13c And 1h Nmr Study Of Complexes Of 2-Pyridinethione And 4-Pyridinethione With Zn(Ii), Cd(Ii) And Hg(Ii) Halides

Proton and carbon-13 NMR has been used to study complexes of 2-pyridinethione (in its basic and deprotonated forms) and 4-pyridinethione with zinc(II), cadmium(II) and mercury(II) halides. The variations in the carbon-13 and proton chemical shifts are discussed.

Visual ecology of Indian carpenter bees II: adaptations of eyes and ocelli to nocturnal and diurnal lifestyles

Most bees are diurnal, with behaviour that is largely visually mediated, but several groups have made evolutionary shifts to nocturnality, despite having apposition compound eyes unsuited to vision in dim light. We compared the anatomy and optics of the apposition eyes and the ocelli of the nocturnal carpenter bee, Xylocopa tranquebarica, with two sympatric species, the strictly diurnal X. leucothorax and the occasionally crepuscular X. tenuiscapa. The ocelli of the nocturnal X. tranquebarica are unusually large (diameter ca. 1 mm) and poorly focussed. Moreover, their apposition eyes show specific visual adaptations for vision in dim light, including large size, large facets and very wide rhabdoms, which together make these eyes 9 times more sensitive than those of X. tenuiscapa and 27 times more sensitive than those of X. leucothorax. These differences in optical sensitivity are surprisingly small considering that X. tranquebarica can fly on moonless nights when background luminance is as low as 10(-5) cd m(-2), implying that this bee must employ additional visual strategies to forage and find its way back to the nest. These strategies may include photoreceptors with longer integration times and higher contrast gains as well as higher neural summation mechanisms for increasing visual reliability in dim light.

Genetic analysis of foot-and-mouth disease virus serotype A of Indian origin and detection of positive selection and recombination in leader protease- and capsid-coding regions

The leader protease (L-pro) and capsid-coding sequences (P1) constitute approximately 3 kb of the foot-and-mouth disease virus (FMDV). We studied the phylogenetic relationship of 46 FMDV serotype A isolates of Indian origin collected during the period 1968-2005 and also eight vaccine strains using the neighbour-joining tree and Bayesian tree methods. The viruses were categorized under three major groups - Asian, Euro-South American and European. The Indian isolates formed a distinct genetic group among the Asian isolates. The Indian isolates were further classified into different genetic subgroups (<5% divergence). Post-1995 isolates were divided into two subgroups while a few isolates which originated in the year 2005 from Andhra Pradesh formed a separate group. These isolates were closely related to the isolates of the 1970s. The FMDV isolates seem to undergo reverse mutation or onvergent evolution wherein sequences identical to the ancestors are present in the isolates in circulation. The eight vaccine strains included in the study were not related to each other and belonged to different genetic groups. Recombination was detected in the L-pro region in one isolate (A IND 20/82) and in the VP1 coding 1D region in another isolate (A RAJ 21/96). Positive selection was identified at aa positions 23 in the L-pro (P<0.05; 0.046*) and at aa 171 in the capsid protein VP1 (P<0.01; 0.003**).

Beta-Ketoacyl-ACP Synthase I/II from Plasmodium falciparum (PfFabB/F)-Is it B or F?

Condensing enzymes play an important and decisive role in terms of fatty acid composition of any organism. They can be classified as condensing enzymes involved in initiating the cycle and enzymes involved in elongating the initiated fatty acyl chain. In E. coli, two isoforms for the elongation condensing enzymes (FabB and FabF) exists whereas Plasmodium genome contains only one isoform. By in vitro complementation studies in E. coli CY244 cells, we show that PfFabB/ functions like E. coli FabF as the growth of the mutant cells could rescued only in the presence of oleic acid. But unlike bacterial enzyme, PfFabB/F does not increase the cis-vaccenic acid content in the mutant cells upon lowering the growth temperature. This study thus highlights the distinct properties of P. falciparum FabF which sets it apart from E. coli and most other enzymes of this family, described so far.

Fluctuation phenomena in electrochemistry part II. Modelling the noise sources

A discussion of the modelling of the primary and secondary noise sources introduced in the formalism of fluctuation phenomena in a previous report is presented. It is illustrated that the generalisation of the modelling of noise sources in mass transport as given by Tyagai is limited in its applicability. A general procedure for the same is discussed in detail.

Effect of Structural Modification on the Quantum-Size Effect in II-VI Semiconducting Nanocrystals

The electronic structure of group II-VI semiconductors in the stable wurtzite form is analyzed using state-of-the-art ab initio approaches to extract a simple and chemically transparent tight-binding model. This model can be used to understand the variation in the bandgap with size, for nanoclusters of these compounds. Results complement similar information already available for same systems in the zinc blende structure. A comparison with all available experimental data on quantum size effects in group II-VI semiconductor nanoclusters establishes a remarkable agreement between theory and experiment in both structure types, thereby verifying the predictive ability of our approach. The significant dependence of the quantum size effect on the structure type suggests that the experimental bandgap change at a given size compared to the bulk bandgap, may be used to indicate the structural form of the nanoclusters, particularly in the small size limit, where broadening of diffraction features often make it difficult to unambiguously determine the structure.

