A chitotetrose specific lectin from Luffa acutangula :Physico-chemical properties and the assignment of orientation of sugars in the lectin binding site

A chitooligosaccharide specific lectin (Luffa acutangula agglutinin) has been purified from the exudate of ridge gourd fruits by affinity chromatography on soybean agglutininglycopeptides coupled to Sepharose-6B. The affinity purified lectin was found homogeneous by polyacrylamide gel electrophoresis, in sodium dodecyl sulphate-polyacrylamide gels, by gel filtration on Sephadex G-100 and by sedimentation velocity experiments. The relative molecular weight of this lectin is determined to be 48,000 ± 1,000 by gel chromatography and sedimentation equilibrium experiments. The sedimentation coefficient (S20, w) was obtained to be 4·06 S. The Stokes’ radius of the protein was found to be 2·9 nm by gel filtration. In sodium dodecyl sulphate-polyacrylamide gel electrophoresis the lectin gave a molecular weight of 24,000 in the presence as well as absence of 2-mercaptoethanol. The subunits in this dimeric lectin are therefore held by non-covalent interactions alone. The lectin is not a glycoprotein and circular dichroism spectral studies indicate that this lectin has 31% α-helix and no ß-sheet. The lectin is found to bind specifically to chitooligosaccharides and the affinity of the lectin increases with increasing oligosaccharide chain length as monitored by near ultra-violetcircular dichroism and intrinsic fluorescence titration. The values of ΔG, ΔΗ and ΔS for the binding process showed a pronounced dependence on the size of the oligosaccharide. The values for both ΔΗ and ΔS show a significant increase with increase in the oligosaccharide chain length showing that the binding of higher oligomers is progressively more favoured thermodynamically than chitobiose itself. The thermodynamic data is consistent with an extended binding site in the lectin which accommodates a tetrasaccharide. Based on the thermodynamic data, blue shifts and fluorescence enhancement, spatial orientation of chitooligosaccharides in the combining site of the lectin is assigned.

Effect of surface resistance on gas absorption accompanied by a chemical reaction in a gas - liquid contactor

An analysis of gas absorption accompanied by chemical reaction in the presence of interfacial resistance is presented. The analysis indicates that the effect of interfacial resistance on interphase mass transfer is significantly higher in presence of a reaction compared to the pure absorption case. For fixed values of surface resistance and contact time, the difference between the amount of gas transferred across the interface with and without surface resistance increases as the value of reaction velocity increases. For ranges of contact time and surface resistance of practical relevance, the influence of surface resistance is too high to be neglected while designing gas-liquid contactors.

Crystallization Kinetics and Electrical Relaxation of BaO-0.5Li(2)O-4.5B(2)O(3) Glasses

Transparent glasses in the composition BaO-0.5Li(2)O-4.5B(2)O(3) (BLBO) were fabricated via the conventional melt-quenching technique. X-ray powder diffraction combined with differential scanning calorimetric (DSC) studies carried out on the as-quenched samples confirmed their amorphous and glassy nature, respectively. The crystallization behavior of these glasses has been studied by isothermal and nonisothermal methods using DSC. Crystallization kinetic parameters were evaluated from the Johnson-Mehl-Avrami equation. The value of the Avrami exponent (n) was found to be 3.6 +/- 0.1, suggesting that the process involves three-dimensional bulk crystallization. The average value of activation energy associated with the crystallization of BLBO glasses was 317 +/- 10 kJ/mol. Transparent glass-ceramics were fabricated by controlled heat-treatment of the as-quenched glasses at 845 K/40 min. The dielectric constants for BLBO glasses and glass-ceramics in the 100 Hz-10 MHz frequency range were measured as a function of the temperature (300-925 K). The electrical relaxation and dc conductivity characteristics were rationalized using electric modulus formalism. The imaginary part of the electric modulus spectra was modeled using an approximate solution of the Kohlrausch-Williams-Watts relation. The temperature-dependent behavior of stretched exponent (beta) was discussed for the as-quenched and heat-treated BLBO glasses.

