Organocatalytic asymmetric direct vinylogous Michael addition of α,β-unsaturated γ-butyrolactam to nitroolefins

The first organocatalytic enantioselective direct vinylogous Michael reaction of α,β-unsaturated γ-butyrolactam to nitroolefins is developed using cinchona alkaloids as the catalysts. Both product enantiomers are accessible with moderate to good enantioselectivity.

Organocatalytic asymmetric direct vinylogous Michael addition of alpha,beta-unsaturated gamma-butyrolactam to nitroolefins

The first organocatalytic enantioselective direct vinylogous Michael reaction of alpha,beta-unsaturated gamma-butyrolactam to nitroolefins is developed using cinchona alkaloids as the catalysts. Both product enantiomers are accessible with moderate to good enantioselectivity.

Perfect Static Balance of Linkages by Addition of Springs But Not Auxiliary Bodies

A linkage of rigid bodies under gravity loads can be statically counter-balanced by adding compensating gravity loads. Similarly, gravity loads or spring loads can be counterbalanced by adding springs. In the current literature, among the techniques that add springs, some achieve perfect static balance while others achieve only approximate balance. Further, all of them add auxiliary bodies to the linkage in addition to springs. We present a perfect static balancing technique that adds only springs but not auxiliary bodies, in contrast to the existing techniques. This technique can counter-balance both gravity loads and spring loads. The technique requires that every joint that connects two bodies in the linkage be either a revolute joint or a spherical joint. Apart from this, the linkage can have any number of bodies connected in any manner. In order to achieve perfect balance, this technique requires that all the spring loads have the feature of zero-free-length, as is the case with the existing techniques. This requirement is neither impractical nor restrictive since the feature can be practically incorporated into any normal spring either by modifying the spring or by adding another spring in parallel. DOI: 10.1115/1.4006521]

Catalytic Asymmetric Direct Vinylogous Michael Addition of Deconjugated Butenolides to Maleimides for the Construction of Quaternary Stereogenic Centers

Competition under control: A practical and efficient direct asymmetric vinylogous Michael reaction of deconjugated butenolides has been developed (see scheme). The products of this reaction, highly functionalized chiral succinimides, are obtained in excellent yield with high diastereoselectivity (up to d.r.=18:1) and outstanding enantioselectivity (up to e.r.=99.5:0.5).

Effect of Mg addition on microstructural, mechanical and environmental properties of Nb-Si eutectic composite

The paper reports the effect of addition of small amount of Mg on the mechanical and oxidation properties of Nb-Nb3Si eutectic composites in Nb-Si system under the condition of suction casting. Mg addition increases the volume fraction of primary dendrites of Nb solid solution. This phase contains significant amount of strengthening precipitates. Two different precipitates are identified. The large plate shaped precipitates are that of hcp phase, while fine coherent precipitates have the structure similar to recently identified delta-Nb11Si2 phase. The Mg addition improves both the strength and ductility of the composite at room temperature (similar to 1.4 GPa and similar to 5% engineering strain) as well as at 700 degrees C(similar to 1.2 GPa and similar to 7% engineering strain). The presence of Mg results in a complex barrier layer which significantly increases the oxidation resistance up to a temperature of at least 1000 degrees C. (C) 2012 Elsevier B.V. All rights reserved.

Force and ATP hydrolysis dependent regulation of RecA nucleoprotein filament by single-stranded DNA binding protein

In Escherichia coli, the filament of RecA formed on single-stranded DNA (ssDNA) is essential for recombinational DNA repair. Although ssDNA-binding protein (SSB) plays a complicated role in RecA reactions in vivo, much of our understanding of the mechanism is based on RecA binding directly to ssDNA. Here we investigate the role of SSB in the regulation of RecA polymerization on ssDNA, based on the differential force responses of a single 576-nucleotide-long ssDNA associated with RecA and SSB. We find that SSB outcompetes higher concentrations of RecA, resulting in inhibition of RecA nucleation. In addition, we find that pre-formed RecA filaments de-polymerize at low force in an ATP hydrolysis- and SSB-dependent manner. At higher forces, re-polymerization takes place, which displaces SSB from ssDNA. These findings provide a physical picture of the competition between RecA and SSB under tension on the scale of the entire nucleoprotein SSB array, which have broad biological implications particularly with regard to competitive molecular binding.

