Enantiodiscrimination of racemic electrophiles by diketopiperazine enolates: asymmetric synthesis of methyl 2-amino-3-aryl-butanoates and 3-methyl-aspartates

Enolates of (S)-N,N′-bis-(p-methoxybenzyl)-3-iso-propylpiperazine-2,5-dione exhibit high levels of enantiodiscrimination in alkylations with (RS)-1-aryl-1-bromoethanes and (RS)-2-bromoesters, affording substituted diketopiperazines containing two new stereogenic centres in high de. Deprotection and hydrolysis of the resultant substituted diketopiperazines provides a route to the asymmetric synthesis of homochiral methyl 2-amino-3-aryl-butanoates and 3-methyl-aspartates in high de and ee.     

On Quantum Team Games

Recently Liu and Simaan (2004) convex static multi-team classical games have been introduced. Here they are generalized to both nonconvex, dynamic and quantum games. Puu's incomplete information dynamical systems are modified and applied to Cournot team game. The replicator dynamics of the quantum prisoner's dilemma game is also studied.     

Determination of trace levels of diosmin in a pharmaceutical preparation by adsorptive stripping voltammetry at a glassy carbon electrode.

A systematic study on the electrochemical behavior of diosmin in Britton-Robinson buffer (pH 2.0-10.0) at a glassy carbon electrode (GCE) was made. The oxidation process of the drug was found to be quasi-reversible with an adsorption-controlled step. The adsorption stripping response was evaluated with respect to various experimental conditions, such as the pH of the supporting electrolyte, the accumulation potential and the accumulation time. The observed anodic peak current at +0.73 V vs. Ag/AgCl reference electrode increased linearly over two orders of magnitude from 5.0x10(-8) M to 9.0x10(-6) M. A limit of detection down to 3.5x10(-8) M of diosmin at the GCE was achieved with a mean recovery of 97+/-2.1%. Based on the electrochemical data, an open-circuit accumulation step in a stirred sample solution of BR at pH 3.0 was developed. The proposed method was successfully applied to the determination of the drug in pharmaceutical formulations. The results compared favorably with the data obtained via spectrophotometric and HPLC methods.     

Instabilities in the Chapman-Enskog Expansion and Hyperbolic Burnett Equations

It is well-known that the classical Chapman-Enskog procedure does not work at the level of Burnett equations (the next step after the Navier-Stokes equations). Roughly speaking, the reason is that the solutions of higher equations of hydrodynamics (Burnett's, etc.) become unstable with respect to short-wave perturbations. This problem was recently attacked by several authors who proposed different ways to deal with it. We present in this paper one of possible alternatives. First we deduce a criterion for hyperbolicity of Burnett equations for the general molecular model and show that this criterion is not fulfilled in most typical cases. Then we discuss in more detail the problem of truncation of the Chapman-Enskog expansion and show that the way of truncation is not unique. The general idea of changes of coordinates (based on analogy with the theory of dynamical systems) leads finally to nonlinear Hyperbolic Burnett Equations (HBEs) without using any information beyond the classical Burnett equations. It is proved that HBEs satisfy the linearized H-theorem. The linear version of the problem is studied in more detail, the complete Chapman-Enskog expansion is given for the linear case. A simplified proof of the Slemrod identity for Burnett coefficients is also given.     

Studying the process of ionization of hydrogen in conditions of its forced delivery to a porous nickel oxide electrode

The hydrogen ionization process is studied experimentally on an industrial sintered nickel oxide electrode in models of sealed nickel-metal hydride batteries. It is shown that the hydrogen ionization rates that are reached during overcharge by high current densities in conditions of forced gas delivery into the electrode pores (up to 40 mA cm^?2) exceed the self-discharge rate of a nickel-hydrogen battery by two orders of magnitude. Up to 70% of hydrogen delivered into the compact assembly block undergoes ionization during forced charge of models of sealed nickel-metal hydride batteries with a closed hydrogen cycle. Two independent methods (potentiostatic and manometric) are used to determine the relationship between rates of hydrogen ionization with the degree of the electrode filling with gas and perform estimation of the process intensity at a unit reaction surface. It is established that, in conditions of forced gas delivery, practically all the hydrogen oxidation current is generated at the surface of the nickel oxide electrode beneath thin films of an electrolyte solution at the rate of 4–5 mA cm^?2. It is shown that the hydrogen oxidation rate on a nickel oxide electrode filled in part by gas is independent of the electrode potential, probably because of a tangible contribution made by diffusion limitations to the overall hampering of the process.     

