Rhodotorula aurantiaca penicillin V acylase: Active site characterization and fluorometric studies

Penicillin V acylase (PVA), a member of newly evolved Ntn-hydrolase superfamily, is a pharmaceutically important enzyme to produce 6-aminopenicillanic acid. Active site characterization of recently purified monomeric PVA from Rhodotorula aurantiaca (Ra-PVA), the yeast source, showed the involvement of serine and tryptophan in the enzyme activity. Modification of the protein with serine and tryptophan specific reagents such as PMSF and NBS showed partial loss of PVA activity and substrate protection. Ra-PVA was found to be a multi-tryptophan protein exhibiting one tryptophan, in native and, four in its denatured condition. Various solute quenchers and substrate were used to probe the microenvironment of the putative reactive tryptophan through fluorescence quenching. The results obtained indicate that the tryptophan residues of Ra-PVA were largely buried in hydrophobic core of the protein matrix. Quenching of the fluorescence by acrylamide was collisional. Acrylamide was the most effective quencher amongst all the used quenchers, which quenched 71.6% of the total intrinsic fluorescence of the protein, at a very less final concentration of 0.1 M. Surface tryptophan residues were found to have predominantly more electropositively charged amino acids around them, however differentially accessible for ionic quenchers. Denaturation led to shift in λ_max from 336, in native state, to 357 nm and more exposed to the solvent, consequently increase in fluorescence quenching with all quenchers. This is an attempt towards the conformational studies of Ra-PVA.     

Electrochemical behavior of different structural states of the alloy Ti60Ni40

Potentiodynamic polarization studies were carried out on nanocrystalline I, nanocrystalline II and nanocrystalline III states having crystallite size 35 ± 5 nm, 18 ± 2 nm and 10 ± 2 nm of the alloy Ti₆₀Ni₄₀ in 1 M H₂SO₄ aqueous medium. It was observed that the nanocrystalline III state exhibits superior corrosion resistance as compared to the nanocrystalline II and nanocrystalline I states of the alloy Ti₆₀Ni₄₀. XPS studies were also performed after corrosion test and it was observed that nanocrystalline III state contains only Ti²⁺ and Ti⁴⁺ species whereas nanocrystalline I and nanocrystalline II state contains Ti²⁺, Ti³⁺and Ti⁴⁺ along with some unoxidized metallic Ti⁰ in the case of nanocrystalline I state. Thus the small crystallite size and the presence of only Ti²⁺ and Ti⁴⁺ species in the form of TiO and TiO₂ leads to the formation of a protective oxide film which is adherent, stable and improves the corrosion resistance of the nanocrystalline III state of the alloy Ti₆₀Ni₄₀.     

Cobalt-catalyzed aziridination with diphenylphosphoryl azide (DPPA): direct synthesis of N-phosphorus-substituted aziridines from alkenes

A new catalytic aziridination system that consists of cobalt(II) tetraphenylporphyrin [Co(TPP)] as the catalyst and diphenylphosphoryl azide (DPPA) as the nitrene source has been developed. The cobalt-based catalytic system allows direct synthesis of N-phosphorus-substituted aziridines from alkenes with dinitrogen as the byproduct. Cobalt ion seems essential to the catalytic aziridination with DPPA as no or only trace amounts of the desired products were observed with other metal complexes of tetraphenylporphyrin.     

The temperature-dependent electrical transport properties of liquid Sn using pseudopotential theory

We present the calculations of electrical resistivity, thermo-electric power and thermal conductivity based on the self-consistent approximation. The pseudopotential due to Hasegawa et al. [J. Non-Cryst. Solids 117/118, 300 (1990) M. Hasegawa, K. Hoshino, M. Watabe, and H. Young, J. Non-Cryst. Solids 117/118, 300 (1990).[Crossref], [Web of Science ®] , [Google Scholar]] for full electron–ion interaction, which is valid for all electrons and contains the repulsive delta function to achieve the necessary s-pseudisation, was used in the calculation. Temperature dependence of structure factor is achieved through temperature-dependent potential parameter in the pair-potential. The outcome of the present study is discussed in the light of other such results and with predictions of Wiedemann and Franz law up to moderately high temperature. Specially, high-temperature resistivity data necessitates the careful investigation of electron energy dispersion close to the Fermi level and possible metal to non-metal transition while going from dense-fluid to low density-fluid state. In the absence of experimental data at high temperature, these findings may serve as future guideline.     

