temperatura de Transição
4.
Spectrochim Acta A Mol Biomol Spectrosc ; 134: 465-72, 2015 Jan 05.
Artigo em Inglês | MEDLINE | ID: mdl-25036455

RESUMO

Five metal complexes derived the reactions of 4-allyl-1-(2-hydroxybenzoyl) thiosemicarbazide (L(1)) with MX2 (M=Co(2+), Cu(2+) and Zn(2+) ions; X=Cl(-) in case of Co(2+) and Cu(2+) ions and Cl(-) and Ac(-) in case of Zn(2+) ion) in EtOH were synthesized and characterized. The results suggested that the binary and ternary complexes have the general formulae, [Cu(L(1)-2H)(EtOH)], [Co(L(1)-2H)(H2O)2]⋅H2O and [Zn(L(1)-2H) (H2O)1/2]⋅½EtOH, [Cu2(dipy)(L(1)-2H)(OH)2(H2O)], [Co(dipy)(L(1)-2H)]⋅4H2O and [Zn(dipy)(L(1)-2H)]. The binary and ternary complexes were characterized by elemental analyses, molar conductivities, spectral (IR, UV-vis; (1)H NMR, mass), thermal (TGA, DTG) and magnetic moments measurements. The mode of chelation is suggested using spectral data. The existence of OH group in the ternary complexes is confirmed from the results of IR, mass and (1)H NMR spectra. All the geometries of the ligands and the complexes are confirmed using DFT method from DMOL(3). The biological activity for the L(1) and two metal complexes were tested against DNA.


Assuntos
2,2'-Dipiridil/química , Compostos Alílicos/química , Complexos de Coordenação/química , Semicarbazidas/química , 2,2'-Dipiridil/farmacologia , Compostos Alílicos/farmacologia , Animais , Bovinos , Complexos de Coordenação/farmacologia , DNA/química , Clivagem do DNA/efeitos dos fármacos , Espectroscopia de Ressonância Magnética , Modelos Moleculares , Semicarbazidas/farmacologia , Espectrofotometria Infravermelho , Espectrofotometria Ultravioleta
5.
Spectrochim Acta A Mol Biomol Spectrosc ; 130: 546-52, 2014 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-24813284

RESUMO

Metal complexes of Fe3+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+, Hg2+, Pd2+ or Pt2+ with 2,5-hexanedione bis(thiosemicarbazone), HBTS; have been prepared and spectroscopically investigated. The empirical formulae of the complexes were suggested based on the elemental analysis. Single crystal of Pd(II) has been solved to be cis-form of square-planar geometry by the X-ray crystallography. 1H and 13C NMR spectra have been recorded for HBTS, Zn(II), Cd(II), Hg(II), Pd(II) and Pt(II) complexes, in DMSO-d6, showing the mode of chelation. The ligand acts as a neutral or a binegative tetradentate (N2S2) or neutral bidentate on the basis of FT-IR. The magnetic moments and electronic spectra provide information about the geometry of the complexes which supported by calculating the ligand field parameters for the Co(II) and Fe(III) complexes. The Ni(II) complex has subnormal magnetic moment (0.71 BM) indicative of a mixed stereochemistry of square-planar and tetrahedral structure. [Cu(HBTS-2H)] measured 0.93 BM indicating high interaction between the copper centers. The ligand may be ordered at the top of the spectrochemical series which giving high ligand field splitting energy (10 Dq=17,900 cm(-1) for Co2+ complex). The mass spectra of some complexes proved their stable chemical formulae while the TGA depicts the degradation steps and the final residue. In evaporating the mother liquor during the preparation of HBTS, new compound is obtained naming 1-(2,5-dimethyl-1H-pyrrol-yl)thiourea and its crystal was solved.


