Chemical modification of sheep plasma glycoprotein

Glycoprotein isolated from sheep plasma was chemically modified, and the effect of chemical modification on biological activities and immunological cross reactions has been studied. The removal of sialic acid resulted in a change in the “overall conformation” of the glycoprotein as evidenced by a decrease in viscosity of the glycoprotein solution and an increased susceptibility of the glycoprotein to proteolytic enzymes. Sialic acid-free glycoprotein no longer inhibited the tryptic activity or prolonged the clotting time of plasma. However, it could react with the antiserum to sheep plasma glycoprotein. The periodate oxidation of sheep plasma glycoprotein resulted in a complete loss of inhibition of trypsin activity, prolongation of plasma clotting time, and the ability to cross-react with the rabbit antiserum. The significance of periodate oxidation in relation to the possible sequence of sugars in the carbohydrate prosthetic group in the glycoprotein is discussed. Iodination and heating in buffers of acid and alkaline pH values of sheep plasma glycoprotein resulted in complete loss of trypsin activity and ability to prolong plasma clotting time. Iodination of the glycoprotein did not affect the immunological cross-reactivity.

Error Checking Digit for Nonconventional Chemical Codes

In handling large volumes of data such as chemical notations, serial numbers for books, etc., it is always advisable to provide checking methods which would indicate the presence of errors. The entire new discipline of coding theory is devoted to the study of the construction of codes which provide such error-detecting and correcting means.l Although these codes are very powerful, they are highly sophisticated from the point of view of practical implementation

Mycobacterium tuberculosis nucleoid-associated DNA-binding protein H-NS binds with high-affinity to the Holliday junction and inhibits strand exchange promoted by RecA protein

A number of studies have shown that the structure and composition of bacterial nucleoid influences many a processes related to DNA metabolism. The nucleoid-associated proteins modulate not only the DNA conformation but also regulate the DNA metabolic processes such as replication, recombination, repair and transcription. Understanding of how these processes occur in the context of Mycobacterium tuberculosis nucleoid is of considerable medical importance because the nucleoid structure may be constantly remodeled in response to environmental signals and/or growth conditions. Many studies have concluded that Escherichia coli H-NS binds to DNA in a sequence-independent manner, with a preference for A-/T-rich tracts in curved DNA; however, recent studies have identified the existence of medium- and low-affinity binding sites in the vicinity of the curved DNA. Here, we show that the M. tuberculosis H-NS protein binds in a more structure-specific manner to DNA replication and repair intermediates, but displays lower affinity for double-stranded DNA with relatively higher GC content. Notably, M. tuberculosis H-NS was able to bind Holliday junction (HJ), the central recombination intermediate, with substantially higher affinity and inhibited the three-strand exchange promoted by its cognate RecA. Likewise, E. coli H-NS was able to bind the HJ and suppress DNA strand exchange promoted by E. coli RecA, although much less efficiently compared to M. tuberculosis H-NS. Our results provide new insights into a previously unrecognized function of H-NS protein, with implications for blocking the genome integration of horizontally transferred genes by homologous and/or homeologous recombination.

A chemical approach to an understanding of the fast ion conduction in silver iodide-silver oxysalt glasses

A number of AgI based fast ion conducting glasses, with a general formula AgI---Ag2O---MxOy (MxOy=MoO3, SeO3, WO3, V2O5, P2O5, GeO2, B2O3, As2O3, CrO3) have been studied. A chemical approach is made to investigate the origin of fast ion conduction in these glasses. An index known as Image tructural Image npinning Image umber, SUN (S), has been defined for the purpose, based on the unscreened nuclear charge of silver ions and the equilibrium lectronegativities of the halide-oxyanion matrix in these glasses. The variation of the glass transition temperature, Tg, conductivity, σ, and the energy of activation, Ea, with the concentration of AgI are discussed in the light of the structural unpinning number. Conductivities increase uniformly in any given glass series as a smooth function of S and level off at very high values. The entire range of conductivity appears to vary as ln Image , where ln σ0 corresponds roughly to the conductivity of the hypothetical AgI glass and “a” is a constant which could be obtained as the slope in the graph of ln Ea versus S. It is suggested that the increase in the concentration of AgI beyond 75–80 mole% in the glass is not advantageous from the conductivity point of view.

Chemical potentials of oxygen for fayalite-quartz-lron and fayalite-quartz-magnetite equilibria

