Chemical modifications of natural triterpenes—glycyrrhetinic and boswellic acids: evaluation of their biological activity

Synthetic analogues of naturally occurring triterpenoids; glycyrrhetinic acid, arjunolic acid, and boswellic acids, by modification of A-ring with a cyano- and enone-functionality, have been reported. A novel method of synthesis of α-cyanoenones from isoxazoles is reported. Bioassays using primary mouse macrophages and tumor cell lines indicate potent anti-inflammatory and cytotoxic activities associated with cyano-enones of boswellic acid and glycyrrhetinic acid.

Kinetics of Pressureless Infiltration of Al-Mg Melts into Porous Alumina Preforms

Effective “hydrodynamic” radii governing infiltration kinetics of reactive Al-Mg melts into alumina preforms were found to be three orders of magnitude smaller than the average pore size of the packed bed and also smaller compared with the kinetics for a nonreactive system. A sinusoidal capillary model was developed to predict flow kinetics within the packed bed. For the reactive system, two factors were ascribed for additional melt retardation: (1) different intrinsic wettabilities of the two liquids on alumina, thereby leading to significantly different “effective” local contact angles; and (2) local solute depletion from the meniscus, which was incorporated as a time-dependent contact angle.

Synthesis of multiwall carbon nanotubes by chemical vapor deposition of ferrocene alone

Multiwall carbon nanotubes (MWNTs) filled with Fe nanoparticles (NPs) have been synthesized by thermal chemical vapor deposition of ferrocene alone as the precursor. The MWNTs were grown at different temperatures: 980 and 800 degrees C. Characterization of as-prepared MWNTs was done by scanning and transmission electron microscopy, and X-ray diffraction. The transmission electron microscopy study revealed that Fe NPs encapsulated in MWNTs grown at 980 and 800 degrees C are spherical and rod shaped, respectively. Room-temperature vibrating sample magnetometer studies were done on the two samples up to a field of 1T. The magnetization versus magnetic field loop reveals that the saturation magnetization for the two samples varies considerably, almost by a factor of 4.6. This indicates that Fe is present in different amounts in the MWNTs grown at the two different temperatures. (C) 2009 Elsevier Ltd. All rights reserved.

Photocatalytic degradation of methyl methacrylate copolymers

The photolytic and photocatalytic degradation of the copolymers poly(methyl methacrylate-co-butyl methacrylate) (MMA–BMA), poly(methyl methacrylate-co-ethyl acrylate) (MMA–EA) and poly(methyl methacrylate-co-methacrylic acid) (MMA–MAA) have been carried out in solution in the presence of solution combustion synthesized TiO2 (CS TiO2) and commercial Degussa P-25 TiO2 (DP 25). The degradation rates of the copolymers were compared with the respective homopolymers. The copolymers and the homopolymers degraded randomly along the chain. The degradation rate was determined using continuous distribution kinetics. For all the polymers, CS TiO2 exhibited superior photo-activity compared to the uncatalysed and DP 25 systems, owing to its high surface hydroxyl content and high specific surface area. The time evolution of the hydroxyl and hydroperoxide stretching vibration in the Fourier transform-infrared (FT-IR) spectra of the copolymers indicated that the degradation rate follows the order MMA–MAA > MMA–EA > MMA–BMA. The same order is observed for the rate coefficients of photocatalytic degradation. The photodegradation rate coefficients were compared with the activation energy of pyrolytic degradation. In degradation by pyrolysis, it was observed that MMA–BMA was the least stable followed by MMA–EA and MMA–MAA. The observed contrast in the order of thermal stability compared to the photo-stability of these copolymers was attributed to the two different mechanisms governing the scission of the polymer and the evolution of the products.

