Role of the leaving group in the base-catalysed hydrolysis of pseudo-esters

The relative insensitivity of the rate of hydrolysis of γ-pseudo-esters to the leaving group compared to that of the normal esters emphasises that the conjugative ability is an important factor in determining the rate of hydrolysis of esters

A Safe Vaccine (DV-STM-07) against Salmonella Infection Prevents Abortion and Confers Protective Immunity to the Pregnant and New Born Mice

Pregnancy is a transient immuno-compromised condition which has evolved to avoid the immune rejection of the fetus by the maternal immune system. The altered immune response of the pregnant female leads to increased susceptibility to invading pathogens, resulting in abortion and congenital defects of the fetus and a subnormal response to vaccination. Active vaccination during pregnancy may lead to abortion induced by heightened cell mediated immune response. In this study, we have administered the highly attenuated vaccine strain delta pmrG-HM-D (DV-STM-07) in female mice before the onset of pregnancy and followed the immune reaction against challenge with virulent S. Typhimurium in pregnant mice. Here we demonstrate that DV-STM-07 vaccine gives protection against Salmonella in pregnant mice and also prevents Salmonella induced abortion. This protection is conferred by directing the immune response towards Th2 activation and Th1 suppression. The low Th1 response prevents abortion. The use of live attenuated vaccine just before pregnancy carries the risk of transmission to the fetus. We have shown that this vaccine is safe as the vaccine strain is quickly eliminated from the mother and is not transmitted to the fetus. This vaccine also confers immunity to the new born mice of vaccinated mothers. Since there is no evidence of the vaccine candidate reaching the new born mice, we hypothesize that it may be due to trans-colostral transfer of protective anti-Salmonella antibodies. These results suggest that our vaccine DV-STM-07 can be very useful in preventing abortion in the pregnant individuals and confer immunity to the new born. Since there are no such vaccine candidates which can be given to the new born and to the pregnant women, this vaccine holds a very bright future to combat Salmonella induced pregnancy loss.

Generation of Cationic Two-Coordinate Group-13 Ligand Systems by Spontaneous Halide Ejection: Remarkably Nucleophile-Resistant (Dimethylamino)borylene Complexes

Spontaneous ejection of chloride from a three-coordinate boron Lewis acid can be effected by employing very electron rich metal substituents and leads to the formation of a sterically unprotected terminal (dimethylamino)borylene complex that has a short metal-boron bond and remarkable resistance to attack by nucleophilic and protic reagents.

Group fission in Nilgiri langurs (Presbytis johnii)

During a field study on habituated groups of wild Nilgiri langurs (Presbytis johnii), four cases of group fission were observed which differed markedly from group changes reported in other species of the same genus. All fissions occurred in groups with more than one mature male and roughly coincided with the onset of loud call vocalization by the second mature male group member. As a result of the fission the founder group factions acquired the structure of a onemale group. The filial factions consisted of both mature males and females and occupied, at least temporarily, a part of, or an area adjacent to, the founder group. During fission, the amount of aggressive interactions between the two mature males increased. However, the majority of agonistic interactions involved ritualized threat and intimidation behavior without physical aggression. In at least three cases the two mature males involved in the fission had not joined recently but had lived in these groups for three years or more. Although the presence of all male bands and single males in the two study populations indicate that male replacement by invasive takeovers may occur, it is suggested that in Nilgiri langurs, noninvasive fissions are probably another common mechanism for the foundation and maintenance of bisexual one-male groups.

Role of hydroxyl group on the mesomorphism of alkyl glycosides:synthesis and thermal behavior of alkyl 6-deoxy-beta-D-glucopyranosides

A homologous series of alkyl 6-deoxy-beta-D-glucopyranoside amphiphiles was prepared,in an effort to identify the role of hydroxyl group in the mesomorphic behavior of alkyl glycosides. Synthesis was performed by a chlorination of the sugar moiety in alkyl-beta-D-glucopyranosides with methylsulfonyl chloride in DMF, followed by a metal mediated dehalogenation to secure alkyl 6-deoxy-beta-D-glucopyranosides, wherein the alkyl chain length varied from C-9 to C-16. The mesomorphic behavior of these 6-deoxy alkyl glycosides was assessed using polarizing optical microscopy, differential scanning calorimetry and X-ray diffraction method. Whereas the lower homologues exhibited a monotropic SmA phase till sub-ambient temperatures, the higher homologues formed a plastic phase. A partial interdigitized bilaye structure of SmA phase is inferred from experimental d-spacing and computationally derived lengths of the molecules. The results were compared with those of normal alkyl glucopyranosides, retained with hydroxyl groups at C-2-C-6 carbons, and alkyl 2-deoxy-glucopyranosides, devoid of a hydroxyl group at C-2 and the comparison showed important differences in the mesomorphic behavior.(C)2010 Elsevier Ireland Ltd. All rights reserved.