EPR-detected photoinduced electron transfer in three structurally related molecular triads

A comparative electron paramagnetic resonance (EPR) study has been performed on a series of structurally related molecular triads which undergo photoinduced electron transfer and differ one from the other in terms of the acceptor or donor moieties. The molecular triads, C-P-C₆₀, TTF-P-C₆₀ and C-P-P_F, share the same free-base, tetraarylporphyrin (P) as the primary electron donor, which after light excitation initiates the electron transfer process, but differ either in terms of the electron acceptor (fullerene derivative, C₆₀, versus fluorinated free-base porphyrin, P_F), or in terms of the final electron donor (carotenoid polyene, C, versus tetrathiafulvalene, TTF). All these molecular triads can be considered artificial photosynthetic reaction centers in their ability to mimic several key properties of the reaction center primary photochemistry. Photoinduced charge separation and recombination have been followed by time-resolved EPR in a glass of 2-methyltetrahydrofuran and in the nematic phase of the uniaxial liquid crystal E-7. All the triads undergo photoinduced electron transfer, with the generation of charge-separated states in both the low-dielectric environment of the 2-methyl-tetrahydrofuran glass and in anisotropic E-7 medium. Different photochemical pathways have been recognized depending on the specific donor and acceptor moieties constituting the molecular triads. In the presence of the tetrathiafulvalene electron donor singlet- and triplet-initiated electron transfer routes are concurrently active. Recombination to the low-lying carotenoid triplet state occurs in the carotene-based triads, while singlet recombination is the only active route for the TTF-P-C₆₀ triad, where a low-lying triplet state is lacking. Long-lived charge separation has been observed in the case of TTF-P-C₆₀: about 8 μs for the singlet-born radical pair in the glassy isotropic matrix and about 7 μs for the triplet-born radical pair in the nematic phase of E-7. For all the molecular triads, a weak exchange interaction (J?1 G) between the electrons in the final spin-correlated radical pair has been evaluated by simulation of the EPR spectra, providing evidence for superexchange electronic interactions mediated by the tetraarylporphyrin bridge.     

Chromatic and opto-mechanical dispersion of some characteristic parameters of optical fiber undergoing macrobending

Bending of optical fiber leads to an induced-anisotropy in the index profile that influences many important guiding fiber parameters. An analytical method is described for the measurement of refractive-index-wavelength dispersion in bent optical fibers. Multiple-beam Fizeau fringes technique at transmission is used to analyze the opto-mechanical properties and induced-index anisotropy in a standard single-mode fiber undergoes pure mechanical macrobending. The shift in Fizeau fringes is employed to evaluate the dispersion of the cladding material of the bent fiber. The radial variations in Cauchy’s coefficients and the associated variations of some fiber parameters due to macrobending are carried out. The radial profiles of some material parameters such as oscillation energy, dispersion energy, lattice energy and material dispersion are measured as well. The presented method is capable to achieve quantitative and qualitative measurements, which is not available with other methods. The method has a good index resolution in the order of 10⁻⁴ and spatial resolution of 1.3 μm.     

On Periodic Solutions of Degenerate Singularly Perturbed Linear Systems with Multiple Elementary Divisor

We establish sufficient conditions for the existence and uniqueness of a periodic solution of a system of linear differential equations with a small parameter and a degenerate matrix of coefficients of derivatives in the case of a multiple spectrum of a boundary matrix pencil. We construct asymptotics of this solution.     

Temperature Stresses in a Piecewise-Homogeneous Cylindrical Shell Caused by the Presence of a Longitudinal Crack

By using the method of generalized conjugation problems, we propose a numerical scheme for investigation of the redistribution of temperature stresses in a piecewise-homogeneous cylindrical shell caused by a longitudinal crack. This scheme is based on systems of integral equations (some of them are singular) to determine the unknown jumps of integral characteristics of the disturbed temperature field and displacements and their derivatives on the line of a crack and on the interface as well as the derivatives of these integral characteristics with respect to the longitudinal coordinate at the interface.     

Barotropic Instability of the Bickley Jet at High Reynolds Numbers

We investigate the linear stability of the Bickley jet in the framework of the beta-plane approximation. Because singular inviscid neutral modes exist in the retrograde case     , it is necessary to add viscosity to interpret them. One of these modes was found in closed form by Howard and Drazin [1] . However, its critical point is at the center of the jet and it was therefore not possible for these authors to ascertain the relationship of this mode to the stability problem or to discuss how to continue the eigenfunction across the singularity.
The viscous critical layer problem associated with this singularity is considerably more difficult than the usual one (which leads to integrals of the Airy function) because     and, consequently, a second-order turning point is involved. Our analysis shows that the Howard–Drazin mode is degenerate in the domain where it is valid as a limit of the viscous problem (wavenumber  α²≤ 9/2  ), that is, it corresponds to both an odd and an even mode. This conclusion is confirmed by direct numerical solution of the Orr–Sommerfeld equation which shows, in addition, that viscosity is destabilizing along portions of the stability boundary. For a retrograde jet, instability is found to occur beyond the inviscid critical value of β, that is, in the region where the flow would be stable according to the Rayleigh–Kuo condition.