X=Y-ZH COMPOUNDS AS POTENTIAL 1,3-DIPOLES .43. METAL-ION CATALYZED ASYMMETRIC 1,3-DIPOLAR CYCLOADDITION REACTIONS OF IMINES AND MENTHYL ACRYLATE

Metallo-azomethine ylides, generated from imines by the action of amine bases in combination with LiBr or AgOAc, undergo cycloaddition with both 1R, 2S, 5R- and 1S, 2R, 5S-menthyl acrylate at room temperature to give homochiral pyrrolidines in excellent yield. The stronger the base the faster the cycloaddition and the greater the yield with: 2-t-butyl-1,1,3,3-tetramethylguanidine > DBU > NEt(3) X-Ray crystal structures of representative cycloadducts establish that the absolute configuration of the newly established pyrrolidine stereocentres is independent of the metal salt and the size of the pyrrolidineC(2)-substituent for a series of aryl and aliphatic imines.

ASYMMETRIC-SYNTHESIS OF S-(+)-4-AMINO-5-HEXYNOIC ACID

4-Amino-5-hexynoic acid is efficiently synthesised in eight steps (overall yield 10%) from commercially available (S)-glutamic acid. The key step was conversion of an aldehyde to an acetylene using diethylmethydiazophosphonate.

Application of Asymmetric Marcus-Hush Theory to Voltammetry in Room-Temperature Ionic Liquids

Asymmetric MarcusHush (AMH) theory is applied for the first time in ionic solvents to model the voltammetric reduction of oxygen in 1-butyl-1-methylpyrrolidinium bis-(trifluoromethylsulfonyl)-imide and of 2-nitrotoluene (2-NT), nitrocyclopentane (NCP), and 1-nitro-butane (BuN) in trihexyltetradecylphosphonium tris(pentafluoroethyl)trifluorophosphate on a gold microdisc electrode. An asymmetry parameter, gamma, was estimated for all systems as -0.4 for the reduction of oxygen and -0.05, 0.25, and 0 +/- 0.05 for the reductions of 2-NT, NCP, and BuN, respectively, which suggests equal force constants of reactants and products in the case of 2-NT and BuN and unequal force constants for oxygen and NCP where the force constants of the oxidized species are greater than the reduced species in the case of oxygen and less than the reduced species in the case of NCP. Previously measured values for a, the Butler-Volmer transfer coefficient, reflect this in each case. Where appreciable asymmetry occurs, AMH theory was seen to parametrize the experimental data better than either Butler-Volmer or symmetric Marcus-Hush theory, allowing additionally the extraction of reorganization energy. This is the first study to provide key physical insights into electrochemical systems in room-temperature ionic liquids using AMH theory, allowing elucidation of the reorganization energies and the relative force constants of the reactants and products in each reaction.

Evaluating fault tolerance on asymmetric multicore systems-on-chip using iso-metrics

The end of Dennard scaling has promoted low power consumption into a firstorder concern for computing systems. However, conventional power conservation schemes such as voltage and frequency scaling are reaching their limits when used in performance-constrained environments. New technologies are required to break the power wall while sustaining performance on future processors. Low-power embedded processors and near-threshold voltage computing (NTVC) have been proposed as viable solutions to tackle the power wall in future computing systems. Unfortunately, these technologies may also compromise per-core performance and, in the case of NTVC, xreliability. These limitations would make them unsuitable for HPC systems and datacenters. In order to demonstrate that emerging low-power processing technologies can effectively replace conventional technologies, this study relies on ARM’s big.LITTLE processors as both an actual and emulation platform, and state-of-the-art implementations of the CG solver. For NTVC in particular, the paper describes how efficient algorithm-based fault tolerance schemes preserve the power and energy benefits of very low voltage operation.

Effect of position of near addition in an asymmetric refractive multifocal intraocular lens on quality of vision

Purpose
To evaluate the impact of the position of an asymmetric multifocal near segment on visual quality.

Setting
Cathedral Eye Clinic, Belfast, United Kingdom.

Design
Retrospective comparative case series.