Stereochemical studies on cyclic peptides. XIII. Energy minimization studies on cyclic hexapeptides having hydrogen bonds

The basic cyclic hexapeptide conformations which accommodate hydrogen bonded β and γ turns in the backbone have been worked out using stereochemical criteria and energy minimization procedures. It was found that cyclic hexapeptides can be made up of all possible combinations of 4 ± 1 hydrogen bonded types I, I', II and II' β turns, giving rise to symmetric conformations having twofold and inversion symmetries as well as nonsymmetric structures. Conformations having exclusive features of 3 ± 1 hydrogen bonded γ turns were found to be possible in threefold and S6 symmetric cyclic hexapeptides. The results show that the cyclic hexapeptides formed by the linking of two β turn tripeptide fragments differ mainly in (a) the hydrogen bonding scheme present in the β turn tripeptides and (b) the conformation at the α-carbon atoms where the two tripeptide fragments link. The different hydrogen bonding schemes found in the component β turns are: 1) a β turn with only a 4 ± 1 hydrogen bond, 2) a type I or I' β turn with 4 ± 1 and 3 ± 1 hydrogen bonds occurring in a bifurcated form and 3) a type II or II' β turn having both the 4 ± 1 and the 3 ± 1 hydrogen bonds with the same acceptor oxygen atom. The conformation at the linking α-carbon atoms was found to lie either in the extended region or in the 3 ± 1 hydrogen bonded γ turn or inverse γ turn regions. Further, the threefold and the S6 symmetric conformations have three γ turns interleaved by three extended regions or three inverse γ turns, respectively. The feasibility of accommodating alanyl residues of both isomeric forms in the CHP minima has been explored. Finally, the available experimental data are reviewed in the light of the present results.

A Theoretical Investigation of the Ni(II)-Catalyzed Hydrovinylation of Styrene

We report a detailed and full computational investigation on the hydrovinylation reaction of styrene with the Ni(II)-phospholane catalytic system, which was originally presumed to proceed through a cationic mechanism involving a nickel hydride intermediate. The following general features emerge from this study on a specific catalyst complex that was found to give quantitative yield and moderate selectivity: (a) the activation barrier for the initiation (18.8 kcal/mol) is higher than that for the reaction due to a low-lying square-planar pentenyl chelate intermediate originating from a Ni(II)-allyl catalyst precursor. Consequently there is an induction period for the catalysis; (b) the exit of product from the catalyst is via a β-H-transfer step instead of the usual β-H elimination pathway, which has a very high activation energy due to a trans effect of the phospholane ligand; (c) the turnover-limiting and enantio- determining transition state is also the β-H-transfer; (d) because of the absence of a hydride intermediate, the unwanted isomerization of the product is prevented; (e) since the enantio-discrimination is decided at the H-transfer stage itself, the configuration of the product in a catalytic cycle influences the enantioselectivity in the subsequent cycle; (f) the trans effect of the sole strong ligand in the d8 square-planar Ni(II), the stability of the η3-benzyl intermediate, and the availability of three coordination sites enable regioselective hydrovinylation over the possible oligomerization/polymerization of the olefin substrates and linear hydrovinylation. This work has also confirmed the previously recognized role of the hemilabile group at various stages in the mechanism.

Generalized Burgers equations and Euler-Painleve transcendents. II

It was proposed earlier [P. L. Sachdev, K. R. C. Nair, and V. G. Tikekar, J. Math. Phys. 27, 1506 (1986)] that the Euler Painlevé equation yy[script `]+ay[script ']2+ f(x)yy[script ']+g(x) y2+by[script ']+c=0 represents the generalized Burgers equations (GBE's) in the same manner as Painlevé equations do the KdV type. The GBE was treated with a damping term in some detail. In this paper another GBE ut+uaux+Ju/2t =(gd/2)uxx (the nonplanar Burgers equation) is considered. It is found that its self-similar form is again governed by the Euler Painlevé equation. The ranges of the parameter alpha for which solutions of the connection problem to the self-similar equation exist are obtained numerically and confirmed via some integral relations derived from the ODE's. Special exact analytic solutions for the nonplanar Burgers equation are also obtained. These generalize the well-known single hump solutions for the Burgers equation to other geometries J=1,2; the nonlinear convection term, however, is not quadratic in these cases. This study fortifies the conjecture regarding the importance of the Euler Painlevé equation with respect to GBE's. Journal of Mathematical Physics is copyrighted by The American Institute of Physics.

