Uronic (hexenuronic) acid profile of ethanol–alkali delignification of giant reed Arundo donax L.

The effect of process variables on uronic acids (UAs) and hexenuronic acids (HexAs) in the annual crop Arundo donax L. during ethanol–alkali pulping has been examined. A substantial loss of UA moieties (up to 90%) was observed by the end of pulping (target kappa number 18) performed with 25% NaOH and 40% EtOH (by volume) within the temperature range of 130–150 °C. At the same time, the progressive formation of HexA in pulp was detected from the early phases of delignification. The proportion of HexA in the residual UA of the final pulp was found to be 84%, indicating almost complete conversion of 4-O-methylglucuronic acid side groups (MeGlcA) of heteroxylan into HexA. The kinetics of UA degradation and HexA formation has been described in terms of three consecutive first-order reaction stages. The overall rate of UA degradation was one order higher than the rate of UA conversion into HexA. The values of apparent activation energy were estimated as 68.6 and 94.7 kJ mol^–1, respectively. The reaction medium alkalinity was shown to be the controlling factor for UA and HexA stability during ethanol–alkali pulping. An increase in alkali charge from 5% to 35% (as NaOH) led to UA loss of 40%, but promoted HexA formation from 11.8 to 20.1 mol g^–1. The addition of organic solvent to the alkaline pulping solution had a similar effect, and about 10% of UA was lost and the content of HexA increased from 6.9 to 10.9 mol g^–1 with an increase in ethanol proportion in the liquor from 20% to 60%.     

Cyclodextrin catalysis of the smiles rearrangement of 4-nitrophenyl salicylate

α- and β-Cyclodextrins accelerate the Smiles rearrangement of 4-nitrophenyl salicylate which proceeds through the mechanism of intramolecular aromatic nucleophilic substitution. The binding and catalytic rate constants were calculated from the dependences of the observed pseudo-first-order rate constants of the rearrangement reaction on cyclodextrin concentration obtained at various pH values. The catalysis was interpreted in terms of a tighter binding of the anionic, highly delocalized δ-complex intermediate than that of the substrate to cyclodextrins.     

Polymerization dynamics of double-stranded biopolymers: chemical kinetic approach

The polymerization dynamics of double-stranded polymers, such as actin filaments, is investigated theoretically using simple chemical kinetic models that explicitly take into account some microscopic details of the polymer structure and the lateral interactions between the protofilaments. By considering all possible molecular configurations, the exact analytical expressions for the growth velocity and dispersion for two-stranded polymers are obtained in the case of the growing at only one end, and for the growth from both polymer ends. Exact theoretical calculations are compared with the predictions of approximate multilayer models that consider only a finite number of the most relevant polymer configurations. Our theoretical approach is applied to analyze the experimental data on the growth and fluctuations dynamics of individual single actin filaments.     

The oxidation kinetic study of mechanically milled ultrafine iron powders by thermogravimetric analysis

Journal of Thermal Analysis and Calorimetry - The effect of mechanical milling on the oxidation kinetics of ultrafine iron powders was investigated by thermogravimetric (TG) analysis. The initial...     

Four-component stereoselective synthesis of tetracyano-substituted piperidines

Research on Chemical Intermediates - A novel four-component stereoselective synthesis of polysubstituted piperidines is reported. The Knoevenagel–Michael–Mannich cascade of two...     

A Jeffrey-fluid model of blood flow in tubes with stenosis

In this paper, we discuss the two-layered Jeffrey-fluid model with mild stenosis in narrow tubes. The blood flow in narrow arteries is treated as a two-fluid model with the suspension of erythrocytes, leukocytes, etc., as a Jeffrey fluid, which is a non-Newtonian fluid, in the core region and plasma, a Newtonian fluid, in the peripheral region. An analytical solution has been obtained for the velocity in the core and peripheral region, volume flow rate, resistance to flow, and wall-shear stress. The effect of Jeffrey-fluid parameters, like the height of stenosis, viscosity, etc., on volume flow rate, resistance to flow (impedance), and wall-shear stress has been discussed graphically. Through the present study, it is found that the wall-shear stress and resistance to flow increases with the increase in height of stenosis and decreases with the increase in the ratio of relaxation time. It is also found that the velocity decreases with an increase in stenosis height in both the core and the peripheral region. A previous result has been also verified.     

Aminohydroxypropane Esters of Hydroxyethylidenebisphosphonic Acid

Abstract

The 1-hydroxyethylidene-1,1-bisphosphonic acid (HEDP) (I) reacts with epichlorohydrine (II) and aminoepoxypropanes (III) in water. Optimum pH for the esterefication is 6–7. The reaction completes in 20–30 h on 60°C at this pH and leads to the mixture of the original HEDP with the mono- and diesters. The mixture of di-Na salts of HEDP and the monochloroester (IV) in ratio 1:1.7 was precipitated from the reaction solution on using of the epichlorohydrine (II). This mixture was used for synthesis of aminoesters (VI a,b) unavailable by direct reaction of HEDP with corresponding aminoepoxides.     

Trimetallic NiCoM catalysts (M = Mn,Fe, Cu) for methane conversion into synthesis gas

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Synthesis of cyclic norspermidine derivative of protohemin IX

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