Probing the role of highly conserved residues in triosephosphate isomerase-analysis of site specific mutants at positions 64 and 75 in the Plasmodial enzyme

Highly conserved residues in enzymes are often found to be clustered close to active sites, suggesting that functional constraints dictate the nature of amino acid residues accommodated at these sites. Using the Plasmodiumfalciparum triosephosphate isomerase (PfTIM) enzyme () as a template, we have examined the effects of mutations at positions 64 and 75, which are not directly involved in the proton transfer cycle. Thr (T) occurring at position 75 is completely conserved, whereas only Gln (Q) and Glu (E) are accommodated at position 64. Biophysical and kinetic data are reported for four T75 (T75S/V/C/N) and two Q64 (Q64N/E) mutants. The dimeric structure is weakened in the Q64E and Q64N mutants, whereas dimer integrity is unimpaired in all four T75 mutants. Measurement of the concentration dependence of enzyme activity permits an estimate of K-d values for dimer dissociation (Q64N=73.79.2nm and Q64E=44.6 +/- 8.4nm). The T75S/V/C mutants have activities comparable to the wild-type enzyme, whereas a fourfold drop is observed for T75N. All four T75 mutants show a dramatic fall in activity between 35 degrees C and 45 degrees C. Crystal structure determination of the T75S/V/N mutants provides insights into the variations in local interactions, with the T75N mutant showing the largest changes. Hydrogen-bond interactions determine dimer stability restricting the choice of residues at position 64 to Gln (Q) and Glu (E). At position 75, the overwhelming preference for Thr (T) may be dictated by the imperative of maintaining temperature stability of enzyme activity.

GRMHD formulation of highly super-Chandrasekhar rotating magnetized white dwarfs: stable configurations of non-spherical white dwarfs

Here we extend the exploration of significantly super-Chandrasekhar magnetized white dwarfs by numerically computing axisymmetric stationary equilibria of differentially rotating magnetized polytropic compact stars in general relativity (GR), within the ideal magnetohydrodynamic regime. We use a general relativistic magnetohydrodynamic (GRMHD) framework that describes rotating and magnetized axisymmetric white dwarfs, choosing appropriate rotation laws and magnetic field profiles (toroidal and poloidal). The numerical procedure for finding solutions in this framework uses the 3 + 1 formalism of numerical relativity, implemented in the open source XNS code. We construct equilibrium sequences by varying different physical quantities in turn, and highlight the plausible existence of super-Chandrasekhar white dwarfs, with masses in the range of 2-3 solar mass, with central (deep interior) magnetic fields of the order of 10(14) G and differential rotation with surface time periods of about 1-10 s. We note that such white dwarfs are candidates for the progenitors of peculiar, overluminous Type Ia supernovae, to which observational evidence ascribes mass in the range 2.1-2.8 solar mass. We also present some interesting results related to the structure of such white dwarfs, especially the existence of polar hollows in special cases.

Ordered Pd2Ge Intermetallic Nanoparticles as Highly Efficient and Robust Catalyst for Ethanol Oxidation

Pd2Ge nanoparticles were synthesized by superhydride reduction of K2PdCl4 and GeCl4. The syntheses were performed using a solvothermal method in the absence of surfactants, and the size of the nanoparticles was controlled by varying the reaction time. The powder X-ray diffraction (PXRD) and transmission electron microscopy data suggest that Pd2Ge nanoparticles were formed as an ordered intermetallic phase. In the crystal structure, Pd and Ge atoms occupy two different crystallographic positions with a vacancy in one of the Ge sites, which was proved by PXRD and energy-dispersive X-ray analysis. The catalyst is highly efficient for the electrochemical oxidation of ethanol and is stable up to the 250th cycle in alkaline medium. The electrochemical active surface area and current density values obtained, 1.41 cm(2) and 4.1 mA cm(-2), respectively, are superior to those of the commercial Pd on carbon. The experimentally observed data were interpreted in terms of the combined effect of adsorption energies of CH3CO and OH radical, d-band center model, and work function of the corresponding catalyst surfaces.