Optical properties change with the addition and diffusion of Bi to As2S3 in the Bi/As2S3 bilayer thin film

The role of Bi layer (thickness similar to 7 nm) on As2S3 film was extensively studied for different optical applications in which Bi (top layer) as active and diffusing layer and As2S3 as barrier (matrix) layer. Bilayer thin films of Bi/As2S3 were prepared from Bi and As2S3 by thermal evaporation technique under high vacuum. The decrease of optical band gap with the addition of Bi to As2S3 has been explained on the basis of density of states and the increase in disorder in the system. It was found that the efficient changes of optical parameters (transmission, optical band gap, refraction) could be realized due to the photo induced diffusion activated by the focused 532 nm laser irradiation and formation of different bonds. The diffusion of Bi into As2S3 matrix increases the optical band gap producing photo bleaching effect. The changes were characterised by different experimental techniques. (C) 2012 Elsevier B.V. All rights reserved.

Synthesis, characterization and thermal degradation of dual temperature- and pH-sensitive RAFT-made copolymers of N,N-(dimethylamino)ethyl methacrylate and methyl methacrylate

Poly{(N,N-(dimethylamino)ethyl methacrylate]-co-(methyl methacrylate)} copolymers of various compositions were synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization at 70 degrees C in N,N-dimethylformamide. The polymer molecular weights and molecular weight distributions were obtained from size exclusion chromatography, and they indicated the controlled nature of the RAFT polymerizations; the polydispersity indices are in the range 1.11.3. The reactivity ratios of N,N-(dimethylamino)ethyl methacrylate (DMAEMA) and methyl methacrylate (MMA) (rDMAEMA = 0.925 and rMMA = 0.854) were computed by the extended KelenTudos method at high conversions, using compositions obtained from 1H NMR. The pH- and temperature-sensitive behaviour were studied in aqueous solution to confirm dual responsiveness of these copolymers. The thermal properties of the copolymers with various compositions were investigated by differential scanning calorimetry and thermogravimetric analysis. The kinetics of thermal degradation were determined by Friedmann and Chang techniques to evaluate various parameters such as the activation energy, the order and the frequency factor. (c) 2012 Society of Chemical Industry

The effect of minor addition of Ni on the microstructural evolution and mechanical properties of suction cast Al-0.14 at. pct Sc binary alloy

Aluminum scandium binary alloys represent a promising precipitation-hardening alloy system. However, the hardness of the binary alloys decreases with the rapid coarsening of Al3Sc precipitate during high-temperature aging. In the current study, we report a new approach to compensate for the loss of mechanical properties by combining rapid solidification with very small ternary addition of transition metal Ni. This addition yields dispersion, and at a critical concentration improves the mechanical properties. We explore additions of a maximum of 0.06 at. pct of Nickel to a binary Al-0.14 at. pct Sc alloy, which yield nickel-rich dispersions. We report two kinds of biphasic dispersions containing AlNi2Sc/Al9Ni2 and alpha-Al/Al9Ni2 phase combinations. The maximum improvement in mechanical properties occurs with the addition of 0.045 at. pct Ni with a yield strength of 239 +/- A 7 MPa for an aging treatment at 583 K (310 A degrees C) for 15 hours. DOI: 10.1007/s11661-013-1624-z (C) The Minerals, Metals & Materials Society and ASM International 2013

Effect of indium addition on microstructural, mechanical and oxidation properties of suction cast Nb-Si eutectic alloy

The paper reports effect of small ternary addition of In on the microstructure, mechanical property and oxidation behaviour of a near eutectic suction cast Nb-19.1 at-%Si-1.5 at-%In alloy. The observed microstructure consists of a combination of two kinds of lamellar structure. They are metal-intermetallic combinations of Nb-ss-beta-Nb5Si3 and Nb-ss-alpha-Nb5Si3 respectively having 40-60 nm lamellar spacings. The alloy gives compressive strength of 3 GPa and engineering strain of similar to 3% at room temperature. The composite structure also exhibits a large improvement in oxidation resistance at high temperature (1000 degrees C).