High-Rate,2-Group ML-Decodable STBCs for 2(m) Transmit Antennas

A Space-Time Block Code (STBC) in K-variables is said to be g-Group ML-Decodable (GMLD) if its Maximum-Likelihood (ML) decoding metric can be written as a sum of g independent terms, with each term being a function of a subset of the K variables. In this paper, a construction method to obtain high-rate, 2-GMLD STBCs for 2(m) transmit antennas, m > 1, is presented. The rate of the STBC obtained for 2(m) transmit antennas is 2(m-2) + 1/2(m), complex symbols per channel use. The design method is illustrated for the case of 4 and 8 transmit antennas. The code obtained for 4 transmit antennas is equivalent to the rate-5/4 Quasi-Orthogonal design (QOD) proposed by Yuen, Guan and Tjung.

A density matrix renormalization group study of low-lying excitations of polythiophene within a Pariser-Parr-Pople model

Symmetrized density-matrix-renormalization-group calculations have been carried out, within Pariser-Parr-Pople Hamiltonian, to explore the nature of the ground and low-lying excited states of long polythiophene oligomers. We have exploited C-2 symmetry and spin parity of the system to obtain excited states of experimental interest, and studied the lowest dipole allowed excited state and lowest dipole forbidden two photon state, for different oligomer sizes. In the long system limit, the dipole allowed excited state always lies below the lowest dipole forbidden two-photon state which implies, by Kasha rule, that polythiophene fluoresces strongly. The lowest triplet state lies below two-photon state as usual in conjugated polymers. We have doped the system with a hole and an electron and obtained the charge excitation gap and the binding energy of the 1(1)B(u)(-) exciton. We have calculated the charge density of the ground, one-photon and two-photon states for the longer system size of 10 thiophene rings to characterize these states. We have studied bond order in these states to get an idea about the equilibrium excited state geometry of the system. We have also studied the charge density distribution of the singly and doubly doped polarons for longer system size, and observe that polythiophenes do not support bipolarons.

Gauge theory of a group of diffeomorphisms. III. The fiber bundle description

A new fiber bundle approach to the gauge theory of a group G that involves space‐time symmetries as well as internal symmetries is presented. The ungauged group G is regarded as the group of left translations on a fiber bundle G(G/H,H), where H is a closed subgroup and G/H is space‐time. The Yang–Mills potential is the pullback of the Maurer–Cartan form and the Yang–Mills fields are zero. More general diffeomorphisms on the bundle space are then identified as the appropriate gauged generalizations of the left translations, and the Yang–Mills potential is identified as the pullback of the dual of a certain kind of vielbein on the group manifold. The Yang–Mills fields include a torsion on space‐time.

Microstructure and Properties of the Spray-Formed and Extruded 7075 Al Alloy

In the present investigation, a very good combination of strength and ductility, 630MPa 0.2% proof stress and 14.8% elongation to fracture in tensile test, has been obtained for the 7075 Al alloy after optimizing the processing parameters for spray forming, hot extruding the spray deposit, and peak aging the samples taken from the extruded rod. The spray deposits contained some porosity but it was almost eliminated on hot extrusion. Electron probe microanalysis revealed that even though spray forming was carried out in an open atmosphere, it did not affect the oxygen content and its distribution in the material on spray forming, because the atomizing argon gas provided a protective cover to molten droplets and prevented their oxidation. The chemical composition of the spray-formed material was found to be almost the same as the raw material, and the major alloying elements were found to be uniformly distributed in the extruded rod.

Intermolecular Chelate Linkage Isomerism of the Hydroxyimino Group in the Nickel(II), Copper(II), and Palladium(II) Complexes of Quadridentate Schiff-base Ligands

The C-nitrosation of bivalent quadridentate β-imino ketone complexes of nickel(II), copper(II), and palladium(II), with nitrosating reagents has been investigated. The chemical analysis and spectroscopic results reveal that one of the α-CH groups of the coordinated lignad undergoes selective nitrosation forming mono(hydroxyimino) derivative. The hydroxyimino group introduced coordinates through either N- or O- atom to metal(II) by dislodging the carbonyl group already coordinated. This gives rise to two linkage isomers, one with N-bonded and the other with O-bonded hydroxyimino group in the case of nickel(II) (except for 1d) and palladium(II), and a single isomer with O-bonded hydroxyimino group in copper(II) complexes. The isomers obtained from 1b and 1i have been separated by column chromatography. In chloroform each of the isomers of nickel(II) isomerizes to give an equilibrium mixture of two isomers, but not those of copper(II) and palladium(II).

Enantioselective and Protecting Group-Free Synthesis of 1-Deoxythionojirimycin, 1-Deoxythiomannojirimycin, and 1-Deoxythiotalonojirimycin

1-Deoxythioglyconojirimycins were synthesized by using a protecting group-free strategy, starting from readily available carbohydrates, in good overall yield. Use of benzyl-triethylammonium tetrathiomolybdate, BnEt3N](2)MoS4, as a sulfur transfer reagent and borohydride exchange resin (BER) reduction of a lactone enabled the efficient synthesis of the title compounds.