RESUMO
In this paper, a coumarin-based Schiff base chemosensor has been synthesized and developed to detect Cu2+ and Zn2+ ions in nanomolar concentrations. The probe selectively distinguishes Cu2+ and Zn2+ from among several metal ions in DMF : H2O (7 : 3, v/v, pH 7.4) HEPES buffer. The structure of the probe and its sensing behavior were investigated by FT-IR, UV-vis, fluorescence, HRMS, and NMR analyses, along with X-ray crystallography and computational studies. CIH detects Zn2+ and Cu2+ using different strategies: CHEF-induced fluorescence enhancement and paramagnetic fluorescence quenching, respectively. Job's plots show a 1 : 1 binding interaction between CIH and Cu2+ or Zn2+ ions. The binding constant values for Cu2+ (1.237 × 105 M-1) and Zn2+ (1.24 × 104 M-1) suggest a better ability for Cu2+ to interact with CIH than Zn2+. An extremely high sensitivity of the probe was highlighted by its very low detection limits (LOD) of 5.36 nM for Cu2+ and 3.49 nM for Zn2+. The regeneration of the probe with the addition of EDTA in its complexes allows the formation of molecular logic gates. CIH has been successfully employed in mitotracking and intracellular detection of Zn2+ and Cu2+ in SiHa cells.
Assuntos
Cobre , Cumarínicos , Corantes Fluorescentes , Bases de Schiff , Zinco , Zinco/análise , Zinco/química , Cumarínicos/química , Cobre/análise , Cobre/química , Humanos , Corantes Fluorescentes/química , Corantes Fluorescentes/síntese química , Bases de Schiff/química , Limite de Detecção , Espectrometria de Fluorescência/métodos , Imagem Óptica/métodosRESUMO
A thiazole-based probe, N'-((2-aminothiazol-5-yl)methylene)benzohydrazide (TBH), has been efficiently synthesized and characterized for the selective and sensitive detection of the neurotransmitter epinephrine (EP). The sensing strategy is based on the use of TBH for sequential colorimetric sensing of Ag+ and EP via in situ formation of Ag nanoparticles (Ag NPs) from the TBH-Ag+ complex. The generated Ag NPs lead to a bathochromic shift in absorption maximum and a change in color of the solution from light brown to reddish brown. TBH-Ag+ shows remarkable selectivity toward EP versus other drugs, common cations, anions, and some biomolecules. Moreover, TBH-Ag+ has a low detection limit for EP at 1.2 nM. The coordination of TBH-Ag+ has been proposed based on Job's plot, Fourier transform infrared spectroscopy (FT-IR), high-resolution mass spectrometry (HRMS), 1H NMR titration, X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray analysis (EDAX), and density functional theory (DFT) studies. The composition and morphology of the generated Ag NPs have been analyzed by XPS, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and dynamic light scattering (DLS). The proposed sensing mechanism for EP has been supported by XPS of Ag after the reaction. Further, the sensitivity of TBH-Ag+ toward EP in brain tissues of an Alzheimer's disease model of mouse has been evaluated. A thorough comparison was done for evaluation of the proposed method.
Assuntos
Doença de Alzheimer , Encéfalo , Colorimetria , Epinefrina , Prata , Tiazóis , Doença de Alzheimer/diagnóstico por imagem , Doença de Alzheimer/diagnóstico , Doença de Alzheimer/metabolismo , Prata/química , Animais , Camundongos , Epinefrina/análise , Tiazóis/química , Encéfalo/metabolismo , Encéfalo/diagnóstico por imagem , Teste de Materiais , Modelos Animais de Doenças , Materiais Biocompatíveis/química , Materiais Biocompatíveis/síntese química , Tamanho da Partícula , Nanopartículas Metálicas/química , Estrutura Molecular , Íons/químicaRESUMO
A diarylethene-based probe (Z)-N'-((2-amino-5-chlorophenyl)(phenyl)methylene)-2-hydroxy benzohydrazide (KBH) has been proficiently developed and its structure has been confirmed by single crystal X-ray diffraction technique. It displays a selective and sensitive colorimetric sensing of Cu2+ ions in aqueous medium with a naked eye colour change from colourless to yellow. It exhibits a significantly low limit of detection as 1.5 nM. A plausible binding mechanism has been proposed using Job's plot, FT-IR, 1H NMR titration, HRMS and DFT studies. The chemosensor is effectively reversible and reusable with EDTA. Test strip kit and real water sample analysis have been shown to establish its practical applicability. Further, the potential of KBH for the early diagnosis of Cu2+ ion-induced amyloid toxicity has been investigated in eye imaginal disc of Alzheimer's disease model of Drosophila 3rd instar larvae. The in-vivo interaction of KBH with Cu2+ in gut tissues of Drosophila larvae establishes its sensing capability in biological system. Interestingly, the in-vivo detection of Cu2+ has been done using bright field imaging which eliminates the necessity of a fluorescent label, hence making the method highly economical.
