Enantioselective one-pot conjugate addition of grignard reagents to cyclic enones followed by amidomethylation

Enantioselective conjugate addition of Grignard reagents to enones, catalyzed by Cu-Taniaphos or Josiphos complex, affords chiral enolates. Ensuing one-pot Mannich reaction with TiCl(4)-generated imine leads to aminocarbonyl compounds with benzyloxycarbonyl-protected nitrogen. Both diastereomers of these compounds are isolated in moderate yields but high enantiomeric purities (up to er 97.5:2.5).     

Oscillation of third-order nonlinear functional differential equations with mixed arguments

The objective of this paper is to offer sufficient conditions for the oscillation of all solutions and other asymptotic properties of the third-order nonlinear functional differential equation $$\left[a(t)\left[x''(t)\right]^{\gamma}\right]' =q(t)f \left(x\left[\tau(t)\right]\right)+p(t)h \left(x\left[\sigma(t)\right]\right)$$ with mixed arguments, where both cases ∫^∞ a ^?1/γ (s)?ds=∞ and ∫^∞ a ^?1/γ (s)?ds<∞ are dealt with. We deduce properties of the studied equations via new comparison theorems. Our results essentially improve and complement earlier ones. We also repair one interesting result of Grace et al.     

Self‐dual and self‐petrie‐dual regular maps

Regular maps are cellular decompositions of surfaces with the “highest level of symmetry”, not necessarily orientation‐preserving. Such maps can be identified with three‐generator presentations of groups G of the form G = 〈a, b, c|a² = b² = c² = (ab)^k = (bc)^m = (ca)² = … = 1〉; the positive integers k and m are the face length and the vertex degree of the map. A regular map (G;a, b, c) is self‐dual if the assignment b?b, c?a and a?c extends to an automorphism of G, and self‐Petrie‐dual if G admits an automorphism fixing b and c and interchanging a with ca. In this note we show that for infinitely many numbers k there exist finite, self‐dual and self‐Petrie‐dual regular maps of vertex degree and face length equal to k. We also prove that no such map with odd vertex degree is a normal Cayley map. Copyright © 2011 Wiley Periodicals, Inc. J Graph Theory 69:152‐159, 2012     

Electrical and dielectric properties of glass system NaPO3–KHSO4

Glass samples have been prepared in the NaPO₃–KHSO₄ binary system with the classical melting, casting and annealing steps. Electrical and dielectrical properties of glass samples were studied. Measurements of DC and AC conductivity and complex electrical permittivity of xNaPO₃–(100 ? x)KHSO₄ glass system were carried out at temperatures ranging from room temperature to temperature located 15 °C below glass transition temperature T_g. Results showed that changes of NaPO₃ concentration considerably affect values of observed parameters. DC conductivity of glass increases as NaPO₃ concentration grows until concentration x = 60. However, beyond this value a sharp decrease of DC conductivity was observed. In addition relaxation times showed abrupt changes at concentration x = 60, corresponding to the lowest relaxation times at the temperature 90 °C.     

Two-photon decays of charmonia from lattice QCD

We make the first calculation in lattice QCD of two-photon decays of mesons. Working in the charmonium sector, using the Lehmann-Symanzik-Zimmermann reduction to relate a photon to a sum of hadronic vector eigenstates, we compute form factors in both the spacelike and timelike domains for the transitions eta c --> gamma*gamma* and chi(c0) --> gamma*gamma*. At the on-shell point, we find approximate agreement with experimental world-average values.     

Determination of the 2,3-pentadienedioic acid enantiomer interconversion energy barrier 1. Classical kinetic approach

A classical kinetic method was used to determine the energy barrier for the inter-conversion of 2,3-pentadienedioic acid enantiomers. Each individual enantiomer was isolated by collecting the appropriate peaks from the HPLC enantiomeric separation, of racemic 2,3-pentadienedioic acid. The isolated enantiomers were racemized at 22 degrees C using various interconversion times. The ratio of enantiomers in each reaction solution was determined by HPLC at 22 degrees C. The corresponding peak areas of the enantiomers and the interconversion times obtained from the HPLC chromatograms were used to calculate both the interconversion rate constants describing (+)--> (-) and (-) --> (+) interconversions as well as the energy barriers. It was confirmed that the interconversion of 2,3-pentadienedioic acid enantiomers is a firstorder kinetic reaction. Both semiempirical and ab initio methods were used to explore the mechanism of the interconversion of 2,3-pentadienedioic acid enantiomers, and to calculate the interconversion energy barrier. Comparison of the interconversion energy barriers found by the ab initio method (deltaG# = 110.7 kJ/mol) and by classical kinetics in the mobile phase solution at 22 degrees C (delta Gapp = 93.9+/-0.2 kJ/mol) shows a difference which may be attributed to the different conditions assumed in the theoretical calculation (i.e., a gaseous state) and the actual experimental conditions (i. e., liquid solution) and a possible catalytic effect of the solution composition.     

