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1.
Artigo em Inglês | MEDLINE | ID: mdl-36537029

RESUMO

The purpose of this research was to investigate the doxorubicin (DOX) adsorption behavior on Fe3O4@Ag-Metal Organic Framework (Fe3O4@Ag-MOF). This adsorbent was effectively prepared using a simple synthetic process. Many instruments, including FTIR, XRD, SEM, TEM, and XPS, were used to characterized the new Fe3O4@Ag-MOF. Additionally, the presented Fe3O4@Ag-surface MOF's area was shown to be 586.06 m2/g with a size of around 43 nm. The composite that was made has magnetic properties that were quite strong (63.3 emu/g). The produced Fe3O4@Ag-MOF was discovered to have a fantastic ability to adsorb the anti-cancer drug DOX, with a 1.72 mmol/g (934.85 mg/g) adsorption capacity. On the basis of changes in temperature, pH, and DOX concentration, the DOX adsorption behavior mechanism was investigated. The adsorption capacity of Fe3O4@Ag-MOF for DOX was greater at pH 7.0, according to experimental data. The adsorption equilibrium also demonstrated that the Langmuir adsorption was regulated the best fit to the extracted data compared with the other models. Additionally, the activation energy of adsorption for DOX onto Fe3O4@Ag-MOF was determined, indicating the chemisorption process. The adsorption kinetics was shown in the well-known kinetic model of the pseudo-second-order. The adsorption thermodynamic measurements were documented according to according to the enthalpy (ΔH°), entropy(ΔS°), and Gibbs free energy (ΔG°) parameters demonstrated that the reaction was endothermic and spontaneous thermodynamic. The adsorption of DOX onto Fe3O4@Ag-MOF from real water samples (tap water, effluent wastewater, and influence wastewater) were investigated. It's interesting that the synthetic adsorbent had great recyclability 72.6 percent in the fifth cycle indicating that it was highly recyclable. After adsorption, the typical Fe3O4@Ag-MOF XRD peak intensities and locations were mostly unchanged throughout adsorption indicates the crystalline phase remained steady. The results indicated that Fe3O4@Ag-MOF were a good candidate for adsorbing the DOX and treating wastewater.


Assuntos
Nanocompostos , Poluentes Químicos da Água , Adsorção , Águas Residuárias , Doxorrubicina , Água/química , Poluentes Químicos da Água/química , Cinética
2.
J Water Health ; 13(4): 970-84, 2015 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-26608759

RESUMO

Most drinking water industries are closely examining options to maintain a certain level of disinfectant residual through the entire distribution system. Chlorine dioxide is one of the promising disinfectants that is usually used as a secondary disinfectant, whereas the selection of the proper monitoring analytical technique to ensure disinfection and regulatory compliance has been debated within the industry. This research endeavored to objectively compare the performance of commercially available analytical techniques used for chlorine dioxide measurements (namely, chronoamperometry, DPD (N,N-diethyl-p-phenylenediamine), Lissamine Green B (LGB WET) and amperometric titration), to determine the superior technique. The commonly available commercial analytical techniques were evaluated over a wide range of chlorine dioxide concentrations. In reference to pre-defined criteria, the superior analytical technique was determined. To discern the effectiveness of such superior technique, various factors, such as sample temperature, high ionic strength, and other interferences that might influence the performance were examined. Among the four techniques, chronoamperometry technique indicates a significant level of accuracy and precision. Furthermore, the various influencing factors studied did not diminish the technique's performance where it was fairly adequate in all matrices. This study is a step towards proper disinfection monitoring and it confidently assists engineers with chlorine dioxide disinfection system planning and management.


Assuntos
Compostos Clorados/análise , Desinfetantes/análise , Água Potável/análise , Óxidos/análise , Purificação da Água/métodos , Monitoramento Ambiental
3.
Environ Technol ; : 1-23, 2023 Nov 12.
Artigo em Inglês | MEDLINE | ID: mdl-37953534

