Free energies of transfer of alkali halides from water to urea-water mixtures at 25°C from EMF measurements

The standard potentials_s E ^o of M/M⁺ (M=Li, Na, K, Rb, and Cs) electrodes in aqueous urea solutions containing 12, 20, 30 and 37% by weight of urea have been determined at 25°C from emf measurements on the cell M(Hg)/MCl (m), solvent/AgCl–Ag, from the activities of metals in amalgams by use of a similar type of cell in water, and from the values of_s E ^o of the Ag/AgCl electrode determined earlier. The standard free energies of transfer of MCl, G _t ^o (MCl), from water to the mixed solvents, computed by use of these values and those for the Ag–AgCl electrode, rise sharply from Li⁺ to Na⁺ but fall from Na⁺ to K⁺ and rather sharply from K⁺ to Cs⁺ with a maximum at Na⁺ in all the solvent compositions. This has been attributed to the superimposition of soft-soft interactions on the electrostatic interactions between the ions and the negative charge centers of the possible hydrogen-bonded solvent complexes in the mixed solvents. Comparison of G _t ^o (i) values for individual ions, obtained by a simultaneous extrapolation procedure, with those in aqueous mixtures of methanol,t-butanol, and dimethyl sulfoxide leads to the conclusion that the solvation of these ions in all these solvents is chiefly dictated by the acid-base type of ion-solvent interactions.     

An expedient, regioselective synthesis of 2-alkylamino- and 2-alkylthiothiazolo[5,4-e]indoles

1-Benzenesulfonyl-5-aminoindole 5, prepared from 5-nitroindole 3, was condensed with alkyl isothiocyanates and separately with carbon disulfide and alkyl bromides/iodides to furnish efficiently the corresponding N-alkyl-thioureidoindoles 6a-c and the alkyl N-(indol-5′-yl)dithiocarbamates 9a-e, respectively. Their cyclisation using N-bromosuccinimide (NBS) and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), in the cold, followed by indolic N-deprotection, furnished regioselectively the 2-alkylamino- and the 2-alkylthiothiazolo[5,4-e]indoles 8a-c and 11a-e, respectively, in good overall yields.     

Size-selective synthesis and stabilization of gold organosol in C(n)TAC: enhanced molecular fluorescence from gold-bound fluorophores

Gold nanoparticles of variable sizes have been synthesized in toluene employing two-phase (water-toluene) extraction of AuCl4- followed by its reduction with sodium borohydride in the presence of a series of cationic surfactants of a homologous series having the general formula C(n)TAC. The solubility features of the gold particles in the organic solvent have been accounted qualitatively by calculating the van der Waals interaction potential between the particles. The effect of thermal energy and medium dielectric constant on the stability of metal particles has been studied by measuring the surface plasmon resonance. The stabilization of surfactant-mediated gold particles as hydrosol or organosol has been elucidated by considering the double-layer interaction as a function of the dielectric constant of the solvent medium. The influence of the counterion of the phase transfer reagent and stabilizing ligand on the photochemical stability of the gold colloids has been investigated. The fluorescence probe 1-methylaminopyrene (MAP) was considered for the surface functionalization of the gold particles, and it has been found that there is an enhancement of molecular fluorescence from the gold-probe assembly.     

Identification of novel alpha-glucosidase inhibitors by screening libraries based on N- [4-(benzyloxy) benzoyl] alanine derivatives

A library of 72 compounds related to N- [4-(benzyloxy) benzoyl]alanine (I) was synthesized, prepared and screened for alpha-glucosidase inhibitory activity. Four compounds showed potent inhibition, six compounds moderate inhibition, and 16 were weak inhibitors. One compound, N- [4-(benzyloxy) benzoyl] serine, was found to be a potent inhibitor of alpha-glucosidase with 100% inhibition at 1 micro M. This inhibitor was at least five times more potent than the lead compound I.     

Identification of inhibitors of DNA topoisomerase II from a synthetic library of glycoconjugates

A library of 24 glycoconjugates related to glycosylated beta-amino acid derivative (I) was been prepared and screened against DNA topoisomerase-II of the filarial parasite S. cervi. Among these, compound 6 was found to be a potent inhibitor of DNA topoisomerase-II with 95% inhibition at 1.09 microM. Furthermore, compound 6 was at least three times more potent than the lead compound, glycosylated beta-amino acid derivative I.     

Optimisation of physical and mechanical properties of rubber compounds by response surface methodology--Two component modelling using vegetable oil and carbon black

Response surface methodology was used for predicting the optimal composition of vegetable oil and carbon black in rubber compounding. Central composite rotatable design for two variables at five levels was chosen as the experimental design. The data obtained from measurement of properties was fitted as a two variable second order equation and were plotted as contour plots using programme developed in MATLAB v.5. It is observed from the contour plots that the increase in cross-link density caused by the formation of rubber mono-layer from its multi-layer on increasing the carbon black loading upto the central point (50 phr) of experimental region increases 300% modulus and elongation at break and reduces the ultimate properties like tear strength and tensile strength. On the other-hand hardness increases with increase in solid inclusion of carbon black. From the contours it is observed that the addition of vegetable oil upto 2-3 phr, cross-link density increases due to its coupling action leading to increase in hardness and modulus and lowering of ultimate properties like tensile strength and elongation at break. Addition of further amount of vegetable oil shows less coupling and more plasticising effect leading to increase in tear strength, tensile strength and elongation at break and decrease in hardness and 300% modulus.     

Novel Petasis boronic acid-Mannich reactions with tertiary aromatic amines

Tertiary aromatic amines can serve as amine substrates for the Petasis boronic acid-Mannich reaction, providing a practical synthetic route for the CC bond formation of α-(4-N,N-dialkylamino-2-alkyloxyphenyl)carboxylic acids. The scope and limitations of this method have been examined.     

Electrochemical and chemical polymerization of acrylamide

The electrochemical and chemical polymerization of acrylamide (AA) has been studied. The electrolysis of the monomer in N,N-dimethylformamide (DMF) containing (C₄H₉)₄NClO₄ as the supporting electrolyte leads to polymer formation in both anode and cathode compartments. The cathodic polymer dissolves in the reaction mixture and the anodic polymer precipitates during the course of polymerization. A plausible mechanism for the anodic and cathodic initiation reaction has been given. The chemical polymerization of acrylamide that has been initiated by HClO₄ is analogous to its anodic polymerization. The polymer yield increases with an increase in concentration of the monomer and HClO₄. Raising the reaction temperature also enhances the polymerization rate. The overall apparent activation energy of the polymerization was determined to be ca. 19 kcal/mole. The copolymerization of acrylamide was carried out with methyl methacrylate (MMA) in a solution of HClO₄ in DMF. The reactivity ratios are r₁ (AA) = 0.25 and r₂ = 2.50. The polymerization with HClO₄ appears to be by a free radical mechanism. When the polymerization of acrylamide is carried out with HClO₄ in H₂O, a crosslinked water-insoluble gel formation takes place.     

Efficient and Alternative Approach for Preparation of O-Benzoyloximes Using Benzoyl Peroxide

Benzoyl peroxide has been used as a mild and efficient reagent for the preparation of benzoyl ester of oxime in moderate to good yields.