Contribution of texture to the strengthening and fracture in hot-rolled magnesium-12.7 at % cadmium alloy

The grain size dependencies of the yield and fracture stresses in hot rolled Mg-12.7 at % Cd alloy have been measured in the temperature range 77 to 420 K and are found to be in accordance with HalI-Petch type of equations. In hot rolled Mg-12.7 Cd alloy, the HalI-Petch intercept a w is higher than that in hot rolled magnesium, while the slope ky is comparable. The fracture is intercrystalline at 77 K, mixed mode at 300 K and ductile at 420 K. The above flow and fracture behaviours are interpreted in terms of the complimentary effects of texture hardening and solid solution strengthening.

Structure of 7-methyl-1(2)a,1(6)a,3(4)a-trihomocubane-1(6)a,3(4)a-dione,star-c12h12o2- a case of enantiomeric and rotational disorder

M r = 188.22, monoclinic, P21/n, a = 6.219 (2), b= 10.508 (2), c=7.339 (1)A, t= 107.64 (2) °, V= 457 ,/k 3, Z = 2, D m - - 1.360 (3), D x = 1.366 (2)Mgm -3, ~,(MoKa) = 0.7107/~, #= 0.053 mm -I, F(000) = 200, T= 293 K. Final R = 5.8% for 614 significant reflections. The molecule, which does not possess a centre of symmetry, occupies a crystallographic centre of symmetry because of the statistical enantiomeric and rotational disorder. Latticeenergy calculations, based on van der Waals attractive and repulsive potentials, clearly show minima at the observed disordered positions.

Reactivity of Cationic Terminal Borylene Complexes: Novel Mechanisms for Insertion and Metathesis Chemistry Involving Strongly Lewis Acidic Ligand Systems

The reactions of terminal borylene complexes of the type [CpFe(CO)(2)(BNR2)](+) (R = `Pr, Cy) with heteroallenes have been investigated by quantum-chemical methods, in an attempt to explain the experimentally observed product distributions. Reaction with dicyclohexylcarbodiimide (CyNCNCy) gives a bis-insertion product, in which 1 equiv of carbodiimide is assimilated into each of the Fe=B and B=N double bonds to form a spirocyclic boronium system. In contrast, isocyanates (R'NCO, R' = Ph, 2,6-wXy1, CY; XYl = C6H3Me2) react to give isonitrile complexes of the type [CpFe(CO)(2)(CNR')]+, via a net oxygen abstraction (or formal metathesis) process. Both carbodiimide and socyanate substrates are shown to prefer initial attack at the Fe=B bond rather than the B=N bond of the borylene complex. Further mechanistic studies reveal that the carbodiimide reaction ultimately leads to the bis-insertion compounds [CpFe(CO)(2)C(NCy)(2)B(NCY)(2)CNR2](+), rather than to the isonitrile system [CpFe(CO)(2)(CNCy)](+), on the basis of both thermodynamic (product stability) and kinetic considerations (barrier heights). The mechanism of the initial carbodiimide insertion process is unusual in that it involves coordination of the substrate at the (borylene) ligand followed by migration of the metal fragment, rather than a more conventional process: i.e., coordination of the unsaturated substrate at the metal followed by ligand migration. In the case of isocyanate substrates, metathesis products are competitive with those from the insertion pathway. Direct, single-step metathesis reactivity to give products containing a coordinated isonitrile ligand (i.e. [CpFe(CO)(2)(CNR')](+)) is facile if initial coordination of the isocyanate at boron occurs via the oxygen donor (which is kinetically favored); insertion chemistry is feasible when the isocyanate attacks initially via the nitrogen atom. However, even in the latter case, further reaction of the monoinsertion product so formed with excess isocyanate offers a number of facile (low energetic barrier) routes which also generate ['CpFe(CO)(2)(CNR')](+), rather than the bis-insertion product [CpFe(CO)(2)C(NR')(O)B(NR')(O)CNR2](+) (i.e., the direct analogue of the observed products in the carbodiimide reaction).

Expression Profiling of Nucleotide Metabolism-Related Genes in Human Breast Cancer Cells After Treatment with 5-Fluorouracil

5-Fluorouracil (5-FU) is one of the most widely used drugs for treatment of cancers, including breast cancer that exhibits its anticancer activity by inhibiting DNA synthesis and also incorporated into DNA and RNA. The objective of this investigation was to find out the total nucleotide metabolism genes regulated by 5-FU in breast cancer cell line. The breast cancer cell line MCF-7 was treated with the drug 5-FU. To analyze the expression of genes, we have conducted the experiment using 1.7k and 19k human microarray slide and confirmed the expression of genes by semiquantitative reverse transcription-polymerase chain reaction. The expression of 44 genes involved in the nucleotide metabolism pathway was quantified. Of these 44 genes analyzed, transcription of 6 genes were upregulated and 9 genes were downregulated. Earlier studies revealed that the transcription of genes for key enzymes like thymidylate synthase, thymidinekinase, and dihydropyrimidine dehydrogenase are regulated by 5-FU. This study identified some novel genes like thioredoxin reductase, ectonucleotide triphosphate dephosphorylase, and CTP synthase are regulated by 5-FU. The data also reveal large-scale perturbation in transcription of genes not involved directly in the known mechanism of action of 5-FU.