ZnO quantum dots and graphene based heterostructure for excellent photoelastic and highly sensitive ultraviolet photodetector

Heterostructures comprised of zinc oxide quantum dots (ZnO QDs) and graphene are presented for ultraviolet photodetectors (UV PD). Graphene-ZnO QDs-graphene (G-ZnO QDs-G) based PD demonstrated an excellent UV photoresponse with outstanding photoelastic characteristics when illuminated for several cycles with a periodicity 5 s. PD demonstrated faster detection ability with the response and recovery times of 0.29 s in response to much lower UV illumination. A direct variation in photoresponse is revealed with the bias voltage as well as UV illumination intensity. A drastic reduction in the dark current is noticed due to potential barrier formation between adjacent ZnO QDs and the recombination rate reduces by directly transferring photogenerated charge carriers from ZnO QDs to graphene for enhanced the charge mobility.

Efficient and practical synthesis of modular chiral beta-organochalcogeno amines, ArYCH2CH(R)NH2, and single crystal structures of (S) - MsOCH2CH(Bz)NH3+ center dot Cl- and (R)-MsOCH2CH(Ph)NH3+ center dot Cl-

Modular chiral I3-organochalcogeno amines, ArYCH2CH(R)NH2 (4a-4g) where R = Me, Bz, Ph; and ArY = PhS, BzSe and 4-MeOC6H4Te respectively have been synthesized and characterized. Compounds 4a-4g were synthesized (Method II) from chiral aminoalkyl 13-methanesulfonate hydrochlorides, MsOCH2CH(R)NH3+ center dot Cl- (2a-2c) through nucleophilic displacement of MsO- with organochalcogenolate (ArY-). In another attempt (Method I) chiral beta-organotelluro amines (4a-4c) were prepared by deprotection of chiral N-boc I3-organotelluro amides, 4-MeOC6H4TeCH2CH(R)NH-Boc (3a-3c), which in turn, 13,-,1 were made from chiral N-boc 13-methanesulfonate amides (la-lc) and ArTeNa. 1H, and FTIR spectra of all the compounds (3a-3c and 4a-4g) were characteristic. The composition of 3a-3c was determined by elemental analysis. The a]TD values of 3b-3c and 4a-4g were determined. The single crystal structures of (S)-2b and (R)-2c were determined by X-Ray diffraction studies. Both (S)-2b and (R)2c were crystallized in orthorhombic system and the Flack parameter x was found 0.08(12) and 0.00(2) respectively. The crystal of (S)-2b contain two asymmetric units with gauche (A) and staggered (B) conformations. There are NH Cl-, NH-O and CH-O intra and intermolecular secondary interactions in (S)-2b and (R)-2c resulting in supramolecular structures. (C) 2015 Elsevier By. All rights reserved.

HOMOGENIZATION OF A HYPERBOLIC EQUATION WITH HIGHLY CONTRASTING DIFFUSIVITY COEFFICIENTS

We study a hyperbolic problem in the framework of periodic homogenization assuming a high contrast between the diffusivity coefficients of the two components M-epsilon and B-epsilon of the heterogeneous medium. There are three regimes depending on the ratio between the size of the period and the amplitude a, of the diffusivity in B-epsilon. For the critical regime alpha(epsilon) similar or equal to epsilon, the limit problem is a strongly coupled system involving both the macroscopic and the microscopic variables. We also include the results in the non critical case.

HOMOGENIZATION OF A HYPERBOLIC EQUATION WITH HIGHLY CONTRASTING DIFFUSIVITY COEFFICIENTS

We study a hyperbolic problem in the framework of periodic homogenization assuming a high contrast between the diffusivity coefficients of the two components M-epsilon and B-epsilon of the heterogeneous medium. There are three regimes depending on the ratio between the size of the period and the amplitude a, of the diffusivity in B-epsilon. For the critical regime alpha(epsilon) similar or equal to epsilon, the limit problem is a strongly coupled system involving both the macroscopic and the microscopic variables. We also include the results in the non critical case.

