Copper-Catalyzed Asymmetric Alkylation of β-Keto Esters with Xanthydrols

The copper(II) triflate-tert-butyl-bisoxazoline [Cu(OTf)2-t-Bu-BOX]-catalyzed asymmetric alkylation of β-keto esters using free benzylic alcohols such as xanthydrols, as alkylating agents, is herein described for the first time. This green protocol renders in general the corresponding products with good results in terms of both yields and enantioselectivities using different keto esters, even when quaternary stereocenters were created. The scope, limitations and mechanistic aspects of the process are also discussed.

Synthesis of α,β-diamino acid derivatives via asymmetric Mannich reactions of glycine imino esters catalyzed by a chiral phosphoramidite·silver complex

AgOTf·phosphoramidite complexes efficiently catalyze the enantioselective Mannich-type reaction between benzophenone-imine glycine methyl ester and N-tosyl aldimines in the absence of a base. The corresponding syn-adducts, which are the direct precursors of α,β-diamino acids, are obtained with moderate to good syn-diastereoselectivities (up to 9:1) and high enantioselectivities (up to 99% ee).

Microwave-Enhanced Asymmetric Transfer Hydrogenation of N-(tert-Butylsulfinyl)imines

Microwave irradiation has considerably enhanced the efficiency of the asymmetric transfer hydrogenation of N-(tert-butylsulfinyl)imines in isopropyl alcohol catalyzed by a ruthenium complex bearing the achiral ligand 2-amino-2-methylpropan-1-ol. In addition to shortening reaction times for the transfer hydrogenation processes to only 30 min, the amounts of ruthenium catalyst and isopropyl alcohol can be considerably reduced in comparison with our previous procedure assisted by conventional heating, which diminishes the environmental impact of this new protocol. This methodology can be applied to aromatic, heteroaromatic and aliphatic N-(tert-butylsulfinyl)ketimines, leading, after desulfinylation, to the expected primary amines in excellent yields and with enantiomeric excesses of up to 96 %.

Error induced by the estimation of the corneal power and the effective lens position with a rotationally asymmetric refractive multifocal intraocular lens

AIM: To evaluate the prediction error in intraocular lens (IOL) power calculation for a rotationally asymmetric refractive multifocal IOL and the impact on this error of the optimization of the keratometric estimation of the corneal power and the prediction of the effective lens position (ELP). METHODS: Retrospective study including a total of 25 eyes of 13 patients (age, 50 to 83y) with previous cataract surgery with implantation of the Lentis Mplus LS-312 IOL (Oculentis GmbH, Germany). In all cases, an adjusted IOL power (PIOLadj) was calculated based on Gaussian optics using a variable keratometric index value (nkadj) for the estimation of the corneal power (Pkadj) and on a new value for ELP (ELPadj) obtained by multiple regression analysis. This PIOLadj was compared with the IOL power implanted (PIOLReal) and the value proposed by three conventional formulas (Haigis, Hoffer Q and Holladay). RESULTS: PIOLReal was not significantly different than PIOLadj and Holladay IOL power (P>0.05). In the Bland and Altman analysis, PIOLadj showed lower mean difference (-0.07 D) and limits of agreement (of 1.47 and -1.61 D) when compared to PIOLReal than the IOL power value obtained with the Holladay formula. Furthermore, ELPadj was significantly lower than ELP calculated with other conventional formulas (P<0.01) and was found to be dependent on axial length, anterior chamber depth and Pkadj. CONCLUSION: Refractive outcomes after cataract surgery with implantation of the multifocal IOL Lentis Mplus LS-312 can be optimized by minimizing the keratometric error and by estimating ELP using a mathematical expression dependent on anatomical factors.

Design of hybrid asymmetric capacitors in aqueous electrolyte using ZTC and ultraporous activated carbons

The use of two different materials as electrodes allows the construction of asymmetric and hybrid capacitors cells with enhanced energy and power density. This approach is especially well-suited for overcoming the limitations of pseudocapacitive materials that provide a huge capacitance boost, but in a limited potential window. In this work, we introduce the concepts and protocols that are required for a successful design of such systems, which is illustrated by the construction of an asymmetric hybrid cell where a zeolite-templated carbon and an ultraporous activated carbon have been combined.

Solvent-Induced Reversal of Enantioselectivity in the Synthesis of Succinimides by the Addition of Aldehydes to Maleimides Catalysed by Carbamate-Monoprotected 1,2-Diamines

A simple change in the polarity of the solvent allows both enantiomers of substituted succinimides to be obtained in the enantioselective conjugate addition reaction of aldehydes, mainly α,α-disubstituted, to maleimides catalysed by chiral carbamate-monoprotected trans-cyclohexane-1,2-diamines. Using a single enantiomer of the organocatalyst, both enantiomers of the resulting Michael adducts are obtained in high yields by simply changing the reaction solvent from aqueous DMF (up to 84 % ee) to chloroform (up to 86 % ee). Theoretical calculations are used to explain this uncommon reversal of the enantioselectivity; two transition state orientations of different polarities are differently favoured in polar or nonpolar solvents.

Asymmetric effects of online consumer reviews

Consumers tend to seek heuristic information cues to simplify the amount of information involved in tourist decisions. Accordingly, star ratings in online reviews are a critical heuristic element of the perceived evaluation of online consumer information. The objective of this article is to assess the effect of review ratings on usefulness and enjoyment. The empirical application is carried out on a sample of 5,090 reviews of 45 restaurants in London and New York. The results show that people perceive extreme ratings (positive or negative) as more useful and enjoyable than moderate ratings, giving rise to a U-shaped line, with asymmetric effects: the size of the effect of online reviews depends on whether they are positive or negative.