RESUMO

ABSTRACTResearch efforts are focusing on investigating cost-effective and ecologically friendly ways to create nanoparticles as a result of promising developments in green technology (NPs). This experiment focused on the effectiveness of using biochar (TWB) made from coffee waste to extract levofloxacin (LEV) from water. The conclusive results of the trials showed that TWB is an effective adsorbent for removing LEV from liquid solutions. The TWB produced through biological processes underwent comprehensive analysis using techniques such as X-ray diffractometry (XRD), scanning electron microscopy (SEM), Brunauer-Emmett-Teller surface area measurement (BET), X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared (FTIR) spectroscopy. The bioengineered TWB's exceptional crystalline properties, which closely resemble the monoclinic structure of bulk TWB, were confirmed by the XRD analysis. Based on the scanning electron microscopy (SEM) data, the synthesis of TWB Nanoparticles resulted in the formation of spherical particles with an approximate diameter of 40 nm, accompanied by a substantial surface area of 285.55 m²/g. The Pseudo-Second-Order model, which best captured Levofloxacin's adsorption characteristics, was evaluated on the TWB, and the results showed that external mass transfer was the main determinant of response rate. It was also found that the adsorption process was endothermic and spontaneous. The system was optimized using the Box-Behnken design (BBD) methodology. The achieved removal capacity of 1119.19 mg/g utilizing the tested adsorbent was determined to be reasonable when compared to the performance of other previously used adsorbents when evaluating the effectiveness of eliminating LEV. The process of LEV adsorption onto TWB involves a number of different mechanisms, such as ion exchange, π-π interactions, electrostatic pore filling, and hydrogen bonding. Following extensive testing in connection with a real-world sample, the adsorbent demonstrated remarkable efficacy, and it maintained good performance even after undergoing three further regeneration cycles. By adjusting the annealing temperature, we controlled the synthesis of TWB nanoparticles across a range of sizes in order to maximize their antibacterial capabilities. This research utilized a pair of Gram-positive bacteria (Staphylococcus aureus and Bacillus subtilis) and a pair of Gram-negative bacteria (Pseudomonas aeruginosa and Escherichia coli) to evaluate the antibacterial efficacy of TWB.


Green synthesis of biochar via using tea waste.Adsorption studies of harmful pesticides Levofloxacin (LEV).The adsorbents exhibited good reusability for four adsorption/desorption cycles.Adsorption fit with pseudo second order kinetics and Langmuir isotherm model.The adsorption fitted to pseudo-second-order kinetically.This system will provide helpful guidance for coloured effluent treatment.Optimized the results by using Box-Behnken design.

4.
Environ Technol ; : 1-17, 2023 Feb 20.
Artigo em Inglês | MEDLINE | ID: mdl-36749794

RESUMO

The indirect emission had a negative influence on the ecosystem of enormous amounts of harmful dyes into water. Fe3O4@Ag-MOF was successfully fabricated to capture Gentine violet (GV)) as a model example of cationic dye from their aqueous solutions was evaluated in this search as a method to eliminate dyes from water contaminants. FTIR, XPS, BET, TGA, SEM, TEM, and XRD have all been used to study this adsorbent in order to determine its structural and chemical characteristics as well as to interpret its binding mechanisms. According to the results of the characterization, the synthesized composite had a size about 45 nm, a surface area of 856.06 m2/g, and considerable magnetic characteristics (66.2 emug-1). Consequently, we created mesoporous surfaces that had a strong ability to interface and absorb GV dye. It is possible to use the pseudo-second order rate equation to characterize the kinetic profile., while the Langmuir equation fits isotherm models. At pH 9, maximum sorption capacities can reach 1.68 mmol.g-1. Additionally, the investigations of temperature profiles indicated the endothermic process and Thermodynamic parameters were discovered as, ΔG°, ΔH° and ΔS° The synthesized adsorbent had an interestingly high reusability of > 92 percent up to the sixth cycle. These findings revealed that a mixture of electrostatic interactions, π-π stacking, hydrogen bonds, and pore filling were involved in the GV adsorption mechanism. Fe3O4@Ag-MOF was successful in demonstrating its effectiveness as a point-of-use colour collection candidate from actual dyeing effluents.

