Hexavalent Chromium-Thioacetamide Redox System Initiated Polymerization of Acrylonitrile

Polymerization of acrylonitrile initiated by the Cr⁶⁺/thioacetamide redox system was studied in nitrogen atmosphere in the temperature range 35–45°C. The rate of polymerization and the rate of Cr⁶⁺ ion disappearance were measured. The effect of certain water-miscible organic solvents, neutral electrolytes, and complexing agents on the rate of polymerization was investigated. Chromic acid alone did not initiate the polymerization under deaerated and undeaerated conditions. Depending on the results obtained, a suitable kinetic scheme was proposed and various rate parameters were evaluated.     

Novel Copolymers of Styrene and Alkyl and Alkoxy Ring‐Trisubstituted Methyl 2‐Cyano‐3‐phenyl‐2‐propenoates

Electrophilic trisubstituted ethylene monomers, akyl and alkoxy ring‐trisubstituted methyl 2‐cyano‐3‐phenyl‐2‐propenoates, RC₆H₂CH[dbnd]C(CN)CO₂CH_3, (where R is 2,3‐dimethyl‐4‐methoxy, 2,5‐dimethyl‐4‐methoxy‐, 2,3,4‐trimethoxy‐, 2,4,5‐trimethoxy, 2,4,6‐trimethoxy, and 2,4‐dimethoxy‐3‐methyl), were synthesized by the piperidine catalyzed Knoevenagel condensation of ring‐substituted benzaldehydes and methyl cyanoacetate, and characterized by CHN elemental analysis, IR, ¹H‐ and ¹³C‐NMR. Novel copolymers of the ethylenes and styrene were prepared at equimolar monomer feed composition by solution copolymerization in the presence of a radical initiator (AIBN) at 70°C. The composition of the copolymers was calculated from nitrogen analysis, and the structures were analyzed by IR, ¹H and ¹³C NMR, GPC, DSC, and TGA. High T_g of the copolymers in comparison with that of polystyrene indicates a substantial decrease in chain mobility of the copolymer due to the high dipolar character of the trisubstituted ethylene monomer unit. The gravimetric analysis indicated that the copolymers decompose in the 283–306°C range.     

Polyphenyl-as-triazines from Perfluoroalkyleneamidrazones

Abstract

High molecular weight polyphenyl-as-triazines were prepared at ambient temperature by the cyclopolycondensation of perfluoroglutaramidrazone and perfluoroadipamidrazone with various bis(1,2-dicarbonyl) monomers. The effect which the perfluoroalkylene group had upon certain chemical and physical properties of the polymers was determined. Thermal evaluation involved TGA, DSC, TMA, and isothermal weight loss studies of films at 232 °C in air. The polymers exhibited excellent hydrolytic stability as evidenced by retention of n _inh after boiling in water (24 hr) and 10% sodium hydroxide solution (8 hr). A stable uncyclized intermediate was isolated from the reaction of perfluoroadipamidrazone and benzil which was cyclized to the phenyl-as-triazine model compound [3,3′ -perfluorotetramethylenedi (5,6-diphenyl-as-triazine)].     

Using Metal Complex Ion-Molecule Reactions in a Miniature Rectilinear Ion Trap Mass Spectrometer to Detect Chemical Warfare Agents

The gas-phase reactions of a series of coordinatively unsaturated [Ni(L)_n]^y+ complexes, where L is a nitrogen-containing ligand, with chemical warfare agent (CWA) simulants in a miniature rectilinear ion trap mass spectrometer were investigated as part of a new approach to detect CWAs. Results show that upon entering the vacuum system via a poly(dimethylsiloxane) (PDMS) membrane introduction, low concentrations of several CWA simulants, including dipropyl sulfide (simulant for mustard gas), acetonitrile (simulant for the nerve agent tabun), and diethyl phosphite (simulant for nerve agents sarin, soman, tabun, and VX), can react with metal complex ions generated by electrospray ionization (ESI), thereby providing a sensitive means of detecting these compounds. The [Ni(L)_n]²⁺ complexes are found to be particularly reactive with the simulants of mustard gas and tabun, allowing their detection at low parts-per-billion (ppb) levels. These detection limits are well below reported exposure limits for these CWAs, which indicates the applicability of this new approach, and are about two orders of magnitude lower than electron ionization detection limits on the same mass spectrometer. The use of coordinatively unsaturated metal complexes as reagent ions offers the possibility of further tuning the ion-molecule chemistry so that desired compounds can be detected selectively or at even lower concentrations.

Poly-Sugar: Modification of Poly(vinyl Alcohol)

This paper describes the attachment of sugar (sucrose) onto low molecular weight poly(vinyl alcohols) (etherification) to produce a new class of synthetic sweetener. Because of its regulated molecular weight, the new sweetener would pass through the digestive tract and be excreted in its original molecular form. We have termed the new class of sweeteners poly-sugar. The etherification of sucrose with poly(vinyl alcohol) can be carried out either in dimethyl sulfoxide or water. We have prepared poly-sugars with varying degrees of etherification (3.4–5.4). Highly etherified products were bitter, but a poly-sugar with a 4.23 degree of etherification was sweet without any bitter aftertaste.     

Conformation and Hydrolytic Stability of Polysaccharide from Xanthomonas campestris

Xanthomonas campestris polysaccharide in the solid state is stable to 225°C in air and 250°C in inert atmosphere. In solution, even at moderate temperatures, the polymer undergoes hydrolytic degradation via the glycosidic linkages, and occurrence of main-chain scission results in lower solution viscosity. In solution, the polymer can exist in ordered and disordered conformations. In distilled water at temperatures ≤ 50°C, the polymer exists in the disordered conformation. In the presence of salt, acid, or base the polymer exists in the ordered conformation. In the ordered conformation the polymer exhibits a far greater hydrolytic stability. The higher stability of the ordered conformation is especially demonstrated when the polymer is aged in acid or base solutions. Contrary to the expected lower stability of the glycosidic linkages in acid or base than in water, Xanthomonas campestris polysaccharide shows higher stability in these media.     

Present and Future of PLA Polymers

Abstract

Lactic acid-based aliphatic polyesters (PLAs) are well known biocompatible bioresorbable polymers which are being increasingly used as biomaterials for temporary therapeutic applications. Because of their sensitivity to water and the formation of degradation by-products which can be easily metabolized by microorganisms, this type of polymers also has potential to replace commodity polymers in packagings or as mulch films. From an overview of synthesis routes, structural characteristics, and performances, an attempt is made to evaluate the future of PLA polymers insofar as industrial development is concerned.     

Food structure: Roles of mechanical properties and oral processing in determining sensory texture of soft materials

There is a desire to alter food composition to make foods healthier and at the same time not diminish sensory quality. This requires an understanding of key elements of food structure associated with texture perception. Texture, in part, is perceived during oral processing of food. Knowledge of structure–oral processing–texture interrelations could be utilized to develop or prevent specified textural attributes. Overall, the investigation of structure–oral processing–texture interrelations is just starting as a research focus. Factors including non-universal and inconsistent sensory terminology, omission of consideration for structural changes incurred by oral processes, and the lack of cross-disciplinary investigations hamper progress in this field. Consideration of these factors in future investigations on sensory texture will increase the applicability of their findings and bring us closer to understanding the contribution of food structure to sensory texture.