Synthesis and Thermal Transformations of 1-Polyfluoro-Alkyl-2-Trialkylsilylethyl Esters of Phosphorus Acids

Abstract

We have studied the phosphorylation of 1-polyfluorólkyl-2-trialkylsilylethanols (I) with phosphorus acids chlorides.     

Theory of the transition from conductive to convective burning

The experimentally known phenomenon of an abrupt transition from slow conductive to fast convective (penetrative) burning in a confined gas-permeable explosive is discussed. A simple model, involving only the most essential physical ingredients, is formulated and analyzed. A good qualitative agreement between theoretical and experimental dependencies is obtained. The transition is triggered by a localized autoignition in the extended resistance-induced preheat zone formed ahead of the advancing deflagration, provided the pressure difference between hot gas products and gases deep inside the pores of the unburned solid exceeds a certain critical level. In line with observations the critical overpressure increases with diminishing permeability.     

Sequential-dissociation kinetics of non-covalent complexes of DNA with multiple proteins in separation-based approach: General theory and its application

Binding of multiple proteins to DNA is crucial in many regulatory cellular processes. The kinetics of assembly and disassembly of DNA–multiple protein complexes is very difficult to study in detail due to the lack of suitable experimental approaches. A separation-based approach has been recently proposed to resolve disassembly kinetics of such complexes. While conceptually simple, the separation-based approach generates experimental data with very complex patterns. The analysis of these patterns is a challenging problem on its own. Here we report on a mathematical approach that can extract a solution for the experimental data obtained in separation-based analysis of sequential dissociation of a DNA complex with multiple proteins. This case describes the dissociation of proteins one-by-one from the complex. Generally speaking, a mathematical solution of such problems requires calculations of multiple integrals. Our approach reduces this procedure to taking double integrals and constructing their superposition. We tested this approach with the experimental data obtained for three-step sequential dissociation of complexes of DNA with two protein copies.     

NMR line‐fitting quantification of polysaccharide N‐acylurea‐based modification in glycoconjugates of Salmonella Typhi Vi polysaccharide

The polysaccharides modification via carbodiimide reaction is one of the most applied methods for obtaining conjugated vaccines against Salmonella enterica. However, N‐acylurea carbodiimide adduct generated in the process is a critical impurity in carbohydrate‐based vaccines. A quantitative NMR method was developed for assessing the N‐acylurea carbodiimide adduct impurity. The procedure was based on line‐fitting facilities for processing the NMR signals on complex spectra. The method showed good linearity, accuracy and precision under inter‐operator variation (relative standard deviation <5%). Copyright © 2017 John Wiley & Sons, Ltd.     

A comparison of numerical and analytical radiative-transfer solutions for plane albedo of natural waters

Several numerical and analytical solutions of the radiative transfer equation (RTE) were compared for plane albedo in a problem of solar light reflection by sea water. The study incorporated the simplest case—a semi-infinite one-dimensional plane—parallel absorbing and scattering homogeneous layer illuminated by a monodirectional light beam. Inelastic processes (such as Raman scattering and fluorescence), polarization and air-water surface refraction-reflection effects, were not considered. Algorithms were based on the invariant imbedding method and two different variants of the discrete ordinate method (DOM). Calculations were performed using parameters across all possible ranges (single-scattering albedo ω₀ and refracted solar zenith angle θ₁), but with a special emphasis on natural waters. All computations were made for two scattering phase functions, which included an almost isotropic Rayleigh phase function and strongly anisotropic double-peaked Fournier-Forand-Mobley phase function. Models were validated using quasi-single-scattering (QSSA) and exponential approximations, which represent the extreme cases of ω₀→0 and ω₀→1, respectively. All methods yielded relative differences within 1.8% for modeled natural waters. An analysis of plane albedo behavior resulted in the development of a new extended QSSA approximation, which when applied in conjunction with the extended Hapke approximation developed earlier, resulted in a maximum relative error of 2.7%. The study results demonstrated that for practical applications, the estimation of inherent optical properties from observed reflectance can best be achieved using an extended Hapke approximation.