Synthesis and electrochemical studies of charge-transfer complexes of thiazolidine-2,4-dione with σ and π acceptors

In the present work, we report the synthesis and characterization of novel charge-transfer complexes of thiazolidine-2,4-dione (TZD) with sigma acceptor (iodine) and pi acceptors (chloranil, dichlorodicyanoquinone, picric acid and duraquinone). We also evaluated their thermal and electrochemical properties and we conclude that these complexes are frequency dependent. Charge-transfer complex between thiazolidine-2,4-dione and iodine give best conductivity. In conclusion, complex with sigma acceptors are more conducting than with pi acceptors.     

Kinetics and mechanism of the oxidation of some organic sulfides by morpholinium chlorochromate

The oxidation of organic sulfides by morpholinium chlorochromate (MCC) resulted in the formation of the corresponding sulfoxides. The reaction is first order with respect to both MCC and the sulfide. The reaction is catalyzed by toluene‐p‐sulfonic acid (TsOH). The oxidation was studied in 19 different organic solvents. An analysis of the solvent effect by Swain's equation showed that both the cation‐ and anion‐solvating powers of the solvents play important roles. The correlation analyses of the rate of oxidation of 34 sulfides were performed in terms of various single and multiparametric equations. For the aryl methyl sulfides, the best correlation is obtained with Charton's localized‐delocalized‐resonance and localized‐delocalized‐resonance‐steric equations. The oxidation of alkyl phenyl sulfides exhibited a very good correlation in terms of the Pavelich–Taft equation. The polar reaction constants are negative, indicating an electron‐deficient sulfur center in the rate‐determining step. A mechanism involving formation of a sulfonium cation intermediate in the slow step has been proposed. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 41: 65–72, 2009     

A tandem mass spectrometric approach to the identification of O‐glycosylated glargine glycoforms in active pharmaceutical ingredient expressed in Pichia pastoris

Glycoforms of glargine expressed in Pichia pastoris were isolated by high‐performance liquid chromatography and analyzed by a series of chemical and mass spectrometric methods for the identification of various glycoforms, glycosylation position, nature and structure of glycans. Reduction and alkylation, peptide mapping techniques were used to decipher the amino acid site at which glycosylation had taken place. Chemical methods were coupled with mass spectrometry techniques such as electrospray ionization and matrix‐assisted laser desorption/ionization for identification of the glycosylation site. Copyright © 2009 John Wiley & Sons, Ltd.     

On πd elastic scattering using aligned deuteron targets

A theoretical study is made of the advantages to be gained in polarizing a deuteron target by applying an external electric quadrupole field with non-zero asymmetry parameter for carrying outd(π, π)d experiments, in order to determine empirically the helicity amplitudes A, B, C, D characterizing the scattering, without any phase ambiguities.     

“On water” ultrasound-assisted one pot efficient synthesis of functionalized 2-oxo-benzo[1,4]oxazines: First application to the synthesis of anticancer indole alkaloid,Cephalandole A

For the first time, an efficient, simple, synthetic green protocol for the one-pot synthesis of functionalized 2-oxo-benzo[1,4]oxazines 24–29 in water under ultrasound irradiation is presented. As compared to conventional methods, the present protocol avoids traditional chromatography and purification steps and furnished the target molecules in excellent yields (upto 98%) with no side products. The methodology was also demonstrated on gram scale synthesis. Moreover, functionalized 2-oxo-quinoxaline analogues 31–33, another class of bio-active heterocyclic scaffolds, were also prepared using this method. For the first time, this protocol was successfully applied in the synthesis of the anticancer indole alkaloid, Cephalandole A 35.     

Orientation of tie-lines in the phase diagram of DOPC/DPPC/cholesterol model biomembranes

We report the direction of tie-lines of coexisting phases in a ternary diagram of DOPC/DPPC/cholesterol lipid bilayers, which has been a system of interest in the discussion of biological rafts. For coexisting Ld and Lo phases, we find that the orientation angle α of the tie-lines increases as the cholesterol concentration increases and it also increases as temperature increases from T = 15 °C to T = 30 °C. Results at lower cholesterol concentrations support the existence of a different two-phase coexistence region of Ld and So phases and the existence of a three-phase region separating the two two-phase regions. Our method uses the X-ray lamellar D-spacings observed in oriented bilayers as a function of varying hydration. Although this method does not obtain the ends of the tie-lines, it gives precise values (±1°) of their angles α in the ternary phase diagram.     

Pt3Te4 nanoparticles from tellurium nanowires

We report the synthesis of platinum telluride nanoparticles (Pt(3)Te(4) NPs) in the solution phase at room temperature using a template-assisted method. The dendrimeric aggregates formed are composed of several small units of Pt(3)Te(4) NPs of ～4 nm diameter. Tellurium nanowires (Te NWs) are used as the template and the reducing agent in the growth of NPs which occurs due to the galvanic replacement reaction between Te NWs and PtCl(6)(2-). Surface-enhanced Raman scattering (SERS) of the dispersed Pt(3)Te(4) NPs was studied using crystal violet (CV) as the analyte. SERS sensitivity up to 10(-8) M of CV was observed. The Raman enhancement factor (EF) of adsorbed CV on NP aggregates was calculated to be 1.74 × 10(5). The catalytic ability of the as-synthesized Pt(3)Te(4) NPs for the reduction of 4-nitrophenol (4-NP) was studied.