A simple method of estimating the detonation velocity from chemical composition of organic explosives

A simple yet fairly accurate method of calculating the ideal detonation velocity of an organic explosive from a knowledge of the chemical composition alone is proposed. The method is based on the concept that the energetics of a stoichiometrically balanced fuel-oxidizer system is a function of the total oxidizing or reducing valences of the composition. A combination of the valences in the form of Image , where R and P are, respectively, the reducing and oxidizing valences and MW is the molecular weight, has been found to be linearly related to the detonation velocity of the expolosive. The predicting capacity of the method has been found to be superior to other methods in the literature.

Mechanism of adsorption effects on electrode kinetics: Part I: Selection rules in the case of low coverage by molecular surfactants

It is shown that the effect of adsorption of inert molecules on electrode reaction rates is completely accounted for, by introducing into the rate equation, adsorption-induced changes in both the effective electrode area as well as in the electrostatic potential at the reaction site with an additional term for the noncoulombic interaction between the reactant and the adsorbate. The electrostatic potential at the reaction site due to the adsorbed layer is calculated using a model of discretely-distributed molecules in parallel orientation when adsorbed on the electrode with an allowance for thermal agitation. The resulting expression, which is valid for the limiting case of low coverages, is used to predict the types of molecular surfactants that are most likely to be useful for acceleration and inhibition of electrode reactions.

Polymer supported metal complexes as catalysts for oxidation of thiosalts by molecular oxygen IV. Quaternised poly(4-vinyl pyridine) complexes with Cu2+ as template

Copper(II) complexes of quaternised poly(4-vinylpyridine) (PVP) of different degrees of quaternisation and copper content have been prepared by crosslinking the polymer with 1,2-dibromoethane in the presence of Cu2+ ion as template. The stability constant of the PVP---Cu(II) complexes is found to increase with the degree of crosslinking quaternisation of the resin, but the rate at which Cu2+ is adsorbed by the resin decreases. An optimum combination of both stability and rate can be achieved with a moderate degree (31%) of crosslinking. A kinetic study reveals that quaternisation increases significantly the catalytic activity of the complex for the oxidation of S2O2−3 by O2 compared with PVP----Cu(II) without quaternisation, but it deactivates the complex for the oxidation of both S3O2−6 and S4O2−6. The batch reactor oxidation kinetics at pH 2.16, where the rate is observed to be maximum, is well explained by the Langmuir—Hinshelwood model assuming the coordination of both O2 and thioanion to Cu(II) as a precursor to the oxidation reaction.

Resistivity noise in crystalline magnetic nanowires and its implications to domain formation and kinetics

We have investigated the time-dependent fluctuations in electrical resistance, or noise, in high quality crystalline magnetic nanowires within nanoporous templates. The noise increases exponentially with increasing temperature and magnetic field, and has been analyzed in terms of domain wall depinning within the Neel-Brown framework. The frequency-dependence of noise also indicates a crossover from nondiffusive kinetics to long-range diffusion at higher temperatures, as well as a strong collective depinning, which need to be considered when implementing these nanowires in magnetoelectronic devices.

Mass transfer with chemical reaction in a foam bed contactor

On the basis of dodecahedral structure of a foam bed, a model to predict conversion in a foam bed contactor with mass transfer with chemical reaction has been developed. To verify the proposed model, experiments have been carried out in a semi-batch apparatus for the absorption of lean CO2 gas in a foam of sodium hydroxide solution. The proposed model predicts fairly well the experimentally found absorption values.

Mechanism of aminoacylation of tRNA : Influence of spermine on the kinetics of aminoacyl-tRNA synthesis by isoleucyl- and valyl-tRNA synthetases from Mycobacterium smegmatis

Isoleucyl-tRNA synthetase has been purified to homogeneity from Mycobacterium smegmatis. The influence of spermine on the kinetics of valyl-tRNA and isoleucyl-tRNA formation has been investigated by Cleland's method (Cleland, W.W. (1963) Biochim. Biophys. Acta 67, 104–137, 173–187, 188–196). The results suggest that in the presence of spermine and suboptimal concentration of Mg2+, the formation of valyl-tRNA and isoleucyl-tRNA follows a sequential* mechanism. In the presence of an optimal concentration of Mg2+, both valyl-tRNA and isoleucyl-tRNA formation proceeds by a ping-pong mechanism. However, in the presence of spermine and optimal concentrations of Mg2+, valyl-tRNA formation follows the ping-pong mechanism while isoleucyl-tRNA formation follows the sequential mechanism.