Methods
Data from consecutive patients who had bilateral implantation of the Lentis Mplus LS-312 multifocal intraocular lens were divided into 2 groups. One group received inferonasal near-segment placement and the other, superotemporal near-segment placement. A +3.00 diopter (D) reading addition (add) was used in all eyes. The main outcome measures included uncorrected distance visual acuity (UDVA), uncorrected near visual acuity (UNVA), contrast sensitivity, and quality of vision. Follow-up was 3 months.

Results
Patients ranged in age from 43 to 76 years. The inferonasal group comprised 80 eyes (40 patients) and the superotemporal group, 76 eyes (38 patients). The mean 3-month spherical equivalent was −0.11 D ± 0.49 (SD) in the inferonasal group and −0.18 ± 0.46 D in the superotemporal group. The mean postoperative UDVA was 0.14 ± 0.10 logMAR and 0.18 ± 0.15 logMAR, respectively. The mean monocular UNVA was 0.21 ± 0.14 logRAD and 0.24 ± 0.13 logRAD, respectively. No significant differences were observed in the higher-order aberrations, total Strehl ratio (point-spread function), or modulation transfer function between the groups. Dysphotopic symptoms measured with a validated quality-of-vision questionnaire were not significantly different between groups.

Conclusion
Positioning of the near add did not significantly affect objective or subjective visual function parameters.

Asymmetric electrocyclic reactions

This critical review offers an overview of asymmetric electrocyclic processes, where diastereo- or enantioselectivity is a consequence of the influence of a chiral component (be it substrate or catalyst) on the electrocyclic bond-forming process (195 references). © 2011 The Royal Society of Chemistry.

Asymmetric hydrogen flame in a heated micro-channel: role of Darrieus-Landau and thermal-diffusive instabilities

Present work examines numerically the asymmetric behavior of hydrogen/air flame in a micro-channel subjected to a non-uniform wall temperature distribution. A high resolution (with cell size of 25 μm × 25 μm) of two-dimensional transient Navier–Stokes simulation is conducted in the low-Mach number formulation using detailed chemistry evolving 9 chemical species and 21 elementary reactions. Firstly, effects of hydrodynamic and diffusive-thermal instabilities are studied by performing the computations for different Lewis numbers. Then, the effects of preferential diffusion of heat and mass transfer on the asymmetric behavior of the hydrogen flame are analyzed for different inlet velocities and equivalence ratios. Results show that for the flames in micro-channels, interactions between thermal diffusion and molecular diffusion play major role in evolution of a symmetric flame into an asymmetric one. Furthermore, the role of Darrieus–Landau instability found to be minor. It is also found that in symmetric flames, the Lewis number decreases behind the flame front. This is related to the curvature of flame which leads to the inclination of thermal and mass fluxes. The mass diffusion vectors point toward the walls and the thermal diffusion vectors point toward the centerline. Asymmetric flame is observed when the length of flame front is about 1.1–1.15 times of the channel width.

Rational design of a (S)-selective-Transaminase for asymmetric synthesis of (1S)-1-(1,1'-biphenyl 2-yl)ethanamine

Amine transaminases offer an environmentally sustainable synthesis route for the production ofpure chiral amines. However, their catalytic efficiency towards bulky ketone substrates isgreatly limited by steric hindrance and therefore presents a great challenge for industrialsynthetic applications. Hereby we report an example of rational transaminase enzyme design tohelp alleviate these challenges. Starting from the Vibrio fluvialis amine transaminase that has nodetectable catalytic activity towards the bulky aromatic ketone 2-acetylbiphenyl, we employed arational design strategy combining in silico and in vitro studies to engineer the transaminaseenzyme with a minimal number of mutations, achieving an high catalytic activity and highenantioselectivity. We found that by introducing two mutations W57G/R415A detectableenzyme activity was achieved. The rationally designed best variant,W57F/R88H/V153S/K163F/I259M/R415A/V422A, showed an improvement in reaction rateby > 1716-fold towards the bulky ketone under study, producing the corresponding enantiomericpure (S)-amine (ee value of > 99%).