RESUMO
A new anthracene-based probe (E)-N'-(1-(anthracen-9-yl)ethylidene)-2-hydroxybenzohydrazide (AHB) has been efficiently synthesized and characterized by various spectroscopic methods. It exhibits extremely selective and sensitive fluorometric sensing of Al3+ ions with a large enhancement in the fluorescent intensity due to the restricted photoinduced electron transfer (PET) mechanism with a chelation-enhanced fluorescence (CHEF) effect. The AHB-Al3+ complex shows a remarkably low limit of detection at 0.498 nM. The binding mechanism has been proposed based on Job's plot, 1H NMR titration, Fourier transform infrared (FT-IR), high-resolution mass spectrometry (HRMS), and density functional theory (DFT) studies. The chemosensor is reusable and reversible in the presence of ctDNA. The practical usability of the fluorosensor has been established by a test strip kit. Further, the therapeutic potential of AHB against Al3+ ion-induced tau protein toxicity has been tested in the eye of Alzheimer's disease (AD) model of Drosophila via metal chelation therapy. AHB shows great therapeutic potential with 53.3% rescue in the eye phenotype. The in vivo interaction study of AHB with Al3+ in the gut tissue of Drosophila confirms its sensing efficiency in the biological environment. A detailed comparison table included evaluates the effectiveness of AHB.
Assuntos
Alumínio , Doença de Alzheimer , Animais , Alumínio/análise , Alumínio/química , Espectroscopia de Infravermelho com Transformada de Fourier , Doença de Alzheimer/tratamento farmacológico , Drosophila , Corantes Fluorescentes/química , Espectrometria de Fluorescência/métodos , AntracenosRESUMO
Access to 1,3-functionalized azetidines through a diversity-oriented approach is highly sought-after for finding new applications in drug-discovery. To this goal, strain-release-driven functionalization of azabicyclo[1.1.0]-butane (ABB) has generated significant interest. Through appropriate N-activation, C3-substituted ABBs are shown to render tandem N/C3-fucntionalization/rearrangement, furnishing azetidines; although, modalities of such N-activation vis-à-vis N-functionalization remain limited to selected electrophiles. This work showcases a versatile cation-driven activation strategy of ABBs. And capitalizes on the use of Csp3 precursors amenable to forming reactive (aza)oxyallyl cations in situ. Herein, N-activation leads to formation of a congested C-N bond, and effective C3 activation. The concept was extended to formal [3+2] annulations involving (aza)oxyallyl cations and ABBs, leading to bridged bicyclic azetidines. Besides the fundamental appeal of this new activation paradigm, operational simplicity and remarkable diversity should engender its prompt use in synthetic and medicinal chemistry.
RESUMO
The colorimetric and fluorescence responses of a new rhodamine-functionalized probe (E)-2-(((5-chloro-3-methyl-1-phenyl-1H-pyrazol-4-yl)methylene)amino)-3',6'-bis(diethylamino)spiro[isoindoline-1,9'-xanthen]-3-one (RMP) are investigated. RMP has been thoroughly characterized using various spectroscopic tools and single crystal X-ray diffraction. Among different competing cations, it shows highly sensitive colorimetric and "OFF-ON" fluorescence responses towards Al3+, Fe3+and Cr3+metal ions. The spectral shifts are clearly noticeable in the visible region of the absorption spectrum and can be observed with the naked eye. Fluorescence quantum yield, stoichiometric ratio, binding constant and detection limit of RMP towards Al3+, Fe3+and Cr3+metal ions have been calculated. Furthermore, RMP-M3+ complexes are reversible and sensitive to EDTA, which effectively mimics a molecular logic gate. Al3+, Fe3+and Cr3+metal ions have been further applied in intracellular application in model human cells.