The oxygen potentials corresponding to fayalite-quartz-iron (FQI) and fayalite-quartz-magnetite (FQM) equilibria have been determined using solid-state galvanic cells: Pt,Fe + Fe2SiO4 + SiO2/(Y2O3)ZrO2/Fe + \r"FeO,\l"Pt and Pt, Fe3O4 + Fe2SiO4 + SiO2/(Y2O3)ZrO2/Ni + NiO, Pt in the temperature ranges 900 to 1400 K and 1080 to 1340 K, respectively. The cells are written such that the right-hand electrodes are positive. Silica used in this study had the quartz structure. The emf of both cells was found to be reversible and to vary linearly with temperature. From the emf, Gibbs energy changes were deduced for the reactions: 0.106Fe (s) + 2Fe0.947O (r.s.) + SiO2 (qz) → Fe2SiO4 (ol) δG‡= -39,140+ 15.59T(± 150) J mol-1 and 3Fe2SiO4 (ol) + O2 (g) → 2Fe3O4 (sp) + 3SiO2 (qz) δG‡ = -471,750 + 160.06 T±} 1100) J mol-1 The “third-law≓ analysis of fayalite-quartz-wustite and fayalite-quartz-magnetite equilibria gives value for δH‡298 as -35.22 (±0.1) and -528.10 (±0.1) kJ mol-1, respectively, independent of temperature. The Gibbs energy of formation of the spinel form of Fe2SiO4 is derived by com-bining the present results on FQI equilibrium with the high-pressure data on olivine to spinel transformation of Fe2SiO4.

Optimal design of multiproduct batch chemical plant using NSGA-II

The optimal design of a multiproduct batch chemical plant is formulated as a multiobjective optimization problem, and the resulting constrained mixed-integer nonlinear program (MINLP) is solved by the nondominated sorting genetic algorithm approach (NSGA-II). By putting bounds on the objective function values, the constrained MINLP problem can be solved efficiently by NSGA-II to generate a set of feasible nondominated solutions in the range desired by the decision-maker in a single run of the algorithm. The evolution of the entire set of nondominated solutions helps the decision-maker to make a better choice of the appropriate design from among several alternatives. The large set of solutions also provides a rich source of excellent initial guesses for solution of the same problem by alternative approaches to achieve any specific target for the objective functions

Epitaxial growth of Co3O4 films by low temperature, low pressure chemical vapour deposition

The growth of strongly oriented or epitaxial thin films of metal oxides generally requires relatively high growth temperatures or infusion of energy to the growth surface through means such as ion bombardment. We have grown high quality epitaxial thin films of Co3O4 on different substrates at a temperature as low as 400 degreesC by low-pressure metalorganic chemical vapour deposition (MOCVD) using cobalt(II) acetylacetonate as the precursor. With oxygen as the reactant gas, polycrystalline Co3O4 films are formed on glass and Si (100) in the temperature range 400-550 degreesC. Under similar conditions of growth. highly oriented films of Co3O4 are formed on SrTiO3 (100) and LaAlO3 (100). The activation energy for the growth of polycrystalline films on glass is significantly higher than that for epitaxial growth on SrTiO3 (100). The film on LaAlO3 (100) grown at 450 degreesC shows a rocking curve FWHM of 1.61 degrees, which reduces to 1.32 degrees when it is annealed in oxygen at 725 degreesC. The film on SrTiO3 (100) has a FWHM of 0.33 degrees (as deposited) and 0.29 (after annealing at 725 degreesC). The phi -scan analysis shows cube-on-cube epitaxy on both these substrates. The quality of epitaxy on SrTiO3 (100) is comparable to the best of the perovskite-based oxide thin films grown at significantly higher temperatures. A plausible mechanism is proposed for the observed low temperature epitaxy. (C) 2001 Published by Elsevier Science B.V.

Surface chemical studies on pyrite in the presence of polysaccharide-based flotation depressants

The interaction of dextrin and guar gum with pyrite has been investigated through adsorption, flotation, and electrokinetic measurements. The adsorption densities of the polysaccharides onto pyrite reveal a region of higher adsorption density in the pH range 7.5-11, with a maximum around pH 10 for both polymers. The isotherms exhibit Langmuirian behavior. The adsorption density of guar gum onto pyrite is higher than that of dextrin. Electrokinetic measurements indicate a decrease in the electrophoretic mobility values in proportion to the concentration of the polymer added. Co-precipitation tests confirm polymer-ferric species interaction in the bulk solution, especially in the pH range 5.5-8.5. The pH range for higher adsorption, significant co-precipitation, and appreciable depression of pyrite encompass each other. XPS and FTIR spectroscopic studies provide evidence in support of chemical interaction between hydroxylated pyrite and the hydroxyl groups of the polymeric depressants. (C) 2000 Academic Press.

Chronopotentiometry with power-law perturbation functions at an expanding plane electrode with and without a preceding blank period for systems with a coupled first-order homogeneous chemical reaction

The systems formalism is used to obtain the interfacial concentration transients for power-law current input at an expanding plane electrode. The explicit results for the concentration transients obtained here pertain to arbitrary homogeneous reaction schemes coupled to the oxidant and reductant of a single charge-transfer step and the power-law form without and with a preceding blank period (for two types of power-law current profile, say, (i) I(t) = I0(t−t0)q for t greater-or-equal, slanted t0, I(t) = 0 for t < t0; and (ii) I(t) = I0tq for t greater-or-equal, slanted t0, I(t) = 0 for t < t0). Finally the potential transients are obtained using Padé approximants. The results of Galvez et al. (for E, CE, EC, aC) (J. Electroanal. Chem., 132 (1982) 15; 146 (1983) 221, 233, 243), Molina et al. (for E) (J. Electroanal. Chem., 227 (1987) 1 and Kies (for E) (J. Electroanal. Chem., 45 (1973) 71) are obtained as special cases.