Social Experience Is Sufficient to Modulate Sleep Need of Drosophila without Increasing Wakefulness

Organisms quickly learn about their surroundings and display synaptic plasticity which is thought to be critical for their survival. For example, fruit flies Drosophila melanogaster exposed to highly enriched social environment are found to show increased synaptic connections and a corresponding increase in sleep. Here we asked if social environment comprising a pair of same-sex individuals could enhance sleep in the participating individuals. To study this, we maintained individuals of D. melanogaster in same-sex pairs for a period of 1 to 4 days, and after separation, monitored sleep of the previously socialized and solitary individuals under similar conditions. Males maintained in pairs for 3 or more days were found to sleep significantly more during daytime and showed a tendency to fall asleep sooner as compared to solitary controls (both measures together are henceforth referred to as ``sleep-enhancement''). This sleep phenotype is not strain-specific as it is observed in males from three different ``wild type'' strains of D. melanogaster. Previous studies on social interaction mediated sleep-enhancement presumed `waking experience' during the interaction to be the primary underlying cause; however, we found sleep-enhancement to occur without any significant increase in wakefulness. Furthermore, while sleep-enhancement due to group-wise social interaction requires Pigment Dispersing Factor (PDF) positive neurons; PDF positive and CRYPTOCHROME (CRY) positive circadian clock neurons and the core circadian clock genes are not required for sleep-enhancement to occur when males interact in pairs. Pair-wise social interaction mediated sleep-enhancement requires dopamine and olfactory signaling, while visual and gustatory signaling systems seem to be dispensable. These results suggest that socialization alone (without any change in wakefulness) is sufficient to cause sleep-enhancement in fruit fly D. melanogaster males, and that its neuronal control is context-specific.

Primary and rechargeable zinc-air batteries using ceramic and highly stable TiCN as an oxygen reduction reaction electrocatalyst

Primary and secondary zinc-air batteries based on ceramic, stable, one dimensional titanium carbonitride (TiCN) nanostructures are reported. The optimized titanium carbonitride composition by density functional theory reveals their good activity towards the oxygen reduction reaction (ORR). Electrochemical measurements show their superior performance for the ORR in alkaline media coupled with favourable kinetics. The nanostructured TiCN lends itself amenable to be used as an air cathode material in primary and rechargeable zinc-air batteries. The battery performance and cyclability are found to be good. Further, we have demonstrated a gel-based electrolyte for rechargeable zinc-air batteries based on a TiCN cathode under ambient, atmospheric conditions without any oxygen supply from a cylinder. The present cell can work at current densities of 10-20 mA cm(2) (app. 10 000 mA g(-1) of TiCN) for several hours (63 h in the case of 10 mA cm(-2)) with a charge retention of 98%. The low cost, noble metal-free, mechanically stable and corrosion resistant TiCN is a very good alternative to Pt for metal-air battery chemistry.

A noble and single source precursor for the synthesis of metal-rich sulphides embedded in an N-doped carbon framework for highly active OER electrocatalysts

Here, we demonstrate a green and environment-friendly pyrolysis route for the synthesis of metal-rich sulphide embedded in an N-doped carbon (NC) framework in the absence of sulphide ions (S2-). The metal-chelate complex (tris(ethylenediamine) metal(II) sulfate) serves as a new and single source precursor for the synthesis of earth abundant and non-precious hybrid structures such as metal-rich sulphides Co9S8@NC and Ni3S2@ NC when M-II = Co2+ and Ni2+ and counter sulphate (SO42-) ions are the source of S. Both the hybrids show superior OER activity as compared to commercial RuO2.