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61.
Schiff-base (SB) derivatives of Ni(II) and Cu(II) porphyrins endowed with various amine functions (R−NH2),n-butylamine,p-anisidine andm-nitroaniline have been prepared from corresponding formyl porphyrins. Protonation studies of these SB derivatives reveal
a marked red shift of the optical absorption bands in the visible region relative to the unprotonated imines. The magnitude
of the observed red shifts in the protonated derivatives, (SBH+) are found to depend on the electron-withdrawing or electron-donating nature of the R group of the amines. The results of
the optical absorption,1H NMR, EPR, and cyclicovoltammetric studies are illustrative of the fact that protonation of the SB derivatives results in
a localized positive charge,
in the periphery of the porphyrin (p) system. The dibenzo-18-crown-6 interspersedbisporphyrin schiff bases have been prepared fromtrans 4,4′-diamino dibenzo-18-crown-6 and formyl porphyrins. The protonation of these SB derivatives is found to proceed in a concerted
fashion. The cation complexation studies by the crown ether entity in thebisporphyrin systems have been investigated using optical absorption, magnetic resonance and electrochemical methods. The redox
characteristics of the protonated dimeric SB porphyrins reveal that the first oxidation step involves a two-electron transfer
reaction. This is important in view of their possible usage in multielectron transfer reactions of biological and catalytic
interest. 相似文献
62.
63.
Hohyun Kim Moon Sun Jang Jung-Ae Lee Dongjin Pyo Hye-Ran Yoon Hee Joo Lee Kyung Ryul Lee 《Chromatographia》2004,60(5-6):335-339
A sensitive and selective method for the determination of sofalcone in human plasma was established by use of protein precipitation and liquid chromatography-tandem mass spectrometry. Plasma samples were transferred into 96-well plate using an automated sample handling system and spiked with 10 L of 2 g mL–1 internal standard solution (d3-sofalcone). 0.5 mL of acetonitrile was added to the 96-well plate and the plasma samples were then vortexed for 30 sec. After centrifugation, the supernatant was transferred into another 96-well plate and completely evaporated at 40 °C under a stream of nitrogen. The dry residue was reconstituted with mobile phase. All sample transfer and protein precipitation was automated through the application of both the PerkinElmer MultiPROBE II HT and TOMTEC Quadra 96 workstation. The limit of quantitation of sofalcone was 2 ng mL–1 using a sample volume of 0.2 mL for the analysis. The reproducibility of the method was evaluated by analyzing five samples at nine quality control (QC) levels over the nominal concentration range from 2 ng mL–1 to 1000 ng mL–1. Validation of the method showed that the assay has good precision and accuracy. Sofalcone and internal standard produced a protonated precursor ion ([M+H]+) at m/z 451 and 454, and both gave a corresponding product ion at m/z 315. The high sample throughput of the method has been successfully applied to a pharmacokinetic study of sofalcone in human plasma. 相似文献
64.
65.
Gotti R Bertucci C Andrisano V Pomponio R Cavrini V 《Analytical and bioanalytical chemistry》2003,377(5):875-879
The interaction between human serum albumin (HSA) and the acetylcholinesterase inhibitor donepezil, has been studied by means of capillary electrophoresis frontal analysis (CE/FA) and circular dichroism. CE/FA enabled rapid and direct estimation of the quantity of free donepezil present at equilibrium with a physiological level of serum albumin (600 mol L–1). Application of Scatchard analysis enabled estimation of the binding parameters of HSA towards donepezil, such as association constant and number of binding sites on one protein molecule. Furthermore, due to enantioseparation ability shown by HSA on donepezil in CE mode, displacement experiments were carried out using ketoprofen and warfarin as coadditives to the HSA based running buffer. The addition of these compounds reduced the enantioresolution of donepezil by HSA only when used at high concentration. These data were confirmed and corroborated by circular dichroism (CD) experiments. Using CD, bilirubin was also applied as a ligand specific to site III of HSA. The observed behaviour suggested that donepezil could be considered a ligand with independent binding to sites I and II; although site III is not the highest affinity site, indirect interaction (i.e. cooperative binding) can be assumed. 相似文献
66.
《Journal of Molecular Structure》2002,616(1-3):259-264
The molecular structure of the title complex [ZnBr2(C7H6N2)2] was investigated by X-ray diffraction and IR spectroscopy methods. Molecules of zinc(II) complex crystallize in the triclinic crystal system with cell constants a=7.526(2) Å, b=7.8971(8) Å, c=13.431(1) Å, Z=2 and V=791.3(2) Å3. In the molecular structure, the Zn atom is coordinated tetrahedrally by two Br− anions and two benzimidazole ligands. Intramolecular steric repulsions between Br− anions and benzimidazole groups have been caused to cis configuration around the central metal atom. 相似文献
67.