Assuntos
Carbono/química , Complexos de Coordenação/química , Espectrofotometria , Espectroscopia de Infravermelho com Transformada de Fourier , Tiossemicarbazonas/química , Tioureia/química , Cor , Cristalização , Cristalografia por Raios X , Ligantes , Espectroscopia de Ressonância Magnética , Magnetismo , Espectrometria de Massas , Metais/química , Solventes , Termogravimetria
6.
Spectrochim Acta A Mol Biomol Spectrosc ; 129: 307-13, 2014 Aug 14.
Artigo em Inglês | MEDLINE | ID: mdl-24747853

RESUMO

The reaction between 2,5-hexanedione and salicylic acid hydrazide produced two compounds: 2,5-hexanedione bis(salicyloylhydrazone) [HDSH] (ethanol insoluble) and N-(2,5-dimethyl-1H-pyrrol-1-yl)-2-hydroxybenzamide [DPH] (ethanol soluble). HDSH formed complexes with Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Hg(II) and Pd(II) which are characterized by elemental analyses, spectra (IR, (1)H NMR, ESR and MS), thermal and magnetic measurements. The crystals of [Ni(HDSH-2H)(EtOH)(H2O)] and [Cu(HDSH-2H)] were solved having octahedral and square-planar geometries, respectively. The other complexes have the formulae [Co(HDSH-2H)(H2O)2], [Cu(HDSH-H)2], [Zn(HDSH-2H)(H2O)2], [Cd2(HDSH-4H)(H2O)4], [Cd2(HDSH-2H)(H2O)4Cl2]; [Hg(HDSH-2H)] and [Pd2(HDSH-4H)(H2O)4]. The obtained complexes are stable in air and non-hygroscopic. The magnetic moments and electronic spectra of the complexes provide different geometries. The ESR spectra support the mononuclear geometry for [Cu(HDSH-2H)] and [Cu(HDSH-H)2]. The thermal decomposition of the complexes revealed the coordinated waters as well as the end product which is in most cases the metal oxide. The crystal structure of N-(2,5-dimethyl-1H-pyrrol-1-yl)-2-hydroxybenzamide is solved by X-ray technique.


Assuntos
Benzamidas/química , Complexos de Coordenação/química , Cobre/química , Hexanonas/química , Hidrazonas/química , Níquel/química , Benzamidas/síntese química , Complexos de Coordenação/síntese química , Cristalografia por Raios X , Hexanonas/síntese química , Hidrazonas/síntese química , Modelos Moleculares , Análise Espectral
7.
Artigo em Inglês | MEDLINE | ID: mdl-24530707

RESUMO

A single crystal of adipic acid dihydrazide, ADH, has been analyzed. Its reaction with Co(2+), Ni(2+), Cu(2+), Zn(2+), Cd(2+), Hg(2+), Ag(+), Pd(2+) and/or Pt(2+) gave homometallic and heterometallic complexes which are characterized by partial elemental analysis, spectra (MS, ESR, (1)H NMR, electronic; IR), thermal analysis and magnetic measurements. Some complexes: Zn(0.73)Cu(ADH)Cl4·H2O; Zn(0.71)Hg(0.36)(ADH)Cl4·H2O; Zn(0.65)Cd(0.46)(ADH)Cl4·½H2O; Zn(0.75)Co(0.41)(ADH-2H)Cl2·3H2O; Cd0.85Co0.43(ADH)Cl4·½EtOH were isolated having nonstiochiometric metal ratios. The ligand behaves as a neutral (bidentate or tetradentate) and/or binegative tetradentate. A square-pyramid, square-planar and tetrahedral structures were proposed for the homo Co(II), Cu(II) and Ni(II) complexes, respectively. A similar and different stereochemistry around each metal ion (tetrahedral+tetrahedral; tetrahedral+square-planar; tetrahedral+tetrahedral and/or tetrahedral+octahedral) was suggested for the heterometallic complexes. Some complexes were found highly stable with stability point >240 °C; the most stable is [HgNi(ADH-2H)Cl2]. The presence of diamagnetic atom (Zn, Cd or Hg) reduces the magnetic moments and gave anomalous moments. The degradation steps and the hydrated complexes are confirmed through the TGA study. The order of covalency of [Zn(0.73)Cu(ADH)Cl4]·H2O, [CdCu(ADH)Cl4]·H2O and [HgCu(ADH-2H)Cl2] matches with the size of the second metal (Zn complex>Cd complex>Hg complex). Some heterometallic complexes were found nonstoichiometric through the analysis of their metal content and supported by TGA.


