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81.
82.
The ab initio calculation of the title compound was carried out at HF as well as DFT level of theory. The full geometry optimization of the ligand was carried out using 6-31G(d) basis set. The results obtained were correlated with the single crystal X-ray data, also reported in this paper, shows close resemblance between these two. The influence of electron correlation effects also was studied by carrying out geometry optimization at the MP2 level. The attempts were also made to ascertain the most stable tautomer of the said compound. 相似文献
83.
KailasaSuresh Kumar Kanchi Suvardhan Dasari Rekha B. Jayaraj Pattium Chiranjeevi 《Helvetica chimica acta》2005,88(5):1022-1027
A facile, rapid, and sensitive spectrophotometric method for the determination of propoxur in insecticidal formulations, fortified water, vegetables, agricultural wastewater, and agricultural soil samples has been elaborated. The proposed method is based on the hydrolysis of propoxur under basic conditions, followed by instantaneous azo coupling of the resulting 2‐isopropoxyphenol with the anilines 2a – c . This yielded the orange‐red chromophore 3a (λmax=at 470 nm), the pale‐red coupling product 3b (490 nm), or the red derivative 3c (478 nm), which are stable for 46 h, 38 h, and 24 h, respectively, and could be readily analyzed spectrophotometrically. 相似文献
84.
Devendra K. Rastogi Suresh K. Sahni Vidya B. Rana Satendra K. Dua 《Transition Metal Chemistry》1978,3(1):56-60
Summary Dimeric manganese(II)and iron(II)complexes, (ML)2, derived from benzoyl hydrazones ofo-hydroxyaryl aldehydes and ketones arc described and characterised by elemental analyses and by conductance, molecular weight, magnetic, electronic and i.r. spectral measurements. The dimeric nature of the complexes is revealed by i.r. spectra which show bands atca. 885 Mn2+ and 820 cm–1 Fe2+, characteristic of ring vibrations. The i.r. spectra reveal the terdentate nature of the ligands. The electronic spectra in dimethylformamide are consistent with the tetrahedral nature of the complexes. The appreciable lowering in
eff is attributed to the presence of exchange interactions between two paramagnetic atomsvia oxygen bridges.Reprints of this article are not available. 相似文献
85.
From the roots of oat (Avena sativa) a second antibiotic active glycoside, avenacine B, was isolated in addition to the main glycoside avenacine A. In the aglycone of A the double bond could not be established contrary to the statement in the literature but an aldehyde group in addition to the keto group was identified and therefore the proposed structure has to be revised. In the aglycone of B the —CH2OH-group of A has been substituted by CH3. The structures of the sugar chains in both glycosides have been determined, in avenacine A as [β-d-gluco-pyranosyl(1 → 4)-[β-d-glucopyranosyl (1 → 2)]-α-l-arabinosyl (1)- and in B as [β-d-glucopyranosyl (1 → 4)]-β-d-glucopyranosyl (1)-. 相似文献
86.
Summary Xylenol orange reacts very sensitively with gallium(III), indium (III) and thallium(III) to form reddish violet colored chelates having max 560 nm in case of Ga and In and max 590 nm in case of Ti at PH 4.0. The molar ratio for all the chelates is 1 1 (metal reagent). Optimum conditions including the range for adherence to Beer's law, effect of PH on the color intensity, effect of excess reagent, and sensitivity are reported for the photometric determination of these metal ions using Xylenol orange.
Zusammenfassung Xylenolorange reagiert sehr empfindlich mit Gallium(III), Indium(III) und Thallium(III) unter Bildung rötlich-violetter Chelate mit einem Absorptionsmaximum bei 560 nm im Falle von Ga und In bzw. 590 nm für Tl bei pH 4,0. Das Molverhältnis ist in jedem Fall 11. Die besten Arbeitsbedingungen, der Gültigkeitsbereich des Beerschen Gesetzes, der Einfluß des PH auf die Farbintensität und des Reagensüberschusses sowie die Empfindlichkeit werden für die photometrische Bestimmung der genannten Ionen angegeben.相似文献
87.