Bhowmik BB Ganguly P 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,62(4-5):808-813
The spectral (both absorption and fluorescence) and photoelectrochemical studies of a few selective dyes, namely, anionic erythrosin B, neutral riboflavin and cationic safranin O have been carried out in aqueous solution of triton X-100, a neutral surfactant. The results show that the ionic dyes, erythrosin B and safranin O form 1:1 electron donor-acceptor (EDA) or charge-transfer (CT) complexes with triton X-100 both in the ground and excited states, whereas neutral dye riboflavin in its excited state forms 1:1 complex with triton X-100. In these complexes, the dyes act as electron acceptors whereas triton X-100 acts as an electron donor. The fluorescence spectra of erythrosin B and safranin O in presence of triton X-100 show enhancement of fluorescence intensity with red and blue shifts respectively while riboflavin shows normal quenching of fluorescence. A good correlation has been found among photovoltage generation of the systems consisting of these dyes and triton X-100, spectral shift due to complex formation and thermodynamic properties of these complexes. 相似文献
68.
Gutiérrez-Dabán A Fernández-Espinosa AJ Ternero-Rodríguez M Fernández-Alvarez F 《Analytical and bioanalytical chemistry》2005,381(3):721-736
The size distribution of polycyclic aromatic hydrocarbons (PAH) was determined for airborne particles from a large city with high vehicular traffic. The analytical method was optimised and validated using NIST standard reference material (SRM 1649a Urban Dust). The 16 priority PAH listed in the US-EPA were Soxhlet-extracted from filtered particulate matter and then fractionated using on-column chromatography. The aromatic fraction was quantified by gas chromatography-mass spectrometry. Real samples of particles collected in Seville (Spain) were analysed using the validated method. Values for the total concentration of PAH in the air, as well as the concentrations of each PAH in six particle-size ranges were obtained. Values of the PAH in TSP, PM10, PM2.5 and PM1 were assessed. 相似文献
69.
ADSORPTION OF 2,4-D ON MODIFIED HYPERCROSSLINKED POLYSTYRENE (NDA-99) AND XAD-4 RESIN 总被引:1,自引:0,他引:1
The adsorption behavior of pesticide 2,4-dichlorophenoxyacetic acid (2,4-D) in aqueous solution has been investigated using a hypercrosslinked polystyrene adsorbent (NDA-99) modified by dimethylamine group as well as a nonionic macroporous adsorbent (XAD-4). The Langmuir and Freundlich isotherm models were employed to fit the experimental data to describe adsorption mechanism. It shows that NDA-99 resin exhibits an adsorption affinity for 2,4-D higher than XAD-4 resin owing to its exceptional micropore structure and the amine group of the hypercrosslinked matrix.Further studies indicate that the hydrogen bonding interaction and the stronger π-π conjugation play a significant role in the course of the adsorption of 2,4-D on NDA-99 resin, which is in agreement with the IR spectroscopic results and the △E values of HOMO (the highest occupied molecular orbit) of adsorbent and LUMO (the lowest unoccupied molecular orbit) of adsorbate calculated from the MINDO/3 model. 相似文献
70.
A. Moghimi Sh. Sheshmani A. Shokrollahi H. Aghabozorg M. Shamsipur G. Kickelbick M. Carla Aragoni V. Lippolis 《无机化学与普通化学杂志》2004,630(4):617-624
A novel 1:2 proton transfer self‐associated compound LH2 , (GH+)2(pydc2—), was synthesized from the reaction of dipicolinic acid, pydcH2, (2, 6‐pyridinedicarboxylic acid), and guanidine hydrochloride, (GH+)(Cl—). The characterization was performed using IR, 1H and 13C NMR spectroscopy and single‐crystal X‐ray diffraction. LH2 · H2O crystallizes in the space group C2/c of the monoclinic system and contains eight molecules per unit cell. The unit cell dimensions are: a = 26.480(5)Å, b = 8.055(2)Å, c = 14.068(3)Å. The first coordination complex (GH)2[Cd(pydc)2] · 2H2O, was prepared using LH2 and cadmium(II) iodide, and characterized by 1H and 13C NMR spectroscopy and X‐ray crystallography. The crystal system is triclinic with space group P1¯ with one molecule per unit cell. The unit cell dimensions are: a = 8.5125(7)Å, b = 11.0731(8)Å, c = 13.2404(10)Å. The cadmium(II) atom is six‐coordinated with a distorted octahedral geometry. The two pydc2— units are almost perpendicular to each other. The protonation constants of the building blocks of the pydc‐guanidine adduct, the equilibrium constants for the reaction of pydc2— with guanidine and the stoichiometry and stability of the Cd2+ complex with LH2 in aqueous solution were accomplished by potentiometric pH titration. The solution studies strongly support a self‐association between pydc2— and GH+ with a stoichiometry for the CdII complex similar to that observed for the isolated crystalline complex. In fact, the [Cd(pydc)2]2— complex was found as the most abundant species in solution (> 90 %) at a pH >5. 相似文献