Mobile-phase pH influence on the retention of some benzoic acid derivatives in reversed-phase chromatography

Five end-capped octadecyl RP stationary phases, among which one was a polar embedded stationary phase, were tested for the analysis of benzoic acid derivatives using two mobile phases with or without addition of formic acid (water pH was measured by a common approach; pH of water with addition of formic acid was 3.0 and without formic acid 5.8). The influence of mobile-phase pH on the retention of benzoic acid derivatives was under study. Consequently, Purospher-STAR and Alltima columns provided symmetrical peaks for benzoic acid derivatives at pH 3.0 and also at pH 5.8. Reprosil and Symmetry stationary phases showed poor peak shapes at higher pH of the mobile phase. Differences between the tested columns may be caused by surface heterogeneity. Another reason may be the presence of some atoms creating additional adsorption sites on the surface of Reprosil and Symmetry stationary phases. This can lead to enhanced silanol activity resulting in peak tailing. The addition of formic acid into the mobile phase improved peak shapes. The polar embedded C18 stationary-phase Synergi-Fusion-RP appeared as not a suitable column for the analysis of benzoic acid derivatives. Synergi-Fusion-RP provided asymmetrical peaks even if formic acid was added into the mobile phase.     

Novel furanoid alpha-substitued alpha-amino acid as a potent turn mimic in peptide synthesis

A stereoselective approach has been developed to the new sugar amino acid and potential potent turn mimic 5-O-(tert-butyldimethylsilyl)-3-deoxy-1,2-O-isopropylidene-3-methoxycarbonylamino-alpha-D-xylofuranose 3-C-carboxylic acid (12), via the [3,3]-sigmatropic rearrangement of allylic thiocyanates (Z)-6 and (E)-7, prepared from D-xylose. The synthesis of a new dipeptide 13 is also described.     

Computational study of the mechanism of Bcl-2 apoptotic switch

In spite of attention devoted to molecular mechanisms of apoptosis, the details of functioning of one crucial component–the Bcl-2 apoptotic switch–are not completely understood. There are two competing mechanisms of its internal working—the indirect activation and the direct activation. In the absence of conclusive experimental data, we have used computational modeling to assess the properties of both mechanisms and their suitability to act as a biological switch. Since the two mechanisms form opposite poles of continuum of Bcl-2 molecular interaction models, we have constructed more general models including these two models as extreme cases. By studying the relationship between model parameters and the steady-state response we have found optimal interaction patterns which reproduce the behavior of the Bcl-2 apoptotic switch. Our results show, that stimulus–response ultrasensitivity is negatively affected by spontaneous activation of Bcl-2 effectors. We found that ultrasensitivity requires effectors activation, mediated by another subgroup of Bcl-2 proteins—activators. We have shown that the auto-activation of monomeric effector forms provides an ultrasensitivity enhancing feedback loop. Thorough robustness analysis revealed that the interaction pattern postulated in the direct activation hypothesis is able to conserve stimulus–response switching characteristics for wide range changes of its internal parameters. The robustness of the switch against the variation of the reaction parameter is strongly reduced for the intermediate hybrid model and even more for the indirect part of the models. Computer simulations of the more general model presented here suggest, that stimulus–response ultrasensitivity is an emergent property of the direct activation model that is unlikely to occur in the model of indirect activation. Introduction of indirect-model-specific interactions does not provide a better explanation of the Bcl-2 switch functionality compared to the direct model.     

Trace elemental analysis by laser-induced breakdown spectroscopy—Biological applications

Laser-Induced Breakdown Spectroscopy (LIBS) is a sensitive optical technique capable of fast multi-elemental analysis of solid, gaseous and liquid samples. Since the late 1980s LIBS became visible in the analytical atomic spectroscopy scene; its applications having been developed continuously since then. In this paper, the use of LIBS for trace element determination in different matrices is reviewed. The main emphasis is on spatially resolved analysis of microbiological, plant and animal samples.