Assuntos
Colorimetria , Corantes Fluorescentes , Humanos , Rodaminas/química , Corantes Fluorescentes/química , Espectrometria de Fluorescência/métodos , Metais , Cátions , PirazóisRESUMO
A novel catalytic system of a nickel(II) complex of (E)-N'-((2-amino-5-chlorophenyl)(phenyl)methylene)-2-hydroxy-benzohydrazide (APH) supported on graphene oxide (GO) has been prepared. Detailed characterization of the synthesized catalyst has been carried out using NMR, FTIR, HRMS, PXRD, Raman, SEM, TEM, EDX and XPS. Its catalytic efficiency has been explored for the synthesis of various bis(indolyl)methane derivatives. The optimized reaction conditions prove that the catalyst is highly efficient, performs under mild conditions and is required in a very small amount (2 wt%). A diversified library of bis(indolyl)methane derivatives containing various electron donating and withdrawing substituents has been developed in high to excellent yields. The catalyst is equally efficient towards heterocyclic aldehydes. Moreover, owing to the strong covalent interaction between the APH-Ni(II) complex and GO, the catalyst shows outstanding recyclability for six subsequent cycles without any significant loss in activity.
RESUMO
A novel quinazoli-4-one based ionic liquid, 1-(3-aminopropyl)-3-methyl-4-oxo-3,4-dihydroquinazolin-1-ium bromide (QIL) for fluorometric determination of dissolved ammonia has been successfully synthesized and characterized by spectroscopic techniques such as 1H and 13C NMR, FTIR and HRMS spectrometry. In the proposed method, QIL is converted to a fluorescent derivative by the reaction with ammonia in aqueous medium. The excitation and emission wavelengths were 250 and 436 nm, respectively. Remarkably with the reaction time of >1 s, the binding constant and detection limit was found to be 6.43 × 108 M-1 and 0.73 × 10-8 M, respectively. QIL is found to be highly selective as no interference is observed from various cations, anions, organic molecules and amino acids. The sensing mechanism was further validated by the density functional theory studies. The fluorophore exhibited great sensing property in 3.0-14.0 pH range, hence, it can be employed in diverse matrices. In addition, the fluoro-sensor is highly reversible and reusable in the presence of ctDNA molecule. Moreover, a live-cell imaging study of QIL in Drosophila larval gut tissue has also been carried out to investigate the cell permeability of QIL and its efficiency for selective detection of NH3 in cellular micro environment. To show practical applicability of the fluoro-sensor, test strip kit has been constructed. A detailed comparison table has been shown to evaluate the efficiency of this method.
Assuntos
Líquidos Iônicos , Amônia , Corantes Fluorescentes/química , ÁguaRESUMO
Metal ions such as Co2+, Cu2+ and Zn2+ have extensive applications in biological and industrial realms, but the toxicity caused by these ions poses a serious threat to mankind. However, there is no report in the literature on the development of a chemosensor for distinguishable detection of these toxic ions. Addressing this challenge, a multifunctional probe as a basic pH indicator with both colorimetric and fluorescence turn-on responses has been reported. The probe selectively discriminates Co2+, Cu2+ and Zn2+ ions with brown, dark yellow and greenish yellow colors, respectively, in DMF : water (9 : 1 v/v, HEPES 10 mM). Additionally, a fluorescence turn-on response specific to Zn2+ has also been observed. The sensing mechanism has been explored using UV-Vis, fluorescence spectroscopy and 1H NMR titration and confirmed with computational results. The inhibition of CîN isomerization and excited state intramolecular proton transfer (ESIPT) along with chelation enhanced fluorescence emission (CHEF) result in fluorescence enhancement with Zn2+. Job's plot and HRMS spectra confirm a 1 : 1 (L : M) stoichiometry between the probe and metal ions. The probe is able to exhibit excellent viscochromism in DMF : glycerol medium. Live cell imaging on SiHa cells has been successfully performed for intra-cellular detection of Zn2+ at basic pH. Furthermore, the probe displays its utility in mitotracking and monitoring cytoplasmic viscosity changes in SiHa cells. It is efficiently used to recognize the apoptosis process by displaying an enhancement in fluorescence intensity from cancerous SiHa cells to apoptotic cells.
