An Improved Model for Polyether Production from 1,3‐Propanediol

A dynamic mathematical model is developed for production of Cerenol polyether from 1,3‐propanediol in a batch reactor system. The model accounts for polycondensation reactions and side reactions in the liquid phase and for mass transfer of volatile species to the vapor. Parameters are estimated using measured liquid‐phase concentrations of monomer, oligomers, water, and end groups as well as the mass and composition of condensate collected from the overhead condenser system. The proposed model uses novel probability factors to keep the model equations relatively simple while accounting for the complex influence of superacid catalyst on reaction rates. The model is a significant advance over previous Cerenol models because it better accounts for mass‐transfer rates and for the dynamic behavior of the condenser. In addition, the proposed model accounts for the inhibitory influence of water on polycondensation kinetics due to hydration of hydroxyl ends. The model equations and parameter estimates provide a substantial improvement in fit to the data, especially for long reaction times and high catalyst levels, resulting in a 97% reduction in the value of the weighted least squared objective function compared to equations and parameters from a previous model.     

Maximizers for the Stein–Tomas Inequality

We give a necessary and sufficient condition for the precompactness of all optimizing sequences for the Stein–Tomas inequality. In particular, if a well-known conjecture about the optimal constant in the Strichartz inequality is true, we obtain the existence of an optimizer in the Stein–Tomas inequality. Our result is valid in any dimension.     

S,N-Compounds via Amines and Sulphur Halides

Abstract

The many products got by reactions of amines with sulfur halides are discussed. Special attention is given to the intermediate thionitroso compounds, the N-thiosulfinylamines and the persistent radicals 1,2,3-dithiazolyles. New results about the course of the HERZ reaction are described.     

Book Review: Ion mobility spectrometry, 3rd ed. by G.A. Eiceman,Z. Karpas and H.H. Hill,Jr.

After the first edition, released in 1994 and 228 pages long, followed by the second edition, published in 2005 and now 350 pages in length, CRC press (Taylor & Francis Group, Boca Raton, FL) has now released the third edition of Ion mobility spectrometry at the beginning of this year. The content has been expanded to 428 pages and Herbert H. Hill Jr. is now onboard, working alongside the previous authors Gary Eiceman and Zeev Karpas.     

Monomeric and Dimeric (Aminomethylidene)phosphines and -Arsines

Abstract

In (dimethylaminomethylidene)phosphines (1) [1] and -arsines (2) the internal rotation of the dimethylamino group is hindered by a barrier of 50 to 55 kJmol^?1? analogous to the corresponding amidines. In order to evaluate the influence of this conjugative effect upon the P=C and (P)-C-N bond lengths, single crystal x-ray structure determinations of 1a and 2a have been carried out. For comparison, the cyclic (aminomethylidene)phosphine 1H-1,3-benzazaphosphole 5 [2] as well as the dimeric compounds 3a, 3b, and 3c [3] have been analyzed, too, while the arsenic derivative 6 was studied by others [4]. The diarsetanes 4 could not yet be isolated. The structural results indicate the E=C bonds in 1a, 2a, 5, and 6 to be scarcely elongated, the (E)-C-N bonds, however, to be shortened considerably with respect to the dimers.     

SALS,WAXS and mechanical properties of heat‐treated thermotropic polymers

The influence of heat treatment on the texture, microstructure and tensile mechanical properties of extruded thin films of a series of high‐performance thermotropic liquid crystal polymers (LCPs) was investigated. LCPs based on random units of hydroxybenzoic acid (B), hydroxynaphthoic acid (N), terephthalic acid (TA) and biphenol (BP) were kindly supplied by the former Hoechst Celanese Corp as 50 µm thick extruded tapes. The LCPs, denoted B‐N, COTBP and RD1000, have B and N as common comonomers and vary the other comonomers. Thus, this study also enables the investigation of the influence of monomer composition on microstructure and mechanical properties. Heat treatments were carried out at temperatures close to the solid‐to‐nematic transition (T_s→n) for periods up to 5 h, under dry air conditions. The thermal treatment produced either two endotherms or a small increase of T_s→n (B‐N and RD1000), or increased significantly T_s→n (COTBP). Moreover, when heat treatment was carried out approximately 40°C below the respective T_s→n, the mechanical Young's modulus, E, along the extrusion axis, increased for all LCPs. Strikingly, for COTBP, E increased over 100% relative to the as‐extruded film. The results also showed that the optimum treatment time for improving the Young modulus, under dry air atmosphere, was between 3 and 4 h. Wide‐angle X‐ray scattering showed a significant sharpening of crystalline reflections and concentration of the 002 meridional reflection as a result of thermal treatment, suggesting the elimination of defects and a better alignment of the molecular chains along the extrusion axis. This would explain the increase in tensile modulus. Copyright © 2013 John Wiley & Sons, Ltd.     

Application of UHPLC for the determination of free amino acids in different cheese varieties

A rapid ultra-high performance liquid chromatography (UHPLC) protocol for the determination of amino acids as their respective 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate (AQC) derivatives was successfully applied for assessing free amino acid levels in commercial cheese samples representing typical product groups (ripening protocols) in cheesemaking. Based on the Waters AccQ.Tag? method as a high performance liquid chromatography (HPLC) amino acid solution designed for hydrolyzate analyses, method adaptation onto UHPLC was performed, and detection of AQC derivatives was changed from former fluorescence (λ _Ex 250 nm/λ _Em 395 nm) to UV (254 nm). Compared to the original HPLC method, UHPLC proved to be superior by facilitating excellent separations of 18 amino acids within 12 min only, thus demonstrating significantly shortened runtimes (>35 min for HPLC) while retaining the original separation chemistry and amino acid elution pattern. Free amino acid levels of the analyzed cheese samples showed a high extent of variability depending on the cheese type, with highest total amounts found for original Italian extra-hard cheeses (up to 9,000 mg/100 g) and lowest for surface mold- or bacterial smear-ripened soft cheeses (200–600 mg/100 g). Despite the intrinsic variability in both total and specific concentrations, the established UHPLC method enabled reliable and interference-free amino acid profiling throughout all cheese types, thus demonstrating a valuable tool to generate high quality data for the characterization of cheese ripening.     

Unexpected Ritter Reaction During Acid‐Promoted 1,3‐Dithiol‐2‐one Formation

A series of aryl‐substituted 1,3‐dithiol‐2‐ones was prepared by the Bhattacharya? Hortmann cyclization method. Unexpectedly, a Ritter reaction occurred during the acid‐catalyzed cyclization at the cyano group of the aryl substituents and 1,3‐dithiol‐2‐ones bearing a carboxy or a carboxamide group could be selectively obtained (see 1 and 2a in Scheme 1). The formation of the acid or the amide functionality was temperature‐dependent so that the one or the other group could be introduced selectively by modifying the reaction temperature.