Calix Receptor Edifice; Scrupulous Turn Off Fluorescent Sensor for Fe(III), Co(II) and Cu(II)

Novel Supramolecular fluorescence receptor derived from calix-system i.e. calix[4]resorcinarene bearing dansylchloride as fluorophore was designed and synthesized. The compound was purified by column chromatography and characterized by elemental analysis, NMR and Mass spectroscopy. Tetradansylated calix[4] resorcinarene (TDCR) shows a boat conformation with C₂v symmetry. The complexation behaviour of metal cations [Ag(I), Cd(II), Co(II), Fe(III), Hg(II), Cu(II), Pb(II), Zn(II), U(VI) (1?×?10^-4?M)] with tetra dansylated calix[4]resorcinarene (1?×?10^-6?M) was studied by spectophotometry and spectrofluorometry. Red shift in the absorption spectra led us to conclude that there is strong complexation Fe(III), Co(II) and Cu(II) with TDCR. These metal cations also produce quenching with red shifts in the emission spectra. The maximum quenching in emission intensity was observed in the case of Fe(III) and its binding constant was also found to be significantly higher than that of Co(II) and Cu(II). Quantum yield of metal complexes of Fe(III) was found to be lower in comparison with Co(II) and Cu(II) complexes. Stern Volmer analysis indicates that the mechanism of fluorescence quenching is either purely dynamic, or purely static.     

Causally discontinuous space-times

Along with certain properties of the region where distinguishingness is violated, it is proved that the violation of distinguishingness and reflectingness cannot occur individually.     

Triple differential cross-sections for the fast electron/positron impact ionization of hydrogen and helium in the Glauber approximation

Triple differential cross-section for electron and positron impact ionization of hydrogen and helium are calculated by using the Glauber approximation along with post-collision interaction effects which are estimated classically. The present results are compared with the recent absolute data of Ehrhardt, Jung and coworkers for the electron impact case. The positron impact case is found to lead to a larger binary to recoil peak maxima ratio (compared to the electron impact case) which further increases when post-collision interaction effects are included.     

Magnetogravitational Instability of a Thermally Conducting Rotating Plasma through a Porous Medium

Magnetogravitational instability of an infinite homogeneous, viscous, thermally conducting, rotating plasma flowing through a porous medium has been studied with the help of relevant linearized perturbation equations, using the method of normal mode analysis. Rotation is taken parallel and perpendicular to the magnetic field for both, the longitudinal and the transverse modes of propagation. The joint influence of the various parameters do not, essentially, change the Jeans' criterion but modifies the same. The adiabatic velocity of sound is being replaced by the isothermal one due to the thermal conductivity. Porosity reduces the effects of both, the magnetic field and the rotation, in the transverse mode of propagation, whereas the rotation is effective only along the magnetic field for an inviscid plasma. The viscosity removes the effect of rotation in the transverse mode of propagation.     

Isothermal compressibility and sound velocity of binary liquid systems: Application of hard sphere models

Sound velocity and density were measured in six binary liquid mixtures namely,n-heptane+toluene (I);n-heptane+n-hexane (II); toluene+n-hexane (III); cyclohexane+n-heptane (IV); cyclohexane+n-hexane (V), andn-decane+n-hexane (VI) at 298.15 K. The experimental isothermal compressibility has been evaluated from measured values of density and sound velocity. The isothermal compressibility of these mixtures has been calculated theoretically using different models for the hard sphere equation of state and also using Flory’s statistical theory. The computed values of isothermal compressibility were also compared with the experimentally evaluated values. A satisfactory agreement has been observed.     

Kinetics and mechanism of osmium(VIII)-catalysed and uncatalysed oxidation of aminoalcohols by chloramine-T in alkaline medium

Summary The kinetics of osmium(VIII)-catalysed oxidation of aminoalcohols,viz., 2-aminoethanol, 3-aminopropanol, diethanolamine and triethanolamine, by chloramine-T in alkaline medium have been investigated. The reactions follow a first-order-rate dependence with respect to oxidant. The order in [aminoalcohol] decreases from unity at higher concentrations of aminoalcohols while that in [OH^–] is nearly –1. The oxidation rate is directly proportional to [osmium(VIII)] in primary amino-alcohols, while that is proportional to {k+k [osmium(VIII)]} (where k and k are rate constants) in diethanolamine and triethanolamine. The uncatalysed oxidation of diethanolamine and triethanolamine follows a first-order-rate dependence in each of the oxidant and the sustrate. Suitable mechanisms consistent with the observed kinetic results are proposed.