Assuntos
Adipatos/química , Complexos de Coordenação/química , Cristalografia por Raios X , Espectroscopia de Ressonância de Spin Eletrônica , Elétrons , Espectroscopia de Ressonância Magnética , Espectrometria de Massas , Modelos Moleculares , Conformação Molecular , Espectrofotometria Infravermelho , Temperatura , Termogravimetria
8.
J Trace Elem Med Biol ; 27(4): 267-72, 2013 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-23669311

RESUMO

A highly sensitive and selective technique for the speciation of platinum by cloud point extraction prior to determination by graphite furnace atomic absorption spectrometry (GFAAS) was described. The separation of Pt(II) from Pt(IV) was performed in the presence of 4-(p-chlorophenyl)-1-(pyridin-2-yl)thiosemicarbazide (HCPTS) as chelating agent and Triton X-114 as a non-ionic surfactant. The extraction of Pt(II)-HCPTS complex needs temperature higher than the cloud point temperature of Triton X-114 and pH = 7, while Pt(IV) remains in the aqueous phase. The Pt(II) in the surfactant phase was analyzed by GFAAS, and the concentration of Pt(IV) was calculated by subtraction of Pt(II) from total platinum which was directly determined by GFAAS. The effect of pH, concentration of chelating agent, surfactant, and equilibration temperature were investigated. An enrichment factor of 42 was obtained for the preconcentration of Pt(II) with 50 mL solution. Under the optimum experimental conditions, the calibration curve was linear up to 30 µgL(-1) with detection limit of 0.08 µgL(-1) and the relative standard deviation was 1.8%. No considerable interference was observed due to the presence of coexisting anions and cations. The accuracy of the results was verified by analyzing different spiked samples (tap water, blood plasma and urine). The proposed method was applied to the speciation analysis of Pt in blood plasma and urine with satisfactory results.


Assuntos
Fracionamento Químico/métodos , Grafite/química , Micelas , Platina/sangue , Platina/urina , Espectrofotometria Atômica , Quelantes/química , Humanos , Concentração de Íons de Hidrogênio , Ligantes , Metanol/química , Octoxinol , Concentração Osmolar , Polietilenoglicóis/química , Temperatura , Fatores de Tempo
9.
Spectrochim Acta A Mol Biomol Spectrosc ; 77(1): 297-303, 2010 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-20541453

RESUMO

The molecular modeling and parameters have been calculated to confirm the geometry of oxalyl bis(3,4-dihydroxybenzylidene) hydrazone, H(6)L. The metal complexes of Cr(3+), VO(2+), ZrO(2+), HfO(2+), UO(2)(2+) and MoO(2)(2+) with H(6)L have been prepared and characterized by partial elemental analysis, spectral studies (electronic; IR), thermal analysis and magnetic measurements. The data suggest the formation of polymer complexes with a unit [Cr(H(4)L)(H(2)O)(3)Cl].H(2)O, [VO(H(4)L)(H(2)O)(2)], [Hf(H(4)L)(H(2)O)].H(2)O [UO(2)(H(4)L)(H(2)O)(2)].2H(2)O [MoO(2)(H(4)L)] and [(ZrO)(2)(H(2)L)-(C(2)H(5)OH)(2)]. The ligand behaves as a dibasic bidentate in all complexes except ZrO(2+) which acts as a tetrabasic tetradentate with the two ZrO(2+) ions. An octahedral geometry was proposed for the Cr(3+), HfO(2+), MoO(2)(2+)and UO(2)(2+) complexes and square pyramid for VO(2+). The Cr(3+) is necessary to degrade the DNA of eukaryotic subject completely; the other complexes have little effect. H(6)L was found suitable as a new reagent for the separation and preconcentration of ZrO(2+) ions from different water samples using flotation technique with satisfactory results.