5.
Environ Technol ; : 1-20, 2023 Jun 01.
Artigo em Inglês | MEDLINE | ID: mdl-37248830

RESUMO

In the current investigation, we have reported on the preparation of Na-Mordenite (MOR) modified by tryptophan (MOR-NH2) nanocomposite was synthesized and characterized using FT-IR, XRD, SEM, XPS, and BET that represented that the MOR-NH2 has high surface area 288 m2/g and pore volume 0.38 cm3/g. This composite represented high efficiency in removal of food dye Azorubine (E122) was 1043 mg/g. Study all the factors that affected on the adsorption such as pH, dose, salinity, E122 dye concentration as well as study the adsorption isotherm models that represented that was fitted to Langmuir. Moreover, study the effect of time according to it the adsorption process was fitted to Pseudo-second-order, and the effect of temperature that approved that the reaction was endothermic, spontaneous, and chemisorption process. The MOR-NH2 nanocomposite was tested and proven to effectively inhibit the growth of Escherichia coli ATCC® 25922™ and Staphylococcus aureus ATCC® 25923™ at low concentrations. To the best of our knowledge, this work is the first to report the usage of MOR-NH2 adsorbents for the removal of E122 dye in wastewater samples. The mechanism of interaction between MOR-NH2 and E122 dye was determining as it could be through Hydrogen bonding, pore filling, or through π-π interaction. This research offers a promising solution for purifying water sources that are contaminated with a variety of chemicals, microorganisms, and other contaminants.

6.
RSC Adv ; 12(44): 28364-28375, 2022 Oct 04.
Artigo em Inglês | MEDLINE | ID: mdl-36320495

RESUMO

We present the effective synthesis and structural characterization of three novel imidazolium-thiohydantoin ligands (IMTHs, 5a-c) and their Mn(iii) complexes (Mn(iii)IMTHs, 6a-c) in this study. The findings of elemental analyses, spectral analyses and magnetic measurements will be used to infer the stoichiometry, coordination styles, and geometrical aspects of Mn(iii)IMTHs. The new compounds were evaluated for their chemotherapeutic potential against ESKAPE pathogens and liver cancer (HepG2). According to the MIC and MBC values, the bactericidal and bacteriostatic activities of IMTHs have been significantly improved following coordination with the Mn(iii) ion. The MTT assay results showed that all Mn(iii)IMTHs had the potential to reduce the viability of liver carcinoma (HepG2) cells in a dose-dependent manner, with the BF4-supported complex (6b) outperforming its counterparts (6a and 6c) as well as a clinical anticancer drug (VBL). Additionally, Mn-IMTH2 (6b) showed the highest level of selectivity (SI = 32.05) for targeting malignant cells (HepG2) over healthy cells (HL7702).

7.
Spectrochim Acta A Mol Biomol Spectrosc ; 61(8): 1847-51, 2005 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-15863056

RESUMO

Several dioxouranium(VI) heterochelates with tetradentate monobasic hydrazone compounds (HL(n)) have been synthesized. The heterochelates of the type [(UO2)2(HL(n))(L(n))2(OAc)2(OH2)2]n have been characterized on the basis of elemental analyses, IR and electronic spectra, conductance and magnetic susceptibility measurements. The complexes are polymeric, non-electrolytes, diamagnetic and eight-coordinated. Wilson, G.F. matrix method, Badger's formula, Jones and El-Sonbati equations were used to determine the stretching and interaction force constants from which the U-O bond distances were calculated. The bond distances of these complexes were also investigated.


Assuntos
Hidrazonas/química , Nitrogênio/química , Espectrofotometria Infravermelho/métodos , Eletrólitos/química , Elétrons , Compostos Heterocíclicos , Íons , Compostos Macrocíclicos , Espectroscopia de Ressonância Magnética , Magnetismo , Modelos Químicos , Conformação Molecular , Polímeros/química , Espectrofotometria , Urânio/química
8.
Spectrochim Acta A Mol Biomol Spectrosc ; 137: 1039-49, 2015 Feb 25.
Artigo em Inglês | MEDLINE | ID: mdl-25286116