Assuntos
Corantes Fluorescentes , Metais , Apoptose , Corantes Fluorescentes/química , Concentração de Íons de Hidrogênio , Metais/química , Viscosidade , Zinco/químicaRESUMO
This work presents the synthesis, characterization, crystal structure and spectroscopic investigations of isophthalohydrazide based probe. Among various tested metal ions, the probe selectively detects Al3+ and Cu2+ in aqueous ethanol via fluorometric and colorimetric methods, respectively. It displays a fluorescence "turn-on" response with Al3+ and visual colour change from colourless to yellow with Cu2+. Sensing mechanism is explored with UV-Vis, fluorescence spectroscopy and 1H NMR titration, and confirmed with computational results. Suppression of CN isomerization and photo-induced electron transfer (PET) along with chelation enhanced fluorescence emission (CHEF) result in "turn-on" fluorescence with Al3+ while ligand to metal charge transfer (LMCT) accounts for visual colour change with Cu2+. Job's plot and HRMS confirm 1:2 (L:M) stoichiometry. The probe also exhibits efficient reversibility and reproducibility with EDTA which are successfully mimicked with combinatorial logic gate and truth table. Additionally, solid state applications and bio-imaging investigation on gut tissue of Drosophila 3rd instar larvae are performed.
Assuntos
Colorimetria , Corantes Fluorescentes , Lógica , Reprodutibilidade dos Testes , Espectrometria de FluorescênciaRESUMO
The nature and coordination sites of the Schiff base 3,3'-(1E,1'E)-(1,3-phenylenebis(azan-1-yl-1-ylidene))bis(methan-1-yl-1-ylidene)dinaphthalen-2-ol (APHN) were tuned by its selective reduction to design a highly efficient fluorescent probe, 3,3'-(pyridine-2,6-diylbis(azanediyl))bis(methylene)dinaphthalen-2-ol (RAPHN). The structures of APHN, RAPHN, and the RAPHN-Fe3+ complex were satisfactorily modeled from the results of density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations. RAPHN worked in pure aqueous medium as a turn on-off-on probe of Fe3+ and F-. The fluorescence nature of the probe in the presence and absence of Fe3+/F- was regulated by a set of mechanisms including -CH[double bond, length as m-dash]N isomerization and LMCT. A 2 : 1 (M : L) binding stoichiometry was established from a fluorescence Job's plot and further substantiated from HR-MS studies. The limits of detection of RAPHN for Fe3+ and RAPHN-Fe3+ for F- were found to be 2.49 × 10-7 M and 1.09 × 10-7 M, respectively. The RAPHN probe caused no cytotoxicity in gut tissue of Drosophila even at high concentrations. The probe displayed excellent bioimaging applications for detection of Fe3+ and F- in gut tissue of Drosophila. A combinatorial logic gate was constructed for the proper understanding of the working principle of RAPHN.
Assuntos
Complexos de Coordenação/química , Corantes Fluorescentes/química , Íons/análise , Bases de Schiff/química , Animais , Técnicas Biossensoriais , Linhagem Celular , Teoria da Densidade Funcional , Drosophila , Intestinos/citologia , Cinética , Ligantes , Modelos Moleculares , Naftalenos/química , Espectrometria de FluorescênciaRESUMO
The ligand, N'-(phenyl-pyridin-2-yl-methylene)-thiophene-2-carboxylic acid hydrazide (Hpmtc) derived from thiophene-2-carboxylic acid hydrazide and 2-benzoyl pyridine, and its metal complexes with Co(II), Ni(II), Cu(II) and Zn(II) have been synthesized. These compounds are characterized by elemental analyses, magnetic susceptibility measurements, IR, NMR and UV-Vis spectral studies. The molecular structures of Hpmtc and its Co(II) (1), Ni(II) (2), Cu(II) (3) and Zn(II) (4) complexes are finally determined by X-ray crystallography. Various spectral and single-crystal X-ray diffraction studies suggest that Hpmtc coordinates with metal ions as a monobasic tridentate ligand forming mononuclear distorted octahedral complexes of the type [M(pmtc)2]. The molecular structures of the complexes are stabilized by CHâ¯N, CHâ¯O intermolecular H-bonding, and CHâ¯π and πâ¯π interactions. The DNA binding experiment of the complexes 1, 3 and 4 by UV-Vis absorption, and EB-DNA displacement by fluorescence spectroscopy, reveal an intercalative mode of binding between CT-DNA (calf-thymus DNA) and the metal complexes. These complexes exhibit a moderate ability to cleave pBR322 plasmid DNA. A comparative bovine serum albumin (BSA) protein binding activity of the complexes 1, 3 and 4 has also been determined by UV-Vis absorption and fluorescence spectroscopy. The DNA binding and protein binding studies suggest that the complex 3 exhibits more effective binding activity (Kb=5.54×10(5) and Kq=1.26×10(6) M(-1), respectively) than complexes 1 and 4. However, the complex 1 shows better hydrolytic DNA cleavage activity compared to 3 and 4 complexes.