Relaxation Time of Chemical Reactions from Network Thermodynamics

The relationship for the relaxation time(s) of a chemical reaction in terms of concentrations and rate constants has been derived from the network thermodynamic approach developed by Oster, Perelson, and Katchalsky.Generally, it is necessary to draw the bond graph and the “network analogue” of the reaction scheme, followed by loop or nodal analysis of the network and finally solving of the resulting differential equations. In the case of single-step reactions, however, it is possible to obtain an expression for the relaxation time. This approach is simpler and elegant and has certain advantages over the usual kinetic method. The method has been illustrated by taking different reaction schemes as examples.

Chemical ordering in As-Se glasses: X-ray absorption edge and XPES studies

X-ray absorption edge and X-ray photoelectron spectroscopic studies of As-Se glasses seem to support a chemical ordering model.

Photocatalytic activity of Ag-substituted and impregnated nano-TiO2

Ag-substituted (Ag sub) and Ag-impregnated (Ag imp), anatase phase nano-TiO2 have been synthesized by solution combustion technique and reduction technique, respectively. The catalysts were characterized extensively by powder XRD, TEM, XPS, FT-Raman, UV absorption, FT-IR, TGA, photoluminescence, BET surface area and isoelectric pH measurements. These catalysts were used for the photodegradation of dyes and for the selective photooxidation of cyclohexane to cyclohexanone. The photoactivities of the combustion-synthesized catalysts were compared with those of commercial Degussa P 25 (DP 25) TiO2, and Ag-impregnated DP 25 (Ag DP). For the photocatalytic degradation of dyes, unsubstituted combustion-synthesized TiO2 (CS TiO2) exhibited the highest activity, followed by 1% Ag imp and 1% Ag sub. For the photoconversion of cyclohexane, the total conversion of cyclohexane and the selectivity of cyclohexanone followed the order: 1% Ag sub > DP 25 > CS TiO2 > 1% Ag imp > 1% Ag DP. The kinetics of the photodegradation of dyes and of the photooxidation of cyclohexane were modeled using Langmuir–Hinshelwood rate equation and a free radical mechanism, respectively, and the rate coefficients were determined. The difference in activity values of the catalysts observed for these two reactions and the detailed characterization of these catalysts are described in this study.

Dual Drug Delivery Microcapsules via Layer-by-Layer Self-Assembly

The integration of hydrophobic and hydrophilic drugs in the polymer microcapsule offers the possibility of developing a new drug delivery system that combines the best features of these two distinct classes of material. Recently, we have reported the encapsulation of an uncharged water-insoluble drug in the polymer membrane. The hydrophobic drug is deposited using a layer-by-layer (LbL) technique, which is based on the sequential adsorption of oppositely charged polyelectrolytes onto a charged substrate. In this paper, we report the encapsulation of two different drugs, which are invariably different in structure and in their solubility in water. We have characterized these dual drug vehicular capsules by confocal laser scanning microscopy, atomic force microscopy, visible microscopy, and transmission electron microscopy. The growth of a thin film on a flat substrate by LbL was monitored by UV−vis spectra. The desorption kinetics of two drugs from the thin film was modeled by a second-order rate model.

Mechanistic Aspects of Shape Selection and Symmetry Breaking during Nanostructure Growth by Wet Chemical Methods

The control of shapes of nanocrystals is crucial for using them as building blocks for various applications. In this paper, we present a critical overview of the issues involved in shape-controlled synthesis of nanostructures. In particular, we focus on the mechanisms by which anisotropic structures of high-symmetry materials (fcc crystals, for instance) could be realized. Such structures require a symmetry-breaking mechanism to be operative that typically leads to selection of one of the facets/directions for growth over all the other symmetry-equivalent crystallographic facets. We show how this selection could arise for the growth of one-dimensional structures leading to ultrafine metal nanowires and for the case of two-dimensional nanostructures where the layer-by-layer growth takes place at low driving forces leading to plate-shaped structures. We illustrate morphology diagrams to predict the formation of two-dimensional structures during wet chemical synthesis. We show the generality of the method by extending it to predict the growth of plate-shaped inorganics produced by a precipitation reaction. Finally, we present the growth of crystals under high driving forces that can lead to the formation of porous structures with large surface areas.