RESUMO

N-acryloyl-4-aminosalicylic acid (4-AMSA), monomer (HL) and 5-(4'-alkyl phenylazo)-N-acryloyl-4-aminosalicylic acid (HLn) are synthesized and characterized with various physico-chemical techniques. Thin films of 5-(4'-alkyl phenylazo)-N-acryloyl-4-aminosalicylic acid (HLn) are prepared by spin coating technique. The X-ray diffraction (XRD) patterns of 4-aminosalicylic acid (4-ASA) and its derivatives are investigated in powder and thin film forms. Thermal properties of the compounds are investigated by thermogravemetric analysis (TGA). The optical energy gap and the type of optical transition are investigated in the wavelength range (200-2500 nm) for 4-ASA, HL and HLn. The values of fundamental energy gap (Eg) are in the range 3.60-3.69 eV for all compounds and the type of optical transition is found to be indirect allowed. The onset energy gap Eg(∗) appeared only for azodye compounds is found to be in the range 0.95-1.55 eV depending on the substituent function groups. The refractive index, n, shows a normal dispersion in the wavelength range 650-2500 nm, while shows anomalous dispersion in the wavelength rang 200-650 nm. The dispersion parameters ε∞, εL, Ed, Eo and N/m(∗) are calculated. The photoluminescence phenomena (PL) appear for thin films of 4-ASA and its derivatives show three main emission transitions.


Assuntos
Compostos Azo/química , Membranas Artificiais , Salicilatos/química , Difração de Raios X
9.
Spectrochim Acta A Mol Biomol Spectrosc ; 135: 774-91, 2015 Jan 25.
Artigo em Inglês | MEDLINE | ID: mdl-25150428

RESUMO

An interesting azodye heterocyclic ligand of copper(II), cobalt(II), nickel(II) and uranyl(II) complexes have been synthesized by the reaction of metal salts with 5-(2,3-dimethyl-1-phenylpyrazol-5-one azo)-2-thioxo-4-thiazolidinone (HL) yields 1:1 and 1:2 (M:L) complexes depending on the reaction conditions. The elemental analysis, magnetic moments, spectral (UV-Vis, IR, (1)H and (13)C NMR and ESR) and thermal studies were used to characterize the isolated complexes. The molecular structures of the ligand tautomers are optimized theoretically and the quantum chemical parameters are calculated. The IR spectra showed that the ligand (HL) act as monobasic tridentate/neutral bidentate through the (-N=N), enolic (C-O)(-) and/or oxygen keto moiety groups forming a five/six-membered structures. According to intramolecular hydrogen bond leads to increasing of the complexes stability. The molar conductivities show that all the complexes are non-electrolytes. The ESR spectra indicate that the free electron is in dxy orbital. The calculated bonding parameter indicates that in-plane σ-bonding is more covalent than in-plane π-bonding. The coordination geometry is five/six-coordinated trigonal bipyramidal for complex (1) and octahedral for complexes (2-6). The value of covalency factor ß1(2) and orbital reduction factor K accounts for the covalent nature of the complexes. The activation thermodynamic parameters are calculated using Coats-Redfern and Horowitz-Metzger methods. The synthesized ligand (HL) and its Cu(II) complexes (1, 2 and 4) are screened for their biological activity against bacterial and fungal species. The ligand (HL) showed antimicrobial activities against Escherichia coli. The ligand (HL) and its Cu(II) complexes (2 and 4) have very high antifungal activity against Penicillium italicum. The inhibitive action of ligand (HL), against the corrosion of C-steel in 2M HCl solution has been investigated using potentiodynamic polarization and electrochemical impedance spectroscopy (EIS).


Assuntos
Compostos Azo/química , Corantes/química , Metais/química , Temperatura , Compostos Azo/farmacologia , Bactérias/efeitos dos fármacos , Espectroscopia de Ressonância Magnética Nuclear de Carbono-13 , Corantes/farmacologia , Espectroscopia Dielétrica , Espectroscopia de Ressonância de Spin Eletrônica , Elétrons , Fungos/efeitos dos fármacos , Íons , Cinética , Ligantes , Fenômenos Magnéticos , Testes de Sensibilidade Microbiana , Conformação Molecular , Espectroscopia de Prótons por Ressonância Magnética , Pirazóis/química , Teoria Quântica , Espectrofotometria Infravermelho , Marcadores de Spin , Estereoisomerismo , Termogravimetria , Difração de Raios X
10.
Spectrochim Acta A Mol Biomol Spectrosc ; 140: 111-31, 2015 Apr 05.
Artigo em Inglês | MEDLINE | ID: mdl-25589393