Assuntos
Compostos de Benzil/química , Compostos de Benzil/farmacologia , Hidrazonas/química , Hidrazonas/farmacologia , Animais , Bovinos , Cor , DNA/efeitos dos fármacos , Espectroscopia de Ressonância de Spin Eletrônica , Elétrons , Íons , Magnetismo , Modelos Moleculares , Espectrofotometria Infravermelho , Temperatura , Termogravimetria , Zircônio/química
10.
Spectrochim Acta A Mol Biomol Spectrosc ; 75(5): 1516-22, 2010 May.
Artigo em Inglês | MEDLINE | ID: mdl-20189871

RESUMO

New VO(2+), Mn(2+), Co(2+), Ni(2+) Cu(2+) and Zn(2+) complexes of 2,5-hexanedione bis(isonicotinylhydrazone) [H(2)L] have been synthesized and characterized. The analyses confirmed the formulae: [VO(L)].H(2)O, [Mn(2)(H(2)L)Cl(2)(H(2)O)(6)]Cl(2), [Co(L)(H(2)O)(2)].2H(2)O, [Ni(HL)(OAc)].H(2)O, [Cu(L)(H(2)O)(2)].2H(2)O, [Cu(L)].2H(2)O and [Zn(L)(H(2)O)(2)]. The formulae of [Ni(HL)(OAc)].H(2)O, [Zn(L)(H(2)O)(2)] and [Mn(2)(H(2)L)Cl(2)(H(2)O)(6)]Cl(2), are supported by mass spectra. The molecular modeling of H(2)L is drawn and showed intramolecular hydrogen bonding. The ligand releases two protons during reaction from the two amide groups (NHCO) and behaves as a binegative tetradentate (N(2)O(2)); good evidence comes from the (1)H NMR spectrum of [Zn(L)(H(2)O)(2)]. The ligand has a buffering range 10-12 and pK's of 4.62, 7.78 and 9.45. The magnetic moments and electronic spectra of all complexes provide a square-planar for [Cu(L)].2H(2)O, square-pyramidal for [VO(L)].H(2)O and octahedral for the rest. The ESR spectra support the mononuclear geometry for [VO(L)].H(2)O and [Cu(L)(H(2)O)(2)].2H(2)O. The thermal decomposition of the complexes revealed the outer and inner solvents where the end product in most cases is metal oxide.


Assuntos
Complexos de Coordenação/química , Complexos de Coordenação/síntese química , Hidrazonas/química , Hidrazonas/síntese química , Elementos de Transição/química , Espectroscopia de Ressonância de Spin Eletrônica , Elétrons , Ligantes , Espectroscopia de Ressonância Magnética , Magnetismo , Espectrometria de Massas , Modelos Moleculares , Espectrofotometria Infravermelho , Temperatura , Termogravimetria
11.
Anal Sci ; 23(12): 1403-8, 2007 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-18071226

RESUMO

Ga(III), In(III) and Tl(III) ions in the presence of different sulfate salts have been successfully separated using 1-(3,4-dihydroxybenzaldehyde)-2-acetylpyridiniumchloride hydrazone (DAPCH) loaded on Duolite C20 in batch and column modes. The obtained modified resin as well as the metal complexes was characterized by elemental analysis and infrared spectra. The extraction isotherms were determined at different pH values. Ga(III) and In(III) are sorbed from aqueous solution at pH 2.5 - 3.0 while Tl(III) is sorbed at 2.0. The stripping of the adsorbed ions can be carried out using different concentrations of HCl as eluent. The saturation sorption capacities of Ga(III), In(III) and Tl(III) were 0.82, 0.96 and 0.44 mmol g(-1), where the preconcentration factors are 150, 150 and 100, respectively. The metal(III):Duolite C20-DAPCH ratio was 1:2 for Tl(III) and 1:1 for In(III) and Ga(III). The loaded resin can be regenerated for at least 50 cycles. The utility of the modified resin was tested in aqueous samples and the results show an RSD value of < 5% reflecting their accuracy and reproducibility.