Design of Activated Carbon/Activated Carbon Asymmetric Capacitors

Supercapacitors are energy storage devices that offer a high power density and a low energy density in comparison with batteries. Their limited energy density can be overcome by using asymmetric configuration in mass electrodes, where each electrode works within their maximum available potential window, rendering the maximum voltage output of the system. Such asymmetric capacitors are optimized using the capacitance and the potential stability limits of the electrodes, with the reliability of the design largely depending on the accuracy and the approach taken for the electrochemical characterization. Therefore, the performance could be lower than expected and even the system could break down, if a well thought out procedure is not followed. In this work, a procedure for the development of asymmetric supercapacitors based on activated carbons is detailed. Three activated carbon materials with different textural properties and surface chemistry have been systematically characterized in neutral aqueous electrolyte. The asymmetric configuration of the masses of both electrodes in the supercapacitor has allowed to cover a higher potential window, resulting in an increase of the energy density of the three devices studied when compared with the symmetric systems, and an improved cycle life.

Bertrand Competition with an Asymmetric No-discrimination Constraint. Bruges European Economic Research (BEER) 23/June 2012

Regulators and competition authorities often prevent firms with significant market power or dominant firms from practicing price discrimination. The goal of such an asymmetric no- discrimination constraint is to encourage entry and serve consumers’ interests. This constraint prohibits the firm with significant market power to practice both behaviour-based price discrimination within the competitive segment and third-degree price discrimination across the monopolistic and competitive segments. We find that this constraint hinders entry and reduces welfare when the monopolistic segment is small.

The Relevance of International Spillovers and Asymmetric Effects in the Taylor Rule. CEPS Working Document No. 403, February 2015

Deviations of policy interest rates from the levels implied by the Taylor rule have been persistent before the financial crisis and increased especially after the turn of the century. Compared to the Taylor benchmark, policy rates were often too low. This paper provides evidence that both international spillovers, for instance international dependencies in the interest rate-setting of central banks, and nonlinear reaction patterns can offer a more realistic specification of the Taylor rule in the main industrial countries. The inclusion of international spillovers and, even more, nonlinear dynamics improves the explanatory power of standard Taylor reaction functions. Deviations from Taylor rates tend to be smaller and their negative trend can be eliminated.

Entangled two-photon source using biexciton emission of an asymmetric quantum dot in a cavity

A semiconductor based scheme has been proposed for generating entangled photon pairs from the radiative decay of an electrically pumped biexciton in a quantum dot. Symmetric dots produce polarization entanglement, but experimentally realized asymmetric dots produce photons entangled in both polarization and frequency. In this work, we investigate the possibility of erasing the “which-path” information contained in the frequencies of the photons produced by asymmetric quantum dots to recover polarization-entangled photons. We consider a biexciton with nondegenerate intermediate excitonic states in a leaky optical cavity with pairs of degenerate cavity modes close to the nondegenerate exciton transition frequencies. An open quantum system approach is used to compute the polarization entanglement of the two-photon state after it escapes from the cavity, measured by the visibility of two-photon interference fringes. We explicitly relate the two-photon visibility to the degree of the Bell-inequality violation, deriving a threshold at which Bell-inequality violations will be observed. Our results show that an ideal cavity will produce maximally polarization-entangled photon pairs, and even a nonideal cavity will produce partially entangled photon pairs capable of violating a Bell-inequality.

Iron catalysed assembly of an asymmetric mixed-ligand triple helicate

The 2-pyridinecarbaldehyde isonicotinoyl hydrazone (HPCIH) family of ligands are typically tridentate N,N,O chelators that exhibit very high in vitro activity in mobilizing intracellular Fe and are promising candidates for the treatment of Fe overload diseases. Complexation of ferrous perchlorate with HPCIH in MeCN solution gives the expected six-coordinate complex Fe-II(PCIH)(2). However, complexation of Fe-II with 2-pyridinecarbaldehyde picolinoyl hydrazone (HPCPH, an isomer of HPCIH) under the same conditions leads to spontaneous assembly of an unprecedented asymmetric, mixed-ligand dinuclear triple helical complex Fe-2(II)(PCPH)(2)(PPH), where PPH2- is the dianion of bis(picolinoyl) hydrazine. The X-ray crystal structure of this complex shows that each ligand binds simultaneously to both metal centres in a bidentate fashion. The dinuclear complex exhibits two well separated and totally reversible Fe-III/II redox couples as shown by cyclic voltammetry in MeCN solution.

Asymmetric Bragg mirrors for the reduction of emission wavelength dependence on the viewing angle in organic microcavity light emitting diodes

Organic microcavity light emitting diodes typically exhibit a blue shift of the emitting wavelength with increasing viewing angle. While the wavelength shift can be reduced with the appropriate choice of organic materials and metal mirrors, for further reduction of the emission wavelength shift it is necessary to consider a mirror whose phase shift can partly compensate the effect of the change of optical path within the cavity. In this work, we used a genetic algorithm (GA) to design an asymmetric Bragg mirror in order to minimize the emission wavelength shift with viewing angle. Based on simulation results, the use of asymmetric Bragg mirrors represents a promising way to reduce the emission wavelength shift. Detailed comparison between GA optimized and conventional Bragg mirrors in terms of resonant wavelength dependence on the viewing angle, spectral narrowing, and brightness enhancement is given. (C) 2004 Elsevier B.V. All rights reserved.