Hydrophobic interaction chromatography coupled online with chemical vapour atomic fluorescence spectrometry (HIC-CVGAFS) has been optimized for the analysis of thiolic proteins in denaturing conditions. Proteins are pre-column simultaneously denatured and derivatized in phosphate buffer solution containing 8.0 mol dm−3 urea and p-hydroxymercurybenzoate (PHMB) and the derivatized denatured proteins are separated on a silica HIC Eichrom Propyl column in the presence of 8.0 M urea in the mobile phase. Post-column online reaction of derivatized denatured proteins with bromine, generated in situ by KBr/KBrO3 in HCl medium, allowed the fast conversion of the uncomplexed PHMB and of the PHMB bound to proteins to inorganic mercury also in presence of urea. Hg2+, present in solution as Hg2+-urea complex, is selectively detected by AFS in a Ar/H2 miniaturized flame after sodium borohydride reduction to Hg. Under optimized conditions, online bromine treatment gives a 100±2% recovery of both free and protein-complexed PHMB. Denatured glyceraldehyde-3-phosphate dehydrogenase, aldolase, lactate dehydrogenase, trioso phosphate isomerase and β-lactoglobulin have been examined. As the sensitivity and limit of detection of proteins in the HIC-CVGAFS apparatus depends on number of SH groups reacting with PHMB, the denaturation process, which increases the number of PHMB-reactive thiolic groups in proteins, improves the analytical performances of the described system in protein analysis. The detection limit for the denatured proteins examined was found in the range of 10−10-10−12 mol dm−3, depending on the considered protein, with linear calibration curves spanning over four decades of concentration. 相似文献
88.
D'Souza F Chitta R Gadde S Zandler ME McCarty AL Sandanayaka AS Araki Y Ito O 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(15):4416-4428
Two types of structurally well-defined, self-assembled zinc porphyrin-fullerene conjugates were formed by "two-point" binding strategies to probe the effect of axial ligation or pi-pi-type interactions on the photochemical charge stabilization in the supramolecular dyads. To achieve this, meso-tetraphenylporphyrin was functionalized to possess one or four [18]crown-6 moieties at different locations on the porphyrin macrocycle while fullerene was functionalized to possess an alkyl ammonium cation, and a pyridine or phenyl entities. As a result of the crown ether-ammonium cation complexation, and zinc-pyridine coordination or pi-pi-type interactions, stable zinc porphyrin-fullerene conjugates with defined distance and orientation were formed. Evidence for the zinc-pyridine complexation or pi-pi-type interactions was obtained from the spectral and computational studies. Steady-state and time-resolved emission studies revealed efficient quenching of the zinc-porphyrin singlet excited state in these dyads, and the measured rates of charge separation, k(CS) were found to be slightly better in the case of the dyads held by axial coordination and crown ether-cation complexation. Nanosecond transient absorption studies provided evidence for the electron transfer reactions, and these studies also revealed charge stabilization in these dyads. The lifetimes of the radical ion pairs were found to depend upon the type of porphyrins utilized to form the dyads, that is, porphyrin possessing the crown ether moiety at the ortho position of one of the phenyl rings yielded prolonged charge stabilized states. Addition of pyridine to the supramolecular dyads eliminated the zinc-pyridine coordination or pi-pi-type interactions of the "two-point" bound systems due to the formation of a new zinc-pyridine axial bond thus giving a unique opportunity to probe the effect of axial coordination or pi-pi interactions on k(CS) and k(CR). Under these conditions, the measured electron transfer rates revealed faster k(CS) and slower k(CR) as compared to those obtained in the absence of added pyridine. The evaluated lifetimes of the radical ion-pairs were found to be hundreds of nanoseconds and were longer in the presence of pyridine. 相似文献
89.
Summary The formation of ternary complexes of the MAL3– type [where M = CuII, NiII and ZnII ; A = nitrilotriacetic acid (NTA); L = 1-hydroxy-2-naphthoic acid (1,2 HNA) and 2-hydroxy-1-naphthoic acid (2,1 HNA)] have been studied potentiometrically in 50% v/v aqueous — ethanol (25° and µ = 0.1). Under identical conditions the binary complexes of the 1,2- and 2,1-HNA ligands have also been examined. The values of mixed ligand formation constants KMAL have been found to be lower than KML (first step formation constant of binary complexes) and even less than
(second step formation constant of binary complexes). 相似文献
90.
Kalyan Kali Sen Gupta Saroj Chandra Kumar Pratik Kumar Sen Amalendu Banerjee 《Reaction Kinetics and Catalysis Letters》1988,36(2):423-428
The kinetics of oxidation of methanol by bromate ion in hydrochloric acid medium has been investigated. A mechanism consistent with the experimental observations is suggested.
. , .相似文献