12.
Anal Sci ; 21(11): 1325-35, 2005 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-16317901

RESUMO

1-(2-Hydroxy-4-methoxybenzophenone)-4-phenylthiosemicarbazone (HMBPT) was investigated as a new reagent for the flotation of vanadium(IV). At pH approximately 1.5, vanadium(IV) forms a 1:1 pale-violet complex with HMBPT in aqueous solution. An intense clear violet layer was formed after flotation, by adding an oleic acid (HOL) surfactant. The composition of the float was 1:1 [V(IV)]:[HMBPT]. A highly selective and sensitive spectrophotometric procedure was proposed for the determination of microamounts of V(IV) as its floated complex. The molar absorptivities of the V(IV)-HMBPT and V(IV)-HMBPT-HOL systems were 0.4 x 10(4) and 0.12 x 10(5) L mol(-1) cm(-1) at 560 nm, respectively. The formation constants of the species formed in the presence and absence of HOL were 4.6 x 10(7) and 8.7 x 10(5) L mol(-1), respectively. Beer's law was obeyed up to 1 x 10(-4) mol L(-1) in the aqueous layer as well as in the oleic acid layer. The HMBPT-V(IV) complexes formed in the aqueous solution and scum layer were characterized by elemental analysis, infrared and UV spectrophotometric studies. The mode of chelation between V(IV) and HMBPT is proposed to be due to a reaction between the protonated bidentate HMBPT ligand and V(IV) through the S=C and N=C groups. Interferences from various foreign ions were avoided by adding excess HMBPT and/or Na2S2O3 as a masking agent. The proposed flotation method was successfully applied to the analysis of V(IV) in synthetic mixtures, wastes of power stations, simulated samples and in real ores. The separation mechanism is discussed.


Assuntos
Resíduos Industriais/análise , Centrais Elétricas , Vanádio/análise , Benzofenonas/química , Cátions/química , Quelantes/química , Água Doce/análise , Concentração de Íons de Hidrogênio , Estrutura Molecular , Ácido Oleico/química , Concentração Osmolar , Água do Mar/análise , Espectrofotometria , Espectrofotometria Infravermelho , Espectrofotometria Ultravioleta , Temperatura , Tiossemicarbazonas/química , Vanadatos/análise , Vanadatos/química , Vanádio/química
13.
Urology ; 59(6): 861-4, 2002 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-12031369

RESUMO

OBJECTIVES: To evaluate the role of noncontrast computed tomography (NCCT) in the determination of the cause of obstructive anuria and to compare its accuracy with that of the traditional methods of combined plain abdominal x-ray (KUB) and gray-scale abdominal ultrasonography (US). METHODS: The study included 40 consecutive patients with obstructive anuria. In addition to the routine evaluation, which included history, clinical examination, biochemical profile, KUB, and US, all patients underwent NCCT. The study patients were tested against an age and sex-matched control group that included the normal contralateral kidneys of 57 consecutive patients who underwent KUB, US, and NCCT for acute flank pain during the same study period. The reference standard for the determination of the cause of obstruction was retrograde or antegrade ureterography with or without ureteroscopy or open surgery. The absence of obstruction in the control group was confirmed by nonequivocal normal intravenous urography of the side free of flank pain. Both NCCT and combined KUB and US were compared regarding the sensitivity, specificity, and overall accuracy. RESULTS: The study group had 48 renal units, because obstruction was bilateral in 8 patients and of a solitary kidney in 32. Of the 42 renal units with calculus obstruction, the site of stone impaction was identified in all renal units by NCCT (sensitivity 100%) and in only 25 by combined KUB and US (sensitivity 59.5%)-a significant difference (P = 0.0001). Of the 6 renal units with noncalcular obstruction, both NCCT and US diagnosed the cause of obstruction in 3. The overall sensitivity of NCCT in the determination of the cause of obstructive anuria was 94% and that of combined KUB and US was 58%-a significant difference (P = 0.0001). The specificity of NCCT was not significantly different from that of combined KUB and US (96.5% versus 93%, respectively). The overall accuracy of NCCT was 95% and that of combined KUB and US was 77%-a significant difference (P = 0.0003). CONCLUSIONS: In patients with obstructive anuria, conventional KUB and US could not identify the cause of ureteral obstruction in about 40% of the patients. Under such conditions, NCCT can accurately provide the diagnosis, obviating the need of invasive and expensive diagnostic procedures.