Assuntos
Complexos de Coordenação/síntese química , Complexos de Coordenação/metabolismo , DNA/metabolismo , Hidrazinas/metabolismo , Piridinas/metabolismo , Tiofenos/metabolismo , Animais , Ligação Competitiva , Espectroscopia de Ressonância Magnética Nuclear de Carbono-13 , Bovinos , Complexos de Coordenação/química , Cristalografia por Raios X , Clivagem do DNA , Elétrons , Etídio/metabolismo , Hidrazinas/química , Ligação de Hidrogênio , Ligantes , Fenômenos Magnéticos , Conformação Molecular , Ligação Proteica , Espectroscopia de Prótons por Ressonância Magnética , Piridinas/química , Soroalbumina Bovina/metabolismo , Espectrometria de Fluorescência , Espectrofotometria Infravermelho , Espectrofotometria Ultravioleta , Tiofenos/químicaRESUMO
Primary intrarenal teratomas are uncommon, and their association with renal dysplasia is rarer. We report a case of primary renal teratoma in a 1-year-old child who had undergone a retroperitoneoscopic nephrectomy. Pathologic examination showed evidence for a primary mature teratoma with renal dysplasia.
RESUMO
Cobalt(II), nickel(II), copper(II), zinc(II) and cadmium(II) complexes with two new unsymmetrical ligands, isatin salicylaldehyde oxalic acid dihydrazide (isodh) and isatin salicylaldehyde malonic acid dihydrazide (ismdh) were synthesized and characterized by elemental analyses, electrical conductance, magnetic moments, electronic, NMR, ESR and IR spectral studies. The isodh acts as a dibasic tetra dentate ligand bonding through two >C=N-, a deprotonated phenolate and deprotonated indole enolate groups to the metal. The ismdh ligand shows monobasic tetra dentate behaviour in bonding with metal ion through two >C=N-, indole >C=O and a deprotonated phenolate group. The electronic spectral data suggest 4-coordinate square planar geometry for Co(II), Ni(II) and Cu(II) complexes of isodh, whereas, 6-coordinate octahedral structure for the ismdh complexes. The ESR studies also indicate a square planar and distorted octahedral environment around Cu(II) for isodh and ismdh complexes, respectively. Most of the metal complexes show better antifungal activity than the standard and a significant antibacterial activity against various fungi and bacteria.
Assuntos
Antibacterianos/síntese química , Antibacterianos/farmacologia , Antifúngicos/síntese química , Antifúngicos/farmacologia , Complexos de Coordenação/química , Hidrazonas/química , Compostos Organometálicos/farmacologia , Elementos de Transição/química , Antibacterianos/química , Antifúngicos/química , Bactérias/efeitos dos fármacos , Fungos/efeitos dos fármacos , Testes de Sensibilidade Microbiana , Compostos Organometálicos/síntese química , Compostos Organometálicos/química , Relação Estrutura-Atividade , Elementos de Transição/farmacologiaRESUMO
The title compound, C(15)H(15)N(3)O, was obtained by a condensation reaction between o-amino-acetophenone and benzoyl hydrazine. The mol-ecule displays an E configuration about the C=N bond. Intra-molecular N-Hâ¯N hydrogen bonds are formed between the 2-amino-phenyl and imine groups. In the crystal, dimers are formed between mol-ecules linked by inter-molecular N-Hâ¯O hydrogen bonds from the 2-amino-phenyl group. In addition there are inter-molecular N-Hâ¯O hydrogen bonds between the amine and carbonyl groups of adjacent mol-ecules. The mol-ecule is twisted rather than planar due to a steric inter-action between the central amide group and the two outer benzene rings. The dihedral angles between this central group and the two rings are 23.29â (9) and 24.96â (9)°.