RESUMO

A number of novel polymer complexes of various anions of copper(II), cobalt(II), nickel(II) and uranyl(II) with N(4-(acrylamido)-2-hydroxy benzoic acid) (ABH) have been synthesized and characterized by elemental analysis, IR, 1H NMR, magnetic susceptibility measurements, electronic spin resonance, vibrational spectra and thermal analysis. The molecular structures of the ligand are optimized theoretically and the quantum chemical parameters are calculated. Tentative structures for the polymeric metal complexes due to their potential application are also suggested. The IR data exhibit the coordination of ONO2/OAc/SO4 with the metal ions in the polymeric metal complex. Vibrational spectra indicate coordination of carboxylate oxygen and phenolic OH of the ligand giving a MO4 square planar chromophore. Ligand field ESR spectra support square planar geometry around Cu(II). The thermal decomposition of the polymer complexes were discussed in relation to structure, and the thermodynamic parameters of the decomposition stages were evaluated applying Coast-Redfern and Horowitz-Metzger methods.


Assuntos
Acrilamidas/química , Ácido Salicílico/química , Acrilamidas/síntese química , Espectroscopia de Ressonância de Spin Eletrônica , Espectroscopia de Ressonância Magnética , Modelos Moleculares , Ácido Salicílico/síntese química , Termodinâmica , Termogravimetria
11.
Spectrochim Acta A Mol Biomol Spectrosc ; 147: 200-11, 2015 Aug 05.
Artigo em Inglês | MEDLINE | ID: mdl-25841152

RESUMO

5-(2,3-Dimethyl-1-phenylpyrazol-5-one azo)-2-thioxo-4-thiazolidinone (HL) and its metal complexes with copper(II) (1), cobalt(II) (2) and nickel(II) (3) are synthesized and characterized by physico-chemical techniques. The thermal properties of the ligand (HL) and its metal complexes (1-3) are discussed. The thermal activation energies of decomposition (Ea) of HL and its metal complexes with Cu(II), Co(II) and Ni(II) are found to be 48.76, 36.83, 30.59 and 40.45 kJ/mol, respectively. The frequency and temperature dependence of ac conductivity, dielectric constants for HL and its complexes (1-3) are investigated in the temperature range 300-356 K and frequency range 0.1-100 kHz. Both of the ac conductivity and the values of the thermal activation energy for conduction, as well as the dielectric properties of the complexes of HL are found to depend on the nature of the metallic ions. The values of the thermal activation energies of electrical conductivity decrease with increasing the value of test frequency. The small polarons tunneling (SPT) is the dominant conduction mechanism for the ligand (HL), while for complex (2) the overlapping large tunneling model (OLPT) is the dominant conduction mechanism. The correlated barrier hopping (CBH) is the dominant conduction mechanism for both of the complexes (1) and (3).

12.
Spectrochim Acta A Mol Biomol Spectrosc ; 143: 200-12, 2015 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-25727297

RESUMO

A novel series of (5-(4'-derivatives phenyl azo)-8-hydroxy-7-quinolinecarboxaldehyde) (AQLn) (n=1, p-OCH3; n=2, R=H; and n=3; p-NO2) and their complexes [Cu(AQLn)2]·5H2O are synthesized and investigated. The optimized bond lengths, bond angles and the calculated quantum chemical parameters for AQLn are investigated. HOMO-LUMO energy gap, absolute electronegativities, chemical potentials, and absolute hardness are also calculated. The thermal properties, dielectric properties, alternating current conductivity (σac) and conduction mechanism are investigated in the frequency range 0.1-100kHz and temperature range 293-568K for AQL1-3 and 318-693K for [Cu(AQL1-3)2]·5H2O complexes. The thermal properties are of ligands (AQLn) and their Cu(II) complexes investigated by thermogravimetric analysis (TGA). The temperature and frequency dependence of the real and the imaginary part of the dielectric constant are studied. The values of the thermal activation energy of conduction mechanism for AQLn and their complexes [Cu(AQLn)2]·5H2O under investigation are calculated at different test frequencies. The values of thermal activation energies ΔE1 and ΔE2 for AQLn and [Cu(AQLn)2]·5H2O decrease with increasing the values of frequency. The ac conductivity is found to be depending on the chemical structure of the compounds. Different conduction mechanisms have been proposed to explain the obtained experimental data. The small polaron tunneling (SPT) is the dominant conduction mechanism for AQL1 and its complex [Cu(AQL1)2]·5H2O. The quantum mechanical tunneling (QMT) is the dominant conduction mechanism for AQL2 and its complex [Cu(AQL2)2]·5H2O. The correlated barrier hopping (CBH) is the dominant conduction mechanism for AQL3 and its complex [Cu(AQL3)2]·5H2O, and the values of the maximum barrier height (Wm) are calculated.