Type II beta-turn conformation of pivaloyl-L-prolyl-alpha-aminoisobutyryl-N-methylamide: Theoretical, spectroscopic, and X-ray studies

Pivaloyl-L-Pro-Aib-N-methylamide has been shown to possess one intramolecular hydrogen bond in (CD3)2SO solution, by 1H-nmr methods, suggesting the existence of beta -turns, with Pro-Aib as the corner residues. Theoretical conformational analysis suggests that Type II beta-turn conformations are about 2 kcal mol-1 more stable than Type III structures. A crystallographic study has established the Type II beta-turn in the solid state. The molecule crystallizes in the space group P21 with a = 5.865 Å, b = 11.421 Å, c = 12.966 Å, beta = 97.55°, and Z = 2. The structure has been refined to a final R value of 0.061. The Type II -turn conformation is stabilized by an intramolecular 4 1 hydrogen bond between the methylamide NH and the pivaloyl CO group. The conformational angles are Pro = -57.8°, Pro = 139.3°, Aib = 61.4°, and Aib = 25.1°. The Type II beta-turn conformation for Pro-Aib in this peptide is compared with the Type III structures observed for the same segment in larger peptides.

Interaction of manganese(II) with valinomycin: Observation of mixed complexes

The interaction of antibiotic valinomycin with manganese (II) has been studied using circular dichroism, electron spin resonance and infrared techniques. Results show that Mn(II) forms complexes with valinomycin in both 2:1 (valinomycin-ion-valinomycin sandwich) and 1:1 (equimolar) stoichiometries. The 1:1 type observed here is very different from the well known K+-valinomycin bracelet conformation.

Evidence of episodic brittle faulting in the cratonic part of the Peninsular India and its implications for seismic hazard in slow deforming regions

The region around Waclakkancheri, in the province of Kerala, India, which lies in the vicinity of Palghat-Cauvery ;hear zone (within the Precambrian crystalline terrain), has been a site of microseismic activity since 1989. Earlier studies had identified a prominent WNW-ESE structure overprinting on the E-W trending lineaments associated with Palghat-Cauvery shear zone. We have mapped this structure, located in a chamockite quarry near Desamangalam, Waclakkancheri, which we identify as a ca. 30 km-long south dipping reverse fault. This article presents the characteristics of this fault zone exposed on the exhumed crystalline basement and discusses its significance in understanding the earthquake potential of the region. This brittle deformation zone consists of fracture sets with small-scale displacement and slip planes with embedded fault gouges. The macroscopic as well as the microscopic studies of this fault zone indicate that it evolved through different episodes of faulting in the presence of fluids. The distinct zones within consolidated gouge and the cross cutting relationship of fractures indicate episodic fault activity. At least four faulting episodes can be recognized based on the sequential development of different structural elements in the fault rocks. The repeated ruptures are evident along this shear zone and the cyclic behavior of this fault consists of co-seismic ruptures alternating with inter-seismic periods, which is characterized by the sealed fractures and consolidated gouge. The fault zone shows a minimum accumulated dip/oblique slip of 2.1 m in the reverse direction with a possible characteristic slip of 52 cm (for each event). The ESR dating of fault gouge indicates that the deformation zone records a major event in the Middle Quaternary. The empirical relationships between fault length and slip show that this fault may generate events M >= 6. The above factors suggest that this fault may be characterized as potentially active. Our study offers some new pointers that can be used in other slow deforming cratonic hinterlands in exploring the discrete active faults.

Metal chelates in vinyl polymerization: Kinetics and mechanism of acrylonitrile polymerization initiated by Cu(II) imine complexes

The free radical polymerization of acrylonitrile (AN) initiated by Cu(II) 4-anilino 2-one [Cu(II) ANIPO] Cu(II), 4-p-toluedeno 3-pentene 2-one [Cu(II) TPO], and Cu(II) 4-p-nitroanilino 3-pentene 2-one [Cu(II) NAPO] was studied in benzene at 50 and 60°C and in carbon tetrachloride (CCl4), dimethyl sulfoxide (DMSO), and methanol (MeOH) at 60°C. Although the polymerization proceeded in a heterogeneous phase, it followed the kinetics of a homogeneous process. The monomer exponents were 2 at two different temperatures and in different solvents. The square-root dependence of Rp on initiator concentration and higher monomer exponents accounted for a 1:2 complex formation between the chelate and monomer. The complex formation was shown by ultraviolet (UV) study. The activation energies, kinetics, and chain transfer constants were also evaluated.

Electrochemical phase formation (ECPF) and macrogrowth Part II. Two-rate models

A general theory is evolved for a class of macrogrowth models which possess two independent growth-rates. Relations connecting growth-rates to growth geometry are established and some new growth forms are shown to result for models with passivation or diffusion-controlled rates. The corresponding potentiostatic responses, their small and large time behaviours and peak characteristics are obtained. Numerical transients are also presented. An empirical equation is derived as a special case and an earlier equation is corrected. An interesting stochastic result pertaining to nucleation events in the successive layers is proved.