Diverse functions of restriction-modification systems in addition to cellular defense

Restriction-modification (R-M) systems are ubiquitous and are often considered primitive immune systems in bacteria. Their diversity and prevalence across the prokaryotic kingdom are an indication of their success as a defense mechanism against invading genomes. However, their cellular defense function does not adequately explain the basis for their immaculate specificity in sequence recognition and nonuniform distribution, ranging from none to too many, in diverse species. The present review deals with new developments which provide insights into the roles of these enzymes in other aspects of cellular function. In this review, emphasis is placed on novel hypotheses and various findings that have not yet been dealt with in a critical review. Emerging studies indicate their role in various cellular processes other than host defense, virulence, and even controlling the rate of evolution of the organism. We also discuss how R-M systems could have successfully evolved and be involved in additional cellular portfolios, thereby increasing the relative fitness of their hosts in the population.

Catalytic Asymmetric Direct Vinylogous Michael Addition of gamma-Aryl-Substituted Deconjugated Butenolides to Nitroolefins and N-Phenylmaleimide

Direct asymmetric vinylogous Michael reactions of gamma-aryl-substituted deconjugated butenolides with nitroolefins and N-phenylmaleimide are described using bifunctional thiourea derivatives as the catalyst. The resulting butenolide derivatives containing adjacent quaternary and tertiary stereocenters are obtained in good yields (54-90%) and with excellent enantioselectivities (er up to 99:1) and high diastereoselectivities (dr up to > 20:1).

Synergistic Lewis base and anion-binding catalysis for the enantioselective vinylogous addition of deconjugated butenolides to allenoates

An enantioselective vinylogous umpolung addition of deconjugated butenolides to allenoates has been developed for the first time with the help of synergistic combination of an achiral phosphine and a chiral squaramide, and represents the first example of a catalytic enantioselective C gamma-C gamma bond formation between two different carbonyl partners.

Effect of the Addition of B2O3 on the Density, Microstructure, Dielectric, Piezoelectric and Ferroelectric Properties of K0.5Na0.5NbO3 Ceramics

Boron oxide (B2O3) addition to pre-reacted K0.5Na0.5NbO3 (KNN) powders facilitated swift densification at relatively low sintering temperatures which was believed to be a key to minimize potassium and sodium loss. The base KNN powder was synthesized via solid-state reaction route. The different amounts (0.1-1 wt%) of B2O3 were-added, and ceramics were sintered at different temperatures and durations to optimize the amount of B2O3 needed to obtain KNN pellets with highest possible density and grain size. The 0.1 wt% B2O3-added KNN ceramics sintered at 1,100 A degrees C for 1 h exhibited higher density (97 %). Scanning electron microscopy studies confirmed an increase in average grain size with increasing B2O3 content at appropriate temperature of sintering and duration. The B2O3-added KNN ceramics exhibited improved dielectric and piezoelectric properties at room temperature. For instance, 0.1 wt% B2O3-added KNN ceramic exhibited d (33) value of 116 pC/N which is much higher than that of pure KNN ceramics. Interestingly, all the B2O3-added (0.1-1 wt%) KNN ceramics exhibited polarization-electric field (P vs. E) hysteresis loops at room temperature. The remnant polarization (P (r)) and coercive field (E (c)) values are dependent on the B2O3 content and crystallite size.

Effect of nanoscale boron carbide particle addition on the microstructural evolution and mechanical response of pure magnesium

In this study, the effect of nano-B4C addition on the microstructural and the mechanical behavior of pure Mg are investigated. Pure Mg-metal reinforced with different amounts of nano-size B4C particulates were synthesized using the disintegrated melt deposition technique followed by hot extrusion. Microstructural characterization of the developed Mg/x-B4C composites revealed uniform distribution of nano-B4C particulates and significant grain refinement. Electron back scattered diffraction (EBSD) analyses showed presence of relatively more recrystallized grains and absence of fiber texture in Mg/B4C nanocomposites when compared to pure Mg. The evaluation of mechanical properties indicated a significant improvement in tensile properties of the composites. The significant improvement in tensile ductility (similar to 180% increase with respect to pure Mg) is among the highest observed when compared to the pure Mg based nanocomposites existing in the current literature. The superior mechanical properties of the Mg/B4C nanocomposites are attributed to the uniform distribution of the nanoparticles and the tendency for texture randomization (absence of fiber texture) achieved due to the nano-B4C addition. (C) 2013 Elsevier Ltd. All rights reserved.