Assuntos
Compostos Azo/química , Quelantes/química , Complexos de Coordenação/química , Cobre/química , Quinolinas/química , Compostos Azo/síntese química , Quelantes/síntese química , Complexos de Coordenação/síntese química , Condutividade Elétrica , Modelos Moleculares , Teoria Quântica , Quinolinas/síntese química , Termodinâmica , Termogravimetria
13.
Artigo em Inglês | MEDLINE | ID: mdl-26067934

RESUMO

The coordination behavior of a series of transition metal ions named Cr(III), Fe(III), Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) with a mono negative tridentate guaifenesin ligand (GFS) (OOO donation sites) and 1,10-phenanthroline (Phen) is reported. The metal complexes are characterized based on elemental analyses, IR, (1)H NMR, solid reflectance, magnetic moment, molar conductance, UV-vis spectral studies, mass spectroscopy, ESR, XRD and thermal analysis (TG and DTG). The ternary metal complexes were found to have the formulae of [M(GFS)(Phen)Cl]Cl·nH2O (M=Cr(III) (n=1) and Fe(III) (n=0)), [M(GFS)(Phen)Cl]·nH2O (M=Mn(II) (n=0), Zn(II) (n=0) and Cu(II) (n=3)) and [M(GFS)(Phen)(H2O)]Cl·nH2O (M=Co(II) (n=0), Ni(II) (n=0) and Cd(II) (n=4)). All the chelates are found to have octahedral geometrical structures. The ligand and its ternary chelates are subjected to thermal analyses (TG and DTG). The GFS ligand, in comparison to its ternary metal complexes also was screened for their antibacterial activity on gram positive bacteria (Bacillus subtilis and Staphylococcus aureus), gram negative bacteria (Escherichia coli and Neisseria gonorrhoeae) and for in vitro antifungal activity against (Candida albicans). The activity data show that the metal complexes have antibacterial and antifungal activity more than the parent GFS ligand. The complexes were also screened for its in vitro anticancer activity against the Breast cell line (MFC7) and the results obtained show that they exhibit a considerable anticancer activity.


Assuntos
Antineoplásicos , Complexos de Coordenação , Guaifenesina/química , Elementos de Transição/química , Antibacterianos/síntese química , Antibacterianos/química , Antibacterianos/farmacologia , Antineoplásicos/síntese química , Antineoplásicos/química , Antineoplásicos/farmacologia , Complexos de Coordenação/síntese química , Complexos de Coordenação/química , Complexos de Coordenação/farmacologia , Ensaios de Seleção de Medicamentos Antitumorais , Guaifenesina/síntese química , Guaifenesina/farmacologia , Humanos , Células MCF-7 , Espectroscopia de Ressonância Magnética , Espectrometria de Massas , Testes de Sensibilidade Microbiana , Estrutura Molecular , Espectrofotometria Infravermelho , Termodinâmica , Elementos de Transição/farmacologia
14.
Artigo em Inglês | MEDLINE | ID: mdl-11209866

RESUMO

Several new transition metal complexes derived from 1-acetyl-2-(coumariniminecarboxamide-3-yl)hydrazine (HL) have been prepared and characterized by elemental analyses, 1H-NMR, magnetic susceptibility, IR, UV, EPR and thermal analyses. Stereochemistries are proposed for the complexes on the basis of the spectral and magnetic studies. The i.r. data indicate that the carbonyl oxygen of the carboxamide constituents chelating backbone in most complexes. The visible and EPR spectral studies indicated that the Cu(II) complexes have a tetragonal geometry. From the EPR spectrum of the Cu(II) complexes, various parameters were calculated.


