Thermal degradation of copolymers of styrene and acrylonitrile. I. Preliminary investigation of changes in molecular weight and the formation of volatile products

By the use of thermal volatilization analysis (TVA), 292°C was chosen as a suitable temperature for a preliminary experimental survey of the thermal degradation of styrene–acrylonitrile copolymers. TVA also indicated that there is no fundamental change in reaction mechanism as the acrylonitrile content of the polymer is increased from zero to 33.4% although there is a progressive increase in the rate of volatilization. The increase in the rate of volatilization over that of polystyrene is directly proportional to the acrylonitrile content of the copolymer. From the changes in molecular weight which occur during the reaction it is clear that the primary effect of the acrylonitrile units on stability is to cause an increased rate of chain scission, but there is a small proportion of “weak links” which are associated with the styrene units and which are broken instantaneously at 292°C. The number of monomer molecules liberated per chain scission, the zip length, is about 40 for polystyrene in the initial stages of degradation and decreases only to the order of 20 even in copolymer containing 24.9% acrylonitrile. Thus the unzipping process is not severely affected by the acrylonitrile units; this is borne out by the fact that acrylonitrile appears among the products in very much greater concentrations than from pure polyacrylonitrile. The proportion of larger chain fragments (dimer, trimer, etc.) also increases with acrylonitrile content.     

The overflowing cylinder sixty years on

The overflowing cylinder (OFC) was developed at Kodak sixty years ago and remains an elegant, precise and versatile tool for studying the dynamic surface properties of surfactant solutions today. The principles and design of the OFC are introduced and the use of the OFC to study adsorption kinetics and Marangoni effects is explained. Examples are provided from the study of pure surfactant solutions, mixed surfactants and polymer-surfactant complexes.     

Problems,artifacts and solutions in the INADEQUATE NMR experiment

The INADEQUATE experiment can provide unequalled, detailed information about the carbon skeleton of an organic molecule. However, it also has the reputation of requiring unreasonable amounts of sample. Modern spectrometers and probes have mitigated this problem, and it is now possible to get good structural data on a few milligrams of a typical organic small molecule. In this paper, we analyze the experiment step by step in some detail, to show how each part of the sequence can both contribute to maximum overall sensitivity and can lead to artifacts. We illustrate these methods on three molecules: 1‐octanol, the steroid 17α‐ethynylestradiol and the isoquinoline alkaloid β‐hydrastine. In particular, we show that not only is the standard experiment powerful, but also a version tuned to small couplings can contribute vital structural information on long‐range connectivities. If the delay in the spin echo is long, pairs of carbons with small couplings can create significant double‐quantum coherence and show correlations in the spectrum. These are two‐ and three‐bond correlations in a carbon chain or through a heteroatom in the molecule. All these mean that INADEQUATE can play a viable and important role in routine organic structure determination. Copyright © 2010 John Wiley & Sons, Ltd.     

Sum-frequency spectroscopy of a monolayer of zinc arachidate at the solid-solid interface

Infrared-visible sum-frequency spectroscopy has been used to record the vibrational spectrum of a zinc arachidate monolayer at the interface between a sapphire prism and a fused silica lens. Spectra have been recorded for the monolayer deposited on the prism before, during, and after contact, and as a function of increasing pressure. Sum-frequency spectra are reported of the monolayer under sliding contact. The monolayer is found to be resistant to pressure- and shear-induced conformational disorder. However, frequency shifts, drops in peak intensities, and changes in peak intensity ratios have been observed as the monolayer is placed in contact between the prism and the lens. Transfer of monolayer material between the two surfaces is observed and is confirmed by spectra obtained with a monolayer deposited on the surface of the lens rather than the prism. On one face of the sapphire prism, the monolayer reconstructs to a low symmetry layer, probably due to epitaxy. The epitaxial structure disappeared in contact. Existing models for calculating sum-frequency spectra have been extended to include unit cells containing two molecules and torsion about the terminal C-C bond. This model can explain some, but not all, of the experimental observations.     

An adeno-associated viral vector transduces the rat hypothalamus and amygdala more efficient than a lentiviral vector

Background  

This study compared the transduction efficiencies of an adeno-associated viral (AAV) vector, which was pseudotyped with an AAV1 capsid and encoded the green fluorescent protein (GFP), with a lentiviral (LV) vector, which was pseudotyped with a VSV-G envelop and encoded the discosoma red fluorescent protein (dsRed), to investigate which viral vector transduced the lateral hypothalamus or the amygdala more efficiently. The LV-dsRed and AAV1-GFP vector were mixed and injected into the lateral hypothalamus or into the amygdala of adult rats. The titers that were injected were 1 × 10⁸ or 1 × 10⁹ genomic copies of AAV1-GFP and 1 × 10⁵ transducing units of LV-dsRed.     

Metal complexes of N(4)-substituted analogues of the antiviral drug methisazone {1–methylisatin thiosemicarbazone}

Transition Metal Chemistry -     

Synthesis of dipyrrolo[3,4-a:3,4-c]carbazoles: new kinase inhibitors

Two dipyrrolo[3,4-a:3,4-c]carbazole stereoisomers were unexpectedly obtained by Diels–Alder dimerization of 3-indolylmaleimide. Three dimensional structures of both stereoisomers were confirmed by X-ray analysis. Moreover compound 4 inhibits protein kinases in vitro, especially Pim-3, in the sub-micromolar range.