Analysis method of the angiotensin-I converting enzyme inhibitory activity based on micellar electrokinetic chromatography.

A micellar electrokinetic chromatography (MEKC) method was developed for estimating the angiotensin-I converting enzyme (ACE) inhibitory activity by separating the hippuric acid liberated in the ACE reaction mixture in the presence of an inhibitor, captopril. The hippuric acid was successfully separated and detected by MEKC with a 25 mM sodium dodecyl sulfate solution in a 25 mM phosphate-50 mM borate buffer at pH 7.0; the total analysis took about 5 min. A good linear relationship was observed between the inhibitor and the peak area of hippuric acid release. No significant difference in the ACE inhibitory activity (IC50) of captopril (an antihypertensive medicine) or autolyzed-mushrooms (functional foods) was observed between the conventional method and the MEKC method. The MEKC method was found to be a useful technique for a rapid assay of the ACE inhibitory activity.     

Carbide precipitates in solution-quenched PH13-8 Mo stainless steel: A small-angle neutron scattering investigation

This paper deals with the small-angle neutron scattering (SANS) investigation on solution-quenched PH13-8 Mo stainless steel. From the nature of the variation of the functionality of the profiles for varying specimen thickness and also from the transmission electron microscopy (TEM), it has been established that the small-angle scattering signal predominantly originates from the block-like metallic carbide precipitates in the specimen. The contribution due to double Bragg reflection is not significant in the present case. The single scattering profile has been extracted from the experimental profiles corresponding to different values of specimen thickness. In order to avoid complexity and non-uniqueness of the multi-parameter minimization for randomly oriented polydisperse block-like precipitate model, the data have been analyzed assuming randomly oriented polydisperse cylindrical particle model with a locked aspect ratio.     

Physicochemical studies on hydrophobic PEO‐PPO‐PEO triblock copolymer micelles in SDS micellar environment

The shape, size, aggregation, hydration, and correlation times of water insoluble PEO‐PPO‐PEO triblock copolymer micelles with sodium dodecylsulfate (SDS) micelles were investigated using transport studies and dynamic light scattering technique. From the conductance of micellar solutions of the polymer in 25 mM SDS and 5 mM NaCl, the hydration of polymer micelles were determined using the principle of obstruction of electrolyte migration by the polymer. The asymmetry of the micellar particles of polymer and polymer‐SDS mixed micellar systems in 5 mM NaCl and their average axial ratios were calculated using intrinsic viscosity and hydration data obeying Simha–Einstein equation. Hydration number and micellar sizes were variable with temperature. The shape of the polymer micelles has been ellipsoidal rather than spherical. The micellar volume, hydrodynamic radius, radius of gyration, diffusional coefficients as well as translational, rotational and effective correlation times have been calculated from the absolute values of the axes. The partial molal volume of polymer micelles has also been determined and its comparison with the molar volume of pure polymer suggested a volume contraction due to immobilization of the water phase by the hydrophilic head groups of the polymer. The thermodynamic activation parameters for viscous flow favor a more ordered water structure around polymer micelles at higher temperatures. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2410–2420, 2007     

Magnesium perchlorate as an efficient catalyst for the synthesis of imines and phenylhydrazones

Magnesium perchlorate has been found to be an efficient catalyst for the synthesis of imines and phenylhydrazones by the reaction of carbonyl compounds with amines and phenylhydrazine in high yields at room temperatures and in short times. The condensation of less electrophilic carbonyl compounds with poorly nucleophilic amines affords the imines in excellent yields.     

ZrCl4 as a new and efficient catalyst for the opening of epoxide rings by amines

Zirconium(IV) chloride catalyses the nucleophilic opening of epoxide rings by amines leading to the efficient synthesis of β-amino alcohols. The reaction works well with aromatic and aliphatic amines in short times at room temperature in the absence of solvent. Exclusive trans stereoselectivity is observed for cyclic epoxides. Aromatic amines exhibit excellent regioselectivity for preferential nucleophilic attack at the sterically less hindered position during the reaction with unsymmetrical epoxides. However, in case of styrene oxide, selective formation of the benzylic amine was observed during the reactions with aromatic amines.     

Exploring nucleoside hydrolase catalysis in silico: molecular dynamics study of enzyme-bound substrate and transition state