Assuntos
Benzopiranos/química , Cumarínicos/química , Hidrazinas/química , Ligantes , Metais , Cobalto/química , Cobre/química , Espectroscopia de Ressonância de Spin Eletrônica , Espectroscopia de Ressonância Magnética , Manganês/química , Estrutura Molecular , Níquel/química , Espectrofotometria Infravermelho , Espectrofotometria Ultravioleta , Termodinâmica
15.
Spectrochim Acta A Mol Biomol Spectrosc ; 58(13): 3003-9, 2002 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-12477045

RESUMO

Reaction of 8-hydroxy-7-quinolinecarboxaldehyde (LH) with RuC3 x XH2O afforded the compounds [RuL3] and/or [RuL2CIOH2]. Reactions of LH with RuCl3 x XH2O in the presence of N-heterocyclic bases led to the formation of complexes of type [RuL2 x ClPy] and [RuLCl2(o-Phen)] (Py = pyridine or o-Phen = 1,10-phenanthroline). The amine exchange reactions of coordinated Schiff bases in these complexes have been also carried out which give symmetrical tetradentate Schiff base complexes. These complexes were characterized by a combination of elemental analysis, IR, magnetic susceptibility measurements, 1H, 13C NMR and electronic spectral analysis methods. The spectral data were utilized to compute the important ligand field parameters B, beta and Dq. Electronic spectra show all complexes are octahedral. The B-values suggest a strong covalency in the metal-ligand sigma-bond and the Dq-values indicate a medium-strong ligand field. The stereochemistry and the nature of the complexes are markedly dependent upon the molar ratios of the reactants, the pH of the system and the nature of the anions involved. The ligands behave as bi-(0,0) and tetradentate (N2,O2) donors.


Assuntos
Aldeídos/química , Compostos Heterocíclicos/química , Espectroscopia de Ressonância Magnética , Rutênio/química , Análise Diferencial Térmica , Espectrofotometria Infravermelho , Termogravimetria
16.
Artigo em Inglês | MEDLINE | ID: mdl-12524114

RESUMO

The build-up of polymer metallic supramolecules based on homopolymer (1-acrylamido-2-(2-pyridyl)ethane (AEPH)) and ruthenium, rhodium, palladium as well as platinum complexes has been pursued with great interest. The homopolymer shows three types of coordination behaviour. In the mixed valence paramagnetic trinuclear polymer complexes [(11)+(12)] in the paper and in mononuclear polymer complexes (1)-(5) it acts as a neutral bidentate ligand coordinating through the N-pyridine and NH-imino atoms, while in the mixed ligand diamagnetic poly-chelates, which are obtained from the reaction of AEPH with PdX2 and KPtCl4 in the presence of N-heterocyclic base consisting of polymer complexes (9)+(10), and in monouclear compounds (6)-(8), it behaves as a monobasic bidentate ligand coordinating through the same donor atoms. In mononuclear compounds (13)+(14) it acts as a monobasic and neutral bidentate ligand coordinating only through the same donor atoms. Monomeric distorted octahedral or trimeric chlorine-bridged, approximately octahedral structures are proposed for these polymer complexes. The poly-chelates are of 1:1, 1:2 and 3:2 (metal-homopolymer) stoichiometry and exhibit six coordination. The values of ligand field parameters were calculated. The homopolymer and their polymer complexes have been characterized physicochemically.


Assuntos
Polímeros/química , Quelantes/síntese química , Quelantes/química , Fenômenos Químicos , Físico-Química , Eletroquímica , Ligantes , Estrutura Molecular , Ressonância Magnética Nuclear Biomolecular , Compostos Organometálicos/síntese química , Compostos Organometálicos/química , Paládio/química , Platina/química , Polímeros/síntese química , Ródio/química , Rutênio/química , Espectrofotometria Infravermelho
17.
Artigo em Inglês | MEDLINE | ID: mdl-11905530

RESUMO

Detailed analysis of the electronic structure and properties of some rhodanine derivatives (RDs) is presented. The aim of the present investigation is to pinpoint the electronic structural similarities and differences, among the series of the studied RDs that govern and determine their acidic, basic and co-ordinative properties. The geometries of the studied rhodanine were fully optimized at the level of AMI semi-empirical method. Relative stabilities of the enol/keto isomers have been calculated. Proton affinities and proton detachment energies were computed for the series of rhodanine studied, at the level of AM1 method and compared with the potentiometrically-determined proton-ligand dissociation constants. Zero-point energy and electron correlations have been taken into consideration. pK(H) have been found to increase with increasing electron-donating nature of the substituents. The resulting linear Hammett plots of pK(H) versus the Hammett constant sigma values indicate the co-planarity of the investigated molecules. The evaluated thermodynamic parameters (deltaG, deltaH and deltaS) indicate that the dissociation processes are non-spontaneous, endothermic and entropically unfavourable.