Role of histidine residues in EcoP15I DNA methyltransferase activity as probed by chemical modification and site-directed mutagenesis

Towards understanding the catalytic mechanism of M.EcoP15I [EcoP15I MTase (DNA methyltransferase); an adenine methyltransferase], we investigated the role of histidine residues in catalysis. M.EcoP15I, when incubated with DEPC (diethyl pyrocarbonate), a histidine-specific reagent, shows a time- and concentration-dependent inactivation of methylation of DNA containing its recognition sequence of 5'-CAGCAG-3'. The loss of enzyme activity was accompanied by an increase in absorbance at 240 nm. A difference spectrum of modified versus native enzyme shows the formation of N-carbethoxyhistidine that is diminished by hydroxylamine. This, along with other experiments, strongly suggests that the inactivation of the enzyme by DEPC was specific for histidine residues. Substrate protection experiments show that pre-incubating the methylase with DNA was able to protect the enzyme from DEPC inactivation. Site-directed mutagenesis experiments in which the 15 histidine residues in the enzyme were replaced individually with alanine corroborated the chemical modification studies and established the importance of His-335 in the methylase activity. No gross structural differences were detected between the native and H335A mutant MTases, as evident from CD spectra, native PAGE pattern or on gel filtration chromatography. Replacement of histidine with alanine residue at position 335 results in a mutant enzyme that is catalytically inactive and binds to DNA more tightly than the wild-type enzyme. Thus we have shown in the present study, through a combination of chemical modification and site-directed mutagenesis experiments, that His-335 plays an essential role in DNA methylation catalysed by M.EcoP15I.

The chemical ecology of seed dispersal in monoecious and dioecious figs

In the nursery pollination system of figs (Ficus, Moraceae), flower-bearing receptacles called syconia breed pollinating wasps and are units of both pollination and seed dispersal. Pollinators and mammalian seed dispersers are attracted to syconia by volatile organic compounds (VOCs). In monoecious figs, syconia produce both wasps and seeds, while in (gyno)dioecious figs, male (gall) fig trees produce wasps and female (seed) fig trees produce seeds. VOCs were collected using dynamic headspace adsorption methods on freshly collected figs from different trees using Super Q® collection traps. VOC profiles were determined using gas chromatography–mass spectrometry (GC–MS).The VOC profile of receptive and dispersal phase figs were clearly different only in the dioecious mammal-dispersed Ficus hispida but not in dioecious bird-dispersed F. exasperata and monoecious bird-dispersed F. tsjahela. The VOC profile of dispersal phase female figs was clearly different from that of male figs only in F. hispida but not in F. exasperata, as predicted from the phenology of syconium production which only in F. hispida overlaps between male and female trees. Greater difference in VOC profile in F. hispida might ensure preferential removal of seed figs by dispersal agents when gall figs are simultaneously available.The VOC profile of only mammal-dispersed female figs of F. hispida had high levels of fatty acid derivatives such as amyl-acetates and 2-heptanone, while monoterpenes, sesquiterpenes and shikimic acid derivatives were predominant in the other syconial types. A bird- and mammal-repellent compound methyl anthranilate occurred only in gall figs of both dioecious species, as expected, since gall figs containing wasp pollinators should not be consumed by dispersal agents.

Quantum Chemical Studies on Tropospheric Nucleation Mechanisms Involving Sulfuric Acid

Nucleation is the first step of the process by which gas molecules in the atmosphere condense to form liquid or solid particles. Despite the importance of atmospheric new-particle formation for both climate and health-related issues, little information exists on its precise molecular-level mechanisms. In this thesis, potential nucleation mechanisms involving sulfuric acid together with either water and ammonia or reactive biogenic molecules are studied using quantum chemical methods. Quantum chemistry calculations are based on the numerical solution of Schrödinger's equation for a system of atoms and electrons subject to various sets of approximations, the precise details of which give rise to a large number of model chemistries. A comparison of several different model chemistries indicates that the computational method must be chosen with care if accurate results for sulfuric acid - water - ammonia clusters are desired. Specifically, binding energies are incorrectly predicted by some popular density functionals, and vibrational anharmonicity must be accounted for if quantitatively reliable formation free energies are desired. The calculations reported in this thesis show that a combination of different high-level energy corrections and advanced thermochemical analysis can quantitatively replicate experimental results concerning the hydration of sulfuric acid. The role of ammonia in sulfuric acid - water nucleation was revealed by a series of calculations on molecular clusters of increasing size with respect to all three co-ordinates; sulfuric acid, water and ammonia. As indicated by experimental measurements, ammonia significantly assists the growth of clusters in the sulfuric acid - co-ordinate. The calculations presented in this thesis predict that in atmospheric conditions, this effect becomes important as the number of acid molecules increases from two to three. On the other hand, small molecular clusters are unlikely to contain more than one ammonia molecule per sulfuric acid. This implies that the average NH3:H2SO4 mole ratio of small molecular clusters in atmospheric conditions is likely to be between 1:3 and 1:1. Calculations on charged clusters confirm the experimental result that the HSO4- ion is much more strongly hydrated than neutral sulfuric acid. Preliminary calculations on HSO4- NH3 clusters indicate that ammonia is likely to play at most a minor role in ion-induced nucleation in the sulfuric acid - water system. Calculations of thermodynamic and kinetic parameters for the reaction of stabilized Criegee Intermediates with sulfuric acid demonstrate that quantum chemistry is a powerful tool for investigating chemically complicated nucleation mechanisms. The calculations indicate that if the biogenic Criegee Intermediates have sufficiently long lifetimes in atmospheric conditions, the studied reaction may be an important source of nucleation precursors.