A Multilevel Inverter with Hexagonal and 12-sided Polygonal Space Vector Structure for Induction Motor Drive

This paper proposes a multilevel inverter which produces hexagonal voltage space vector structure in lower modulation region and a 12-sided polygonal space vector structure in the over-modulation region. Normal conventional multilevel inverter produces 6n +/- 1 (n=odd) harmonics in the phase voltage during over-modulation and in the extreme square wave mode operation. However, this inverter produces a 12-sided polygonal space vector location leading to the elimination of 6n 1 (n=odd) harmonics in over-modulation region extending to a final 12-step mode operation. The inverter consists of three conventional cascaded two level inverters with asymmetric dc bus voltages. The switching frequency of individual inverters is kept low throughout the modulation index. In the low speed region, hexagonal space phasor based PWM scheme and in the higher modulation region, 12-sided polygonal voltage space vector structure is used. Experimental results presented in this paper shows that the proposed converter is suitable for high power applications because of low harmonic distortion and low switching losses.

M. bovis BCG induced expression of COX-2 involves nitric oxide-dependent and -independent signaling pathways

In a multifaceted immunity to mycobacterial infection, induced expression of cyclooxygenase-2 (COX-2) by Mycobacterium bovis bacillus Calmette-Guerin (BCG) may act as an important influencing factor for the effective host immunity. We here demonstrate that M. bovis BCG-triggered TLR2-dependent signaling leads to COX-2 and PGE2 expression in vitro in macrophages and in vivo in mice. Further, the presence of PGE2 could be demonstrated in sera or cerebrospinal fluid of tuberculosis patients. The induced COX-2 expression in macrophages is dependent on NF-kappa B activation, which is mediated by inducible NO synthase (iNOS)/NO-dependent participation of the members of Notch1-PI-3K signaling cascades as well as iNOS-independent activation of ERK1/2 and p38 MAPKs. Inhibition of iNOS activity abrogated the M. bovis BCG ability to trigger the generation of Notch1 intracellular domain (NICD), a marker for Notch1 signaling activation, as well as activation of the PI-3K signaling cascade. On the contrary, treatment of macrophages with 3-morpholinosydnonimine, a NO donor, resulted in a rapid increase in generation of NICD, activation of PI-3K pathway, as well as the expression of COX-2. Stable expression of NICD in RAW 264.7 macrophages resulted in augmented expression of COX-2. Further, signaling perturbations suggested the involvement of the cross-talk of Notch1 with members with the PI-3K signaling cascade. These results implicate the dichotomous nature of TLR2 signaling during M. bovis BCG-triggered expression of COX-2. In this perspective, we propose the involvement of iNOS/NO as one of the obligatory, early, proximal signaling events during M. bovis BCG-induced COX-2 expression in macrophages.

5,7-Dimethoxy-2-phenyl-4H-chromen-4-one

The asymmetric unit of the title compound, C17H14O4, contains two independent molecules which differ in the relative orientations of the phenyl rings with repect to the essentially planar [maximum deviations of 0.029 (2) and 0.050 (2) angstrom in the two molecules] chromene fused-ring system, forming dihedral angles of 10.3 (5) and 30.86 (5)degrees in the two molecules. The crystal structure is stabilized by weak C-H center dot center dot center dot O and C-H center dot center dot center dot pi interactions, and pi-pi stacking interactions.

Measurement of Turbulence and pitch of the airstream in the 5'* 7' tunnel of Indian Institute of Science

Abstract is not available.

Topochemical photodimerization of 7-acetoxycoumarin: the acetoxy group as a steering agent

Among the various substituted coumarins investigated only 7-acetoxycoumarin is observed to photodimerize topochemically in the crystalline state and this observation may be of importance in the context of "crystal engineering".

The Structure of 9b-Methyl- 3afl,3b~,5 a~t,9a0h9bfl, 11 afl-perhydrophenanthro-[2,l-b]furan-7-one

C17H2602, M, = 262, triclinic, PI, a = 8.513(2), b = 8.970(2), c = 11.741(3)A, a = 120.51 (5), fl = 93.30(4), y = 68.43(4) ° , V = 708.9,/k 3, Z = 2, D O = 1.213, D e = 1.227 Mg m -a, g(Mo Ka, 2 = 0.7107 ,&) = 0.084 mm -1, F(000) = 288. The structure, solved by direct methods, has been refined to an R value of 5.9% using 1361 intensity measurements. The ring junctions, in sequence from either end of the polycycle, are cis, trans and cis.