RESUMO
Complexes of the type [M(pabh)(H2O)Cl], [M(pcbh)(H2O)Cl] and [M(Hpabh)(H2O)2 (SO4)] where, M = Mn(II), Co(II), Ni(II), Cu(II) and Zn(II); Hpabh = p-amino acetophenone benzoyl hydrazone and Hpcbh = p-chloro acetophenone benzoyl hydrazone have been synthesized and characterized with the help of elemental analyses, electrical conductance, magnetic susceptibility measurements, electronic, ESR and IR spectra, thermal (TGA & DTA) and X-ray diffraction studies. Co(II), Ni(II) and Cu(II) chloride complexes are square planar, whereas their sulfate complexes have spin-free octahedral geometry. ESR spectra of Cu(II) complexes with Hpabh are axial and suggest d(x(2)-y(2) as the ground state. The ligand is bidentate bonding through > C = N--and deprotonated enolate group in all the chloro complexes, whereas, >C = N and >C = O groups in all the sulfato complexes. Thermal studies (TGA & DTA) on [Cu(Hpabh)(H2O)2(SO4)] indicate a multistep decomposition pattern, which are both exothermic and endothermic in nature. X-ray powder diffraction parameters for [Co(pabh)(H2O)Cl] and [Ni(Hpabh)(H2O)2(SO4)] correspond to tetragonal and orthorhombic crystal lattices, respectively. The ligands as well as their complexes show a significant antifungal and antibacterial activity. The metal complexes are more active than the ligand.
Assuntos
Acetofenonas/síntese química , Antibacterianos/síntese química , Hidrazonas/síntese química , Compostos Organometálicos/síntese química , Acetofenonas/farmacologia , Antibacterianos/farmacologia , Cobalto/química , Cobalto/farmacologia , Cobre/química , Cobre/farmacologia , Hidrazonas/farmacologia , Ligantes , Manganês/química , Manganês/farmacologia , Testes de Sensibilidade Microbiana , Níquel/química , Níquel/farmacologia , Compostos Organometálicos/farmacologia , Zinco/química , Zinco/farmacologiaRESUMO
Complexes of the type [Al(HL)(OH)Cl(2)], [M(HL)(OH)(2)Cl] and [M'(HL)(L')(OH)Cl], where HL = 5-iodouracil; HL' = histidine; M = Cr(III), Fe(III) and M' = Al(III), Cr(III), Fe(III), were synthesized and characterized. The complexes are polymeric showing high decomposition points and are insoluble in water and common organic solvents. The mu(eff) values, electronic spectral bands and ESR spectra suggest a polymeric 6-coordinate spin-free octahedral stereochemistry for the Cr(III) and Fe(III) complexes. 5-Iodouracil acts as a monodentate ligand coordinating to the metal ion through the O atom of C((4)) = O while histidine through the O atom of -COO(- ) and the N atom of -NH(2) group. In vivo antitumour effect of 5-iodouracil and its complexes was examined on C(3)H /He mice against P815 murine mastocytoma. As evident from their T/C values, Cr(III) and Fe(III) complexes display significant and higher antitumour activity compared to the 5-iodouracil ligand. The in vitro results of the complexes on the same cells indicate that Cr(III) and Fe(III) complexes show higher inhibition on (3)H-thymidine and (3)H-uridine incorporation in DNA and RNA replication, respectively, at a dose of 5 microg/mL.
Assuntos
Antineoplásicos/química , DNA/antagonistas & inibidores , Metais Pesados/farmacologia , RNA/antagonistas & inibidores , Uracila/análogos & derivados , Alumínio , Animais , Antineoplásicos/farmacologia , Cromo , Histidina , Ferro , Mastocitoma , Metais Pesados/química , Camundongos , Camundongos Endogâmicos , Uracila/química , Uracila/farmacologiaRESUMO
Complexes of the type [M(bssdh)]Cl and [M(dspdh)]Cl, where M = Co(II), Ni(II), Cu(II), Zn(II) and Cd(II); Hbssdh = benzil salicylaldehyde succinic acid dihydrazone, Hdspdh = diacetyl salicylaldehyde phthalic acid dihydrazone have been synthesized and characterized with the help of elemental analyses, electrical conductance, magnetic susceptibility measurements, electronic, ESR and IR spectra and X-ray diffraction studies. Magnetic moment values and electronic spectral transitions indicate a spin free octahedral structure for Co(II), Ni(II) and Cu(II) complexes. IR spectral studies suggest that both the ligands behave as monobasic hexadentate ligands coordinating through three > C = O, two > C = N- and a phenolate group to the metal. ESR spectra of Cu(II) complexes are axial type and suggest d(x(2)-y(2)) as the ground state. X-ray powder diffraction parameters for [Co(bssdh)]Cl and [Co(dspdh)]Cl complexes correspond to an orthorhombic crystal lattice. The ligands as well as their metal complexes show a significant antifungal and antibacterial activity against various fungi and bacteria. The metal complexes are more active than the parent ligands.