The mechanism of action of inosine-uridine nucleoside hydrolase has been investigated by long-term molecular dynamics (MD) simulation in TIP3P water using stochastic boundary conditions. Five MD studies have been performed with enzyme substrate complex (E.S), enzyme substrate complex with protonated His241 (EH.S), enzyme transition state complex (E.TS), enzyme transition state complex with protonated His241 (EH.TS), and His241Ala transition state complex E(H241A).TS. Special attention has been given to the role of His241, which has been considered as the general acid catalyst to assist departure of the leaving nucleobase on the basis of its location in the active site in the X-ray crystal structure (). Yet on the basis of the location in the active site, Tyr229 is closer to the aniline ring of pAPIR as compared to His241. On initiation of MD simulations, His241 does not approach the nucleobase in the structures of EH.S, E.S, EH.TS, and E.TS. In the solvated enzyme, Tyr229, which is a member of the hydrogen bonding network inosine O2'.Asp14.His241.Tyr229.inosine N7, serves as a proton source to the leaving nucleobase. The loss of significant activity of His241Ala mutant is shown to be related to the disruption of the above hydrogen bonded network and the distancing of Tyr229 from inosine N7. The structures of the enzyme complexes with substrate or TS are not visibly altered on protonation of His241, a most unusual outcome. The bell-shaped pH dependence upon pK(app)'s of 7.1 and 9.1 may be attributed to the necessity of the dissociation of Asp10 or Asp15 and the acid form of Tyr229, respectively. In TS, the residue Ile81 migrated closer, whereas Arg233 moved away from the nucleobase. The probability of ribooxocarbenium ion stabilization by Asn168 and Asp14 is discussed. The Asp14-CO(2)(-) is hydrogen bonded to the ribose 2'-OH for 96% of the MD simulation time. Nucleophilic addition of water138 to ribooxocarbenium ion is suggested to be assisted by the proton shuttle from water138 --> Asp10 --> Asp15 --> water pool. An anticorrelation motion between Tyr229-OH and Asn168-OD1 in EH.S and E.S is observed. The relationship of this anticorrelated motion to mechanism, if any, deserves further exploration, perhaps the formation of a near attack conformation.     

Siloxane polymers containing azo moieties synthesized by click chemistry for photo responsive and liquid crystalline applications

Three new types of siloxane‐based photoactive liquid crystalline polymers containing azo side groups were synthesized through the click chemistry route. The polymers having molecular weight range of 14,000–34,000 g mol^?1 were soluble in most of the polar solvents like chloroform, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, and dichloromethane. The photoresponsive trans–cis photoisomerization under UV radiation and cis–trans relaxation process in dark for the polymers were studied. The isomerization rate constants were found to be 0.01–0.04 sec^?1 and 1.16*10^?4–4.67*10^?4 sec^?1, respectively. It has been noted that the polymers showed high intensity absorption for n‐π* in chloroform. Both trans and cis forms of azide monomers having azo moiety exhibited molar extinction coefficient ( ? _max) in the range of 22,000–33,000 L mol^?1 cm^?1. The thermotropic behavior of the polymers was studied by polarizing optical microscope (POM) and differential scanning calorimetry (DSC) experiments. Polymer P1 showed liquid crystalline textures of nematic droplets, whereas P2 showed smectic focal conic texture and nematic droplets. Polymer P1 was also studied for photomechanical bending on exposure to UV radiation. The polymers showed initial degradation temperature in the range of 210–275°C. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Superperiodicity,chaos and coexisting orbits of ion-acoustic waves in a four-component nonextensive plasma

Superperiodicity, chaos and coexisting orbits of ion-acoustic waves (IAWs) are studied in a multi-component plasma consisting of fluid ions, q -nonextensive cold and hot electrons and Maxwellian hot positrons. The significant impacts of the system parameters on superperiodic and nonlinear periodic IAWs are presented. Considering an external periodic perturbation various types of quasiperiodic and chaotic features for IAWs are studied in different parametric ranges through time series’ plots, phase spaces and Lyapunov exponents. It has been observed that there exist some coexisting orbits for IAWs. Coexisting orbits for IAWs in a classical electron–positron–ion plasma system are reported.     

Formation of bamboo-shaped carbon nanotubes on carbon black in a fluidized bed

For the first time, bamboo-shaped multiwalled carbon nanotubes, having diameter of the order of 50 nm, have been grown on carbon black in a fluidized bed in bulk amount. The activation energy for the synthesis of the product was found out to be around 33 kJ/mol in the temperature range of 700−900 °C. The carbon nanotubes were separated from the carbon black by preferential oxidation of the later, the temperature of which was determined by thermogravimetry. The transmission electron microscopy revealed different features of the nanotubes such as “Y” junction, bend, and catalyst filling inside the nanotubes. Small angle neutron scattering was performed on the nanotubes synthesized at different temperatures. The data were fitted into a suitable model in order to find out the average diameter, which decreases with increase in synthesis temperature. The Monte Carlo simulation predicts the same behavior. Based on the above observations, a possible growth mechanism has been predicted. The oscillation in carbon saturation value inside the catalyst in the fluidized bed has been indicated as the responsible factor for the bamboo-shaped structure.     

Accelerating rate calorimeter studies of water-induced thermal hazards of fireworks tip mixture

The objective of this article is to generate thermal decomposition data on fireworks tip mixture, a mixture used to coat the tip of fireworks, for easy ignition. This mixture has reportedly involved in triggering many accidents in fireworks industry. Different quantities of water were added to the mixture and its thermal characteristics were studied. Differential scanning calorimeter was used for screening tests and accelerating rate calorimeter was used for detailed studies in adiabatic and isothermal modes. The self-heat rate data obtained showed onset temperature for different quantity of water, at a range of 80–170 °C. The mixture with 40 % water wt/wt had onset at 80 °C in adiabatic mode. The same mixture on isoaging at 40 °C exhibited exothermic characteristics with a substantial rise in system pressure (57 bar). The heats of exothermic decomposition and Arrhenius kinetics were also computed.