Amino Acid based cationic surfactants in aqueous solution: physicochemical study and application of supramolecular chirality in ketone reduction

The present study provides a molecular understanding of the origin of the chirality in aqueous micelles and its correlation with the proficiency of stereoselective ketone reduction. The effects of varied headgroup architecture on the surface-active properties as well as on other microstructural parameters were studied and correlated to the structural differences of these naturally occurring amino acid containing surfactants (1-4). Micropolarity sensed by pyrene showed that the micelles prepared using 1-4 are mostly hydrated; particularly large headgroup size surfactant produces more polar environment. A theoretical study was done to quantify the varied spatial dissymmetry for all four surfactants. Asymmetric reduction of prochiral ketones was carried out at the aqueous micellar interface of these chiral amphiphiles by exploiting the supramolecular chirality as evidenced from a circular dichroism study. The enantioselectivity of the reduction process is rationally improved through increase in spatial dissymmetry and steric constraint imposed at the micellar interface by the polar head of surfactants.     

Polyhydroxamic Acid Sorbents for Uranium Recovery

Crosslinked polyacrylamides were synthesized by solution polymerization using benzoyl peroxide as the radical initiator. The water–insoluble polymer obtained was functionalized by reacting with hydroxylamine to convert the amide group into hydroxamic acid group. The resultant functionalized polymer was characterized in terms of moisture uptake, elemental composition, IR spectra, thermal stability, exchange capacity and heavy metal sorption. The sorbent, obtained in particulate form, was investigated for its sorption properties with respect to uranium from uranyl nitrate solutions under unstirred batch conditions. This paper will concentrate on preparation, characterization and performance evaluation with respect to uranium sorption as a function of concentration, time, solution pH and temperature. The potential of this sorbent for uranium and other heavy metal ion recovery from sea water is ascertained.     

Thermal Behavior of Bismaleimide-Amine/Vinyl Ester Resin-Styrene Blends

Abstract

Curing of 4,4′-bismaleimido-diphenyl methane-4,4′ -diaminodi-phenyl methane (1:0.3 molar ratios) (BM-A) was carried out in the presence of vinyl ester-styrene resin. The BM-A could be cured at lower temperatures. The char yields of the cured resins depended on the percentage of bismaleimide-amine in the blend.     

Poly-hydroxamic acid (PHA) matrix for gadolinium pre-concentration and removal

A novel hydrophilic, three dimensionally cross-linked, aliphatic backbones with pendant hydroxamic acid (HA) group as functional moiety has been synthesized and utilized targeting removal of gadolinium [Gd(III)] from laboratory waste aqueous effluent. To understand the nature of sorption, gadolinium solution of various concentrations viz., 20, 10, 5.0, 1.0, 0.5 and 0.1 ppm has been contacted with a dose rate of 1 g/100 mL for 2 h. In this study, ICP-AES has been used for determination of concentration (ppm) of gadolinium in feed, filtrate and elute. EDXRF study also ensures the presence of gadolinium in the respective medium. Loaded gadolinium matrix was eluted with 1 N HCl for determining the elution factor (0.98).     

Theoretical modeling of Cu(II), Sr(II), Gd(III), U(VI) sorption from nuclear effluent on PHA resin with experimental validation

Journal of Radioanalytical and Nuclear Chemistry - The sorption capacity of an in–house synthesized novel resin Polyhydraxamic acid(PHA) towards Cu(II), Sr(II), Gd(III), U(VI) ions was...     

High throughput synthesis of ester library utilizing selective molecular reactivity and recognition technology

This paper reports a new solid support reagent that showed high degrees of selective molecular reactivity and molecular recognition in homo-functional reactions (reactions having similar reactive functionality in reactants and products).     

Microwave Induced Synthesis of Geminal Diacetates from Aldehydes Using Envirocat EPZ10® Without Solvent

Summary.  A simple, efficient, and environmentally friendly synthesis of geminal diacetates using Envirocat EPZ10^? under microwave activation and solvent-free conditions is described. Easy separation and recyclability of the catalyst, high reaction rates, high yields, and easy work-up are important advantages of this method. Received November 3, 1999. Accepted November 24, 1999     

Thiol derivatives of arylnaphthylmethane as novel anti-osteoporotic agents

(Mercaptophenyl)naphthylmethane derivatives were synthesized as novel estrogen receptor binding ligands. [4-(Methylsulfonyl)phenyl](naphth-1-yl)ketone shows a very promising activity towards osteoporosis. Correspondence: Sangita, Medicinal and Process Chemistry Division, Central Drug Research Institute, Lucknow 226001, India.     

Surfactant‐Stabilized Small Hydrogel Particles in Oil: Hosts for Remarkable Activation of Enzymes in Organic Solvents

Hydrogels of amino acid based cationic surfactant having C₁₆ tails were used to immobilize heme proteins and enzyme. These hydrogel‐entrapped proteins/enzyme showed remarkable activation when dispersed in organic solvent. The activation effect (ratio of the activity of the hydrogel‐entrapped enzyme in organic solvent to the activity of the native enzyme in water) of cytochrome c increased up to 350‐fold with varying protein and gelator concentration. Hydrogel‐entrapped hemoglobin and horseradish peroxidase (HRP) also showed markedly improved activity in organic solvent. Alteration in the structure of the gelator and its supramolecular arrangement showed that the protein immobilized within amphiphilic networks with larger interstitial space exhibited higher activation. This striking activation of hydrogel‐entrapped proteins stems from the following effects: 1) the hydrophilic domain of the amphiphilic networks facilitates accessibility of the enzyme to the water‐soluble substrate. 2) the surfactant, as an integral part of the amphiphilic network, assists in the formation of a distinct interface through which reactants and products are easily transferred between hydrophilic and hydrophobic domains. 3) Surfactant gelators help in the dispersion and stabilization of gel matrix into small particles in organic solvent, which enhances the overall surface area and results in improved mass transfer. The activation was dramatically improved up to 675‐fold in the presence of nongelating anionic surfactants that helped in disintegration of the gel into further smaller‐sized particles. Interestingly, hydrogel‐immobilized HRP exhibited about 2000‐fold higher activity in comparison to the activity of the suspended enzyme in toluene. Structural changes of the entrapped enzyme and the morphology of the matrix were investigated to understand the mechanism of this activation.     

Mechanism of the Aerobic Homocoupling of Phenylboronic Acid on Au20−: A DFT Study

The mechanism of the gold nanocluster‐catalyzed aerobic homocoupling of arylboronic acids has been elucidated by means of DFT calculations with Au₂₀^? as a model cluster for the Au:[poly(N‐vinylpyrrolidin‐2‐one)] catalyst. We found that oxygen affects the adsorption of phenylboronic acid and, by lowering the energy barrier, a water molecule enhances dissociation of the C?B bond, which is probably the rate‐determining step. The key role of oxygen is in activating the surface of the gold cluster by generating Lewis acidic sites for adsorption and activation of the phenylboronic acid, leading to the formation of biphenyl through a superoxo‐like species. Moreover, the oxygen adsorbed on the Au nanocluster can act as an oxidant for phenylboronic acid, giving phenol as a byproduct. As shown by NBO analysis, the basic aqueous reaction medium facilitates the reductive elimination process by weakening the Au?C bond, thereby enhancing the formation of biphenyl. The coupling of phenyl and reductive elimination of biphenyl occur at the top or facet site with low‐energy‐barrier through spillover of phenyl group on Au NC. The present findings are useful for the interpretation or design of other coupling reactions with Au NC.