Assuntos
Antibacterianos/síntese química , Antibacterianos/farmacologia , Fenômenos Químicos/efeitos dos fármacos , Hidrazonas/síntese química , Hidrazonas/farmacologia , Metais Pesados/química , Antibacterianos/química , Antifúngicos/síntese química , Antifúngicos/química , Antifúngicos/farmacologia , Hidrazonas/química , Ligantes , Magnetismo , Viabilidade Microbiana/efeitos dos fármacos , Estrutura Molecular , Análise EspectralRESUMO
Complexes of the type [M(apash)Cl] and [M(Hapash)(H2O)SO4], where M = Mn(II), Co(II), Ni(II), Cu(II) and Zn(II); Hapash = acetone p-amino acetophenone salicyloyl hydrazone have been synthesized and characterized by elemental analyses, molar conductance, magnetic moments, electronic, ESR and IR spectra, thermal studies (TGA & DTA) and X-ray diffraction studies. The ligand coordinates through two >C=N and a deprotonated enolate group in all the chloro complexes, whereas through two >C=N- and a >C=O group in all the sulfato complexes. The electronic spectra suggest a square planar geometry for Co(II), Ni(II) and Cu(II) chloride complexes and an octahedral geometry for the sulfate complexes. ESR data show an isotropic symmetry for [Cu(apash)Cl] and [Cu(Hapash)(H2O)SO4] in solid state. However, ESR spectra of both Cu(II) complexes indicate the presence of unpaired electron in d x2-y2. The X-ray diffraction parameters for [Co(apash)Cl] and [Cu(Hapash)(H2O)SO4] complexes correspond to a tetragonal and an orthorhombic crystal lattices, respectively. Thermal studies of [Co(apash)Cl] complex shows a multi-step decomposition pattern. Most of the complexes show better antifungal activity than the standard miconazole against a number of pathogenic fungi. The antibacterial activity of these complexes has been evaluated against E. coli and Clostridium sp. which shows a moderate activity.
Assuntos
Acetona/análogos & derivados , Acetofenonas , Anti-Infecciosos , Hidrazonas , Metais/química , Elementos de Transição/química , Acetona/química , Acetona/farmacologia , Acetofenonas/química , Acetofenonas/farmacologia , Anti-Infecciosos/química , Anti-Infecciosos/farmacologia , Bactérias/efeitos dos fármacos , Fungos/efeitos dos fármacos , Humanos , Hidrazonas/química , Hidrazonas/farmacologia , Testes de Sensibilidade Microbiana , Estrutura MolecularRESUMO
This paper describes the preparation of [Cu(bh)2(H2O)2](NO3)2], [Cu(ibh)2(NO3)2], [Cu(ibh)2(H2O)2](NO3)2 and [Cu(iinh)2(NO3)2] (bh = benzoyl hydrazine (C6H5CONHNH2); ibh = isonicotinoyl hydrazine (NC5H4CONHNH2); ibh = isopropanone benzoyl hydrazone (C6H5CONHN=C(CH3)2; iinh = isopropanone isonicotinoyl hydrazone (NC5H4CONHN=C(CH3)2). These copper(II) complexes are characterized by elemental analyses, molar conductances, dehydration studies, ESR, IR and electronic spectral studies. The electronic and ESR spectra indicate that each complex exhibits a six-coordinate tetragonally distorted octahedral geometry in the solid state and in DMSO solution. The ESR spectra of most of the complexes are typically isotropic type at room temperature (300 K) in solid state as well as in DMSO solution. However, all the complexes exhibit invariably axial signals at 77 K in DMSO solution. The trend g(||) > g(perpendicular) > g(e,) observed in all the complexes suggests the presence of an unpaired electron in the d x2-y2 orbital of the Cu(II). The bh and inh ligands bond to Cu(II) through the >C=O and -NH2 groups whereas, ibh and iinh bond through >C=O and >C=N- groups. The IR spectra of bh and ibh complexes also show H-O-H stretching and bending modes of coordinated water.