Assuntos
Anuria/diagnóstico por imagem , Tomografia Computadorizada por Raios X/métodos , Obstrução Ureteral/diagnóstico por imagem , Estudos de Casos e Controles , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , Estudos Prospectivos , Sensibilidade e Especificidade , Ultrassonografia , Cálculos Ureterais/complicações , Cálculos Ureterais/diagnóstico por imagem , Neoplasias Ureterais/complicações , Neoplasias Ureterais/diagnóstico por imagem
14.
Urology ; 59(4): 506-10, 2002 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-11927300

RESUMO

OBJECTIVES: To study the values of the renal resistive index (RI) before and at different points after relief of obstructive anuria and to correlate these values with the corresponding values of serum creatinine and with the recovery of renal function after release of obstruction. METHODS: A total of 32 consecutive patients with obstructive anuria were prospectively evaluated by measurement of RI before drainage and at 3 days, 1 week, 2 weeks, and 4 weeks after drainage. Serum creatinine was measured at all points of the RI examination. Moreover, RI was measured in an age and sex-matched control group of 24 consecutive healthy donors and volunteers. RESULTS: The study included 40 obstructed and 48 normal kidneys. In the obstructed kidneys, the mean RI values decreased significantly from 0.78 +/- 0.05 before drainage to 0.70 +/- 0.09 at 3 days after drainage (P <0.001) with an additional significant reduction to 0.68 +/- 0.08 at 7 days after drainage (P <0.01) and stabilized thereafter. Serum creatinine decreased significantly from 8.4 +/- 4.4 mg/dL before drainage to 4.7 +/- 3.8 mg/dL 3 days after drainage (P <0.001) and then to 3.6 +/- 3.7 mg/dL 7 days after drainage (P <0.001) and stabilized thereafter. The correlation between the RI and serum creatinine at the overall points of measurement was good. Obstructed kidneys were classified into two groups according to the recovery of renal function after obstruction relief: those that showed significant improvement of serum creatinine (24 kidneys, group 1) and those with no significant improvement of serum creatinine (16 kidneys, group 2). In group 1, the difference between the mean RI values before and after drainage was statistically significant (0.78 +/- 0.05 versus 0.64 +/- 0.06, P <0.001); in group 2, the difference between the before and after drainage RI values was not significant (0.781 +/- 0.040 versus 0.779 +/- 0.039). The mean RI of the normal kidneys was 0.66 +/- 0.04. A comparison between the mean RI values of the control group and the mean RI values of the obstructed patients after drainage showed no significant difference in group 1; markedly higher values were noted in group 2 at all points after drainage. CONCLUSIONS: In the setting of acute complete renal obstruction, the RI has a good positive correlation with serum creatinine. Recovery of renal function could not be predicted from the changes in RI before obstruction release. However, a reversal of a previously elevated RI could be used as an early indicator that renal function recovery is likely.


Assuntos
Obstrução Ureteral/fisiopatologia , Adulto , Idoso , Creatinina/urina , Drenagem , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , Nefrostomia Percutânea , Estudos Prospectivos , Resultado do Tratamento , Obstrução Ureteral/terapia , Obstrução Ureteral/urina
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