Formation, isolation and characterization of an AB-biaryl atropisomer of oritavancin

Oritavancin is a semi-synthetic glycopeptide antibiotic which is structurally related to vancomycin. When oritavancin bisphosphate is dried in vacuo with heat, a new compound forms. This new compound is stable only in the solid state and reverts to oritavancin in solution. Highly enriched samples of this compound were obtained by preparative HPLC and the structure of this compound was elucidated by using one and two-dimensional (¹H and ¹³C) NMR spectroscopy in conjunction with computer-assisted molecular modeling. It has been determined that oritavancin adopts a conformation similar to that of vancomycin in solution, while the new compound is the unnatural R-AB-biaryl atropisomer of oritavancin. This is the first observation and isolation of an AB-biaryl atropisomer in an intact member of the vancomycin family of glycopeptide antibiotics.     

Total synthesis of the marine cytotoxic caulibugulones A-D

We report the first total synthesis of the cytotoxic marine alkaloids caulibugulone A-D. This synthesis confirmed the assigned structures and provided sufficient material for further biological testing.     

Target Level Method in Linear Multi-Criterion Problems

We consider the target level method for solving linear multi-criterion maximization problems. The method finds an efficient (Pareto-optimal) vector estimate that is closest in the Chebyshev metric to the target level point specified by the decision maker. The proposed method describes (parametrizes and approximates) the efficient set. In the linear case the number of scalar optimization problems needed to describe the set of efficient vector estimates is substantially reduced. A formula is derived which, under certain conditions, can be used to compute efficient vector estimates without solving any optimization problems. An algorithm based on these results is proposed for two-criterion problems.     

Non-Steady-State Natural Convection in a Model Electrochemical System with Vertical and Horizontal Plane Electrodes

Non-steady-state mass-transfer processes in the electrochemical cells of rectangular cross-section with vertical and horizontal electrodes under the conditions of natural convection are simulated numerically taking into account the diffusion and convection of solely ions discharging at the electrode under limiting-current conditions. The interrelated time variations of the limiting current density at various ratios of the electrode height (length) to the interelectrode distance and the distributions of ion concentration and hydrodynamic velocity over the cell are determined.     

Micromechanisms and Mechanics of Damage and Fracture in Thin Film/Substrate Systems

The purpose of this paper is to review the mechanisms and available theoretical methods for modeling the strength and failure of thin film/substrate systems     

Local chain‐configuration dependence of the mechanisms of the chemical reaction of poly(vinyl chloride). IX. Novel results on stereoselectivity of chlorination reaction

A poly(vinyl chloride) (PVC) sample was chlorinated in solution in the presence of 2,2′‐azobisisobutyronitrile and by the fluid‐bed method. The aim was to evaluate the scope of the stereoselectivity of the chlorination reaction. The quantitative microstructural analysis of the residual PVC with a degree of chlorination was followed by ¹³C NMR spectroscopy. From the evolution of the content of isotactic (mm), heterotactic (mr), and syndiotactic (rr) triads and of mmmm, mmmr, and rmmr isotactic pentads in the unchlorinated parts of the polymer, it was unambiguously inferred that the chlorination reaction proceeds by a stereoselective mechanism in that the mr heterotactic triads are the most reactive structures followed by the isotactic triad at mmmr and rmmr pentads. This conclusion was confirmed on the basis of the Fourier transform infrared results. The results provide valuable information regarding the effect of tacticity and related local conformations in the chemical reactions of PVC. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 508–519, 2003     

On an Inverse Problem for a Parabolic Equation

In this paper, we study the inverse problem of the reconstruction of the right-hand side of special form for a parabolic equation in u in which the coefficients of u _t and u depend on u _(x,t) , with overdetermination given by the integral of the solution over time. The Fredholm property for this problem and the existence and uniqueness theorems in Sobolev spaces are established.     

The Spin-Echo System Reconsidered

Simple models have played an important role in the discussion of foundational issues in statistical mechanics. Among them the spin-echo system is of particular interest since it can be realized experimentally. This has led to inferences being drawn about approaches to the foundations of statistical mechanics, particularly with respect to the use of coarse-graining. We examine these claims with the help of computer simulations.