Chemical Aspects of the Synergistic Hypergolic Ignition in Hybrid Systems with N2O4 as Oxidizer

Synergistic hypergolic ignition with nitrogen tetroxide ( N2O4) as oxidizer has been observed in hybrid systems comprising of a mixture of magnesium and Schiff bases as fuels. The ignition delays (IDs) measured using a modified device, have been compared with those of magnesium-Schiff base-WFNA systems under identical conditions. The ID has been found to vary with the nature of the substitution in both the benzene rings. A linear relationship emerges when the ignition delays are plotted against the Hammett substitution constants (σ). The preignition products of the reaction of N2O4 with magnesium and benzylidineaniline have been analysed to be Mg(NO3)2, benzenediazonium salt and benzaldehyde. Based on the preignition products isolated, a probable reaction mechanism has been proposed. The previously proposed preignition mechanism for the Schiff base-magnesium-WFNA system has been further supported from the present ignition delay data.

A Method for Purifying Bulk Gallium Arsenide by Chemical Vapour Transport

The need for high purity materials for the growth of epitaxial layers of GaAs and the limitations of present source materials are discussed. A for purifying bulk quantitites of GaAs using chemical vapour transport is presented. GaAs is contained in a silica capsule which has a small orifice allow movement of gas between inside and outside. The capsule is contained in a heated tube and hydrogen chloride is used as the transporting agent. Growth rates of 0.1 g/h have been obtained and evidence for the purification is presented along with a discussion of the principles involved. The potentialities of the method for both purification and for the growth of single crystal substrate material are stressed.--AA

Studies on hypomethylation of liver DNA during early stages of chemical carcinogenesis in rat liver

Our finding that the inhibitors of DNA methylation, 5-azacytidine, 5-azadeoxycytidine or adenosine dialdehyde, given after a carcinogen all potentiated initiation suggested that hypomethylation of DNA during repair synthesis of DNA might play a role in the initiation of the carcinogenic process. To examine this aspect further, we have asked the question, do the nodules which develop from initiated cells after promotion with 1% orotic acid exhibit an altered methylation pattern in their DNA? The methylation status of the DNA from nodules has been examined using the restriction endonucleases HpaII/MspI and HhaI which distinguish between methylated and unmethylated cytosines in their nucleotide recognition DNA 5'-CCGG and 5'-GCGC respectively. The proto-oncogenes, c-myc, c-fos and c-Ha-ras, in the DNA were primarily studied in this investigation because of their possible involvement in cell proliferation and/or in cell transformation and tumorigenesis. The results indicate that in the nodule DNA, c-myc and c-fos are hypomethylated in the sequence of CCGG while the c-Ha-ras shows hypomethylation in the alternating GCGC sequence. This methylation pattern seen in the nodule DNA is not found in the DNA of the non-nodular surrounding liver or liver tissue after exposure to promoter or carcinogen alone. It is also not found in the DNA of regenerating liver. It is particularly significant that the methylation patterns in the c-myc and c-Ha-ras regions are similar to those found in several cancer tissues. The results suggest that this methylation pattern is acquired early in the carcinogenic process and raises the question whether it has any bearing on the process.

Interplay between multiple length and time scales in complex chemical systems

Processes in complex chemical systems, such as macromolecules, electrolytes, interfaces, micelles and enzymes, can span several orders of magnitude in length and time scales. The length and time scales of processes occurring over this broad time and space window are frequently coupled to give rise to the control necessary to ensure specificity and the uniqueness of the chemical phenomena. A combination of experimental, theoretical and computational techniques that can address a multiplicity of length and time scales is required in order to understand and predict structure and dynamics in such complex systems. This review highlights recent experimental developments that allow one to probe structure and dynamics at increasingly smaller length and time scales. The key theoretical approaches and computational strategies for integrating information across time-scales are discussed. The application of these ideas to understand phenomena in various areas, ranging from materials science to biology, is illustrated in the context of current developments in the areas of liquids and solvation, protein folding and aggregation and phase transitions, nucleation and self-assembly.

Chemical-shift of the X-ray K-absorption edge of Co in some compounds, complexes and minerals

The chemical-shift of the X-ray K-absorption edge of Co was studied in a large number of compounds, complexes (spinels) and minerals of Co in its different oxidation states having widely different crystal structures and containing different types of bonding and various types of ligands, and were reported collectively, for the first time, in a single paper. A quadratic relationship was established on the basis of least-squares regression analysis to hold between the chemical-shift and the effective charge on the absorbing atom, but the dominance of the linear term was shown. This relation was utilized in evaluating the charge on the Co-ion in a number of minerals. The effect on chemical-shift of oxidation states of the absorbing atom, of the bond length, crystal structure and higher shell atoms of the molecule, and of electronegativity, atomic number and ionic radius of the ligand was discussed.