Biligand metal chelates of 1,10-phenanthroline and several salicyclic acid derivatives in solution

Summary Mixed ligand complexes of copper(II), zinc(II), nickel(II) and cobalt(II) ions involving 1,10-phenanthroline (phen) as primary and 3,5-dinitrosalicylic acid (dnsa), 5-nitrosalicylic acid (nsa), 5-chlorosalicylic acid (csa) and 3,5-dibromosalicylic acid (dbsa) as secondary ligands in solution have been investigated potentiometrically [25°, µ = 0.1 M [NaClO₄], medium 50% v: v aqueous ethanol]. The stability order of mixed ligand complexes with respect to the metal ions obeys the natural order: cobalt(II) < nickel(II) < copper(II) > zinc(II). The stabilities of the heterometal chelates have been compared with the corresponding homometal chelates of the secondary ligands and have been interpreted in terms of metal-ligand effects and coulombic interactions between various ligand anion species present.     

Kinetics and mechanism of the ruthenium(III)-catalyzed oxidation of hydroxy-acids byN-bromosuccinimide

Summary The kinetics of the Ru^III-catalyzed oxidation of the hydroxy acids; lactic, tartaric, malic and citric acids byN-bromosuccinimide in HClO₄ and in the presence of Hg(OAc)₂ have been studied. The reactions exhibit a first order rate dependence with respect to the oxidant and zeroth order rate dependence with respect to substrate. The rate is retarded by [H⁺], accelerated at law Ru^III concentrations but independent of [Ru^III] at higher Ru^III concentrations. A mechanism consistent with the observed kinetic data is proposed.     

Franck-Condon effects in collision-induced electronic energy transfer: I2(E; v = 1,2) + He, Ar

Collisions of I2 in the E electronic state with rare gas atoms result in electronic energy transfer to the D, beta, and D' ion-pair electronic states. Rate constants for each of these channels have been measured when I2 is initially prepared in the J = 55, nu = 1 and 2 levels in the E state. The rate constants and effective hard sphere collision cross sections confirm the trends observed when nu = 0 in the E state is initially prepared: He collisions favor population of the D state, while Ar collisions favor population of the beta state. Final state vibrational level distributions are determined by spectral simulation and are found to be qualitatively consistent with the trends in the Franck-Condon factors. The experimental distributions are also compared to the recent quantum scattering calculations of Tscherbul and Buchachenko.     

Total synthesis of (-)- and (+)-lentiginosine

Total synthesis of (-)-lentiginosine was achieved from D-mannitol using highly stereoselective reactions. Similarly, (+)-lentiginosine was synthesized from L-tartaric acid.     

Palladium(II) complexes of aliphatic amines and their oxidation by chloramine‐T in perchloric acid medium

The formation of palladium(II) complexes with aliphatic amines and their oxidation by chloramine‐T in perchloric acid medium has been studied. The spectrophotometric studies showed the formation of 1:1 and 1:2 complexes between palladium(II) and amine in absence of HClO₄. An increase in [HClO₄] in reaction mixture suppresses the complex formation and in presence of [HClO₄] ～10^?3 mol dm^?3 only a 1:1 complex between palladium(II) and amine has been observed. The effect of Cl^? on the complex formation has also been studied. Palladium(II)‐catalyzed oxidation of these amines by chloramine‐T showed a first‐order dependence of rate with respect to each—oxidant, substrate, catalyst, and H⁺. The mechanism consistent with kinetic data for the oxidation process has been proposed in absence as well as in presence of initial [Cl^?]. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 603–612, 2002     

2-(2-Selenocyanic acid ethyl ester)-1H-benz[de] isoquinoline-1,3-(2H)-dione, synthesis photophysics and interaction with bovine serum albumin: a spectroscopic approach

The compound 2-(2-selenocyanic acid ethyl ester)-1H-benz[de] isoquinoline-1,3-(2H)-dione (SEBID), a ubiquitous, bioactive naphthalimide derivative is expected to possess an anticancer, anti-tumor and other important therapeutic activities of significant potency with low systematic toxicity. In this paper, the synthesis of the compound, photophysics of the newly prepared naphthalimide derivative and its interaction with model transport protein Bovine serum albumin (BSA) have been reported using the absorption and steady state fluorescence spectroscopic techniques exploiting the intrinsic fluorescence emission properties of BSA as a probe. Interaction of this organoselenium compound in different dioxane-water mixtures with increase in the polarity of the medium has been studied spectroscopically. Interaction of SEBID with BSA leads to a dramatic decrease in the fluorescence intensity of BSA, which suggests the binding of SEBID with the tryptophan residue of BSA. Furthermore, different thermodynamic parameters for SEBID-BSA interaction have been calculated. Rationalization of the data has been attempted, particularly in relation to prospective applications in the biomedical research.     

Radical promoted Wagner-Meerwein-type rearrangement of epoxides in camphoric systems using a Ti(III) radical source

[Chemical reaction: see text] A radical based Wagner-Meerwein-type rearrangement has been observed in camphoric systems. The radical was generated from the epoxide using Cp2TiCl as the radical source. The radical initiator Cp2TiCl was prepared in situ from commercially available Cp2TiCl2 and Zn dust in THF under argon.     

Studies on electroosmotic and electrophoretic behavior of cholesterol in aqueous solutions

Electrical properties of cholesterol interfaces have been investigated. For this purpose electroosmotic and hydrodynamic permeation of water, sodium chloride, barium chloride, aluminum chloride, and urea solutions across a cholesterol plug have been investigated. Dependence of electroosmotic permeability on concentration of electrolytes has also been studied. Electrophoretic mobility of cholesterol particles of known size distribution and dispersed in solutions of varying concentrations of electrolytes and urea has also been studied. The data have been used to estimate ζ potentials in order to have a plausible picture of the electrical double layer at the cholesterol/ solution interfaces.     

Antistatic applications of conducting polyaniline

A method is described to impart flexibility and mechanical strength to conducting polyaniline by polymerizing aniline on fabrics and on cellulose papers. The study indicates that these conducting fabrics offer 16–18 dB of shielding effectiveness for the control of electromagnetic interference (EMI) up to a frequency of 10³ MHz.     

NMR spectroscopic study of the inclusion complex of desloratadine with β-cyclodextrin in solution

Desloratadine (DES) is an antihistamine used in the treatment of allergies and chronic urticaria. ¹H NMR spectroscopic study of varying ratios of DES and β-Cyclodextrin (β-CD) in D₂O suggests the formation of a 1:1 inclusion complex formed by the penetration of Cl-substituted aromatic ring into the β-CD cavity. The stoichiometry and binding constant of the complex were determined by Scott’s method.