Assuntos
Rodanina/análogos & derivados , Elétrons , Concentração de Íons de Hidrogênio , Ligantes , Modelos Químicos , Cloreto de Potássio/farmacologia , Prótons , Teoria Quântica , Rodanina/química , Software , Espectrofotometria/métodos , Estereoisomerismo , Temperatura , Termodinâmica
18.
Spectrochim Acta A Mol Biomol Spectrosc ; 58(2): 333-9, 2002 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-11808738

RESUMO

The reaction products of metal(II) salts with 5-sulphamethoxazoleazo-3-phenyl-2-thioxo-4-thiazolidinone (H2L) have been characterized by elemental analyses, magnetic susceptibility, electronic, infrared and electron paramagnetic resonance spectral measurements. The spectral data suggest a square pyramidal structure for Cu(II) and Co(II) complexes and an octahedral for Ni(II) complexes. Various EPR parameters have been calculated. From the electron paramagnetic resonance and spectral data, the orbital reduction factors were calculated. In all case kperpendicular > kparallel which indicates a 2B1g ground state. These five coordinated complex of Cu(II) react further with pyridine forming six coordinate base adduct. The different modes of chelation of the ligand and stereochemistry around the metal ion are discussed.


Assuntos
Compostos Organometálicos/química , Rodanina/química , Cobalto/química , Cobre/química , Espectroscopia de Ressonância de Spin Eletrônica , Níquel/química , Espectrofotometria Infravermelho
19.
Spectrochim Acta A Mol Biomol Spectrosc ; 58(12): 2771-8, 2002 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-12396059

RESUMO

Mono, bis and tris complexes of rhodium(III) oxine (systematic name 8-hydroxy-7-quinolinecarboxaldehyde) and mixed ligand have been prepared. The amine exchange reaction of coordinated Schiff base in these complexes has also been carried out, which gives symmetrical tetradentate Schiff base complexes. The complexes are characterized by elemental and thermal analysis, IR, magnetic and electronic spectral analysis methods were also employed as well as conductivity measurements. An octahedral structure is proposed for all the new complexes in which chloride is attached to the metal ion in 1:1; 1:2 (metal:ligand) ratio. The spectral data were utilized to compute the important ligand field parameter B, beta and Dq. The B-values suggest a strong covalency in the metal-ligand sigma-bond and the Dq-values indicate a medium strong ligand field. 1H NMR spectra show that the tris (ligand) complex is cis isomer. IR spectra show that the ligand is mono-basic bidentate.


Assuntos
Compostos Heterocíclicos com 2 Anéis/química , Compostos Organometálicos/química , Ródio/química , Aldeídos/química , Ligantes , Quinolinas/química , Bases de Schiff/química , Análise Espectral , Estereoisomerismo
20.
Spectrochim Acta A Mol Biomol Spectrosc ; 57(12): 2359-65, 2001 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-11767830

RESUMO

The dissociation constants of 4-(4-chlorophenylazo)-3-methyl-1-[2-hydroxy-3-morphilinopropane-1-yl]-2-pyrazolin-5-one (CAMP) has been determined potentiometrically in 0.1 M KCl and 40% (v/v) ethanol-water mixture. The stepwise stability constants of the formed complexes of Mn2+, Co2+, Ni2+, Cu2+, Zn2+, La3+, Ce3+ and UO(2)2+, with CAMP have been determined. The stability of the formed complexes were found as follows: UO(2)2+ > Ce3+ > La3+ > Mn2+ < Co2+ < Ni2+ < Cu+ > Zn2+. The thermodynamic parameters (deltaG, deltaH and deltaS) for CAMP and its complexes were evaluated and discussed. The dissociation process is non-spontaneous, endothermic and entropically unfavourable. The formation of the complexes have been found to be spontaneous, exothermic or endothermic (depending on the metal) and entropically favourable. The stoichiometries of these complexes were determined spectrophotometrically and conductometrically and indicated the formation of 1:1 and 1:2 (metal:ligand) complexes.


Assuntos
Compostos Azo/química , Metais/química , Pirazóis/química , Pirazolonas , Condutometria , Concentração de Íons de Hidrogênio , Ligantes , Potenciometria , Prótons , Espectrofotometria , Temperatura , Termodinâmica
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