Effect of Chain Length of Alcohol on the Lipase-Catalyzed Esterification of Propionic Acid in Supercritical Carbon Dioxide

The esterification of propionic acid was investigated using three different alcohols, namely, isopropyl alcohol, isobutyl alcohol, and isoamyl alcohol. The variation of conversion with time for the synthesis of isoamyl propionate was investigated in the presence of five enzymes. Novozym 435 showed the highest activity, and this was used as the enzyme for investigating the various parameters that influence the esterification reaction. The Ping-Pong Bi-Bi model with inhibition by both acid and alcohol was used to model the experimental data and determine the kinetics of the esterification reaction.

A novel fibre-coated sorbent for rapid removal of heavy metals from wastewater. Sorption of Zinc(II) from dilute aqueous solutions in the presence of high concentrations of common salts

The commercial acrylic fibre "Cashmilon" was partially hydrolyzed to convert a fraction of its nitrile (-CN) groups to carboxylic acid (-COOH) groups and then coated with polyethylenimine (PEI) resin and cross-linked with glutaraldehyde to produce a novel gel-coated fibrous sorbent with multiple functionalities of cationic, anionic and chelating types, and significantly faster sorption kinetics than bead-form sorbents. The sorption properties of the fibrous sorbent were measured using Zn(II) in aqueous solution as the sorbate to determine the effects of pH and the presence of common ions in the solution on the sorption capacity. The rate of sorption on the gel-coated fibre was measured in comparison with that on Amberlite IRA-68 weak-base resin beads, to demonstrate the marked difference between fibre and bead-form sorbents in their kinetic behaviour.

Studies on the ionic transport and structural investigations of La0.5Li0.5TiO3 perovskite synthesized by wet chemical methods and the effect of Ce, Zr substitution at Ti site

La0.5Li0.5TiO3 perovskite was synthesized by various wet chemical methods. By adopting low temperature methods of preparation lithium loss from the material is prevented. La0.5Li0.5TiO3 (LLTO) was formed with cubic symmetry at 1473 K. LLTO was formed at relatively lower temperature by using hydrothermal preparation method. PVA gel-decomposition route yield tetragonal LLTO on annealing the dried gel at 1473 K. By using gel-carbonate route LiTi2O4 minor phase was found to remain even after heat-treatment at 1473 K. The hydroxylation of LLTO was done in deionized water as well as in dilute acetic acid medium. By hydroxylation process incorporation of hydroxyls and leaching out of Li+ was observed from the material. The Li+ concentration of these compositions was examined by AAS. The electrical conductivities of these compositions were measured by dc and ac impedance techniques at elevated temperatures. The activation energies of electrical conduction for these compositions were estimated from the experimental results. The measured activation energy of Li+ conduction is 0.34 eV. Unhydroxylated samples exhibit only Li+ conduction, whereas, the hydroxylated LLTO show proton conductivity at 298-550 K in addition to Li+ conductivity. The effect of Zr or Ce substitution in place of Ti were attempted. La0.5Li0.5ZrO3 Perovskite was not formed; instead pyrochlore phase (La2Zr2O7) along with monoclinic ZrO2 phases was observed above 1173 K; below 1173 K cubic ZrO2 is stable. (La0.5Li0.5)(2)CeO4 solid solution was formed in the case of Ce substitution at Ti sublattice on heat-treatment up to 1673 K. (c) 2005 Springer Science + Business Media, Inc.