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.

Effect of Crowding Agents, Signal Peptide, and Chaperone SecB on the Folding and Aggregation of E. coli Maltose Binding Protein

SecB, a soluble cytosolic chaperone component of the Secexport pathway, binds to newly synthesized precursor proteins and prevents their premature aggregation and folding and subsequently targets them to the translocation machinery on the membrane. PreMBP, the precursor form of maltose binding protein, has a 26-residue signal sequence attached to the N-terminus of MBP and is a physiological substrate of SecB. We examine the effect of macromolecular crowding and SecB on the stability and refolding of denatured preMBP and MBP. PreMBP was less stable than MBP (ΔTm =7( 0.5 K) in both crowded and uncrowded solutions. Crowding did not cause any substantial changes in the thermal stability ofMBP(ΔTm=1(0.4 K) or preMBP (ΔTm=0(0.6 K), as observed in spectroscopically monitored thermal unfolding experiments. However, both MBP and preMBP were prone to aggregation while refolding under crowded conditions. In contrast to MBP aggregates, which were amorphous, preMBP aggregates form amyloid fibrils.Under uncrowded conditions, a molar excess of SecB was able to completely prevent aggregation and promote disaggregation of preformed aggregates of MBP. When a complex of the denatured protein and SecB was preformed, SecB could completely prevent aggregation and promote folding of MBP and preMBP even in crowded solution. Thus, in addition to maintaining substrates in an unfolded, export-competent conformation, SecB also suppresses the aggregation of its substrates in the crowded intracellular environment. SecB is also able to promote passive disaggregation of macroscopic aggregates of MBP in the absence of an energy source such as ATP or additional cofactors. These experiments also demonstrate that signal peptide can reatly influence protein stability and aggregation propensity.

Topochemical dimerization of non-parallel double bonds: 7-methoxycoumarin

X-ray crystal structure analysis of 7-methoxycoumarin reveals that the reactive double bonds are rotated by about 65° with respect to each other, the centre-to-centre distance between the double bonds being 3.83 Å. In spite of this unfavourable arrangement, photodimerization occurs in the crystalline state yielding the syn-head-tail dimer as the only product. Lattice energy calculations on ground-state molecules in crystals throw light on the mechanism of the reaction.

Molecular convergence of hexosamine biosynthetic pathway and ER stress leading to insulin resistance in L6 skeletal muscle cells

Augmentation of hexosamine biosynthetic pathway (HBP) and endoplasmic reticulum (ER) stress were independently related to be the underlying causes of insulin resistance. We hypothesized that there might be a molecular convergence of activated HBP and ER stress pathways leading to insulin resistance. Augmentation of HBP in L6 skeletal muscle cells either by pharmacological (glucosamine) or physiological (high-glucose) means, resulted in increased protein expression of ER chaperones (viz., Grp78, Calreticulin, and Calnexin), UDP-GlcNAc levels and impaired insulin-stimulated glucose uptake. Cells silenced for O-glycosyl transferase (OGT) showed improved insulin-stimulated glucose uptake (P < 0.05) but without any effect on ER chaperone upregulation. While cells treated with either glucosamine or high-glucose exhibited increased JNK activity, silencing of OGT resulted in inhibition of JNK and normalization of glucose uptake. Our study for the first time, demonstrates a molecular convergence of O-glycosylation processes and ER stress signals at the cross-road of insulin resistance in skeletal muscle.

Synthesis and Characterization of Carbon-Coated LiNi1/3Co1/3Mn1/3O2 in a Single Step by an Inverse Microemulsion Route

Layered LiNi1/3Co1/3Mn1/3O2, which is isostructural to LiCoO2, is considered as a potential cathode material. A layer of carbon coated on the particles improves the electrode performance, Which is attributed to an increase of the grain connectivity and also to protection of metal oxide from chemical reaction. The present work involves in situ synthesis of carbon-coated submicrometer-sized particles of LiNi1/3Co1/3Mn1/3O2 in an inverse microemulsion medium in the presence of glucose. The precursor obtained from the reaction is heated in air at 900 degrees C for 6 h to get crystalline LiNi1/3Co1/3Mn1/3O2. The carbon coating is found to impart porosity as well as higher surface area in relation to bare samples of the compound. The electrochemical characterization studies provide that carbon-coated LiNi1/3Co1/3Mn1/3O2 samples exhibit improved rate capability and cycling performance. The carbon coatings are shown to suppress the capacity fade, which is normally observed for the bare compound. Impedance spectroscopy data provide additional evidence for the beneficial effect of a carbon coating on LiNi1/3Co1/3Mn1/3O2 particles.