NMR identification of C11 to C40 branched hydrocarbons derived from the decomposition of polyisobutylene

The composition of nonvolatile fluids obtained from thermally cracking and hydrogenating polyisobutylene was determined by using a combination of gas chromatography and nuclear magnetic resonance spectroscopy (NMR). This work involved the separation and characterization of a homologous series, C₁₁–C₄₀, of sixteen branched hydrocarbon species consisting of repeating isobutylene structures. As a result of this investigation, useful correlations between NMR spectra and molecular structure for highly branched hydrocarbons were developed. The data demonstrate that these hydrocarbons are unique species characterized by “crowded” and sterically hindered geminal methyl and isolated methylene groups. NMR solvent shift studies in benzene solutions indicate that it is possible to differentiate between maximally crowded geminal methyl groups and between maximally crowded methylene groups in these structures. Results of the benzene-induced solvent effects are discussed with respect to the stereochemistry of these molecules and related to existing solvent shift data. These results suggest that these hydrocarbons are polar or nearly polar materials. Successive losses of isobutylene units from stabilized tertiary radicals can account for the formation of the major species identified in these fluids. Higher carbon numbered species have lower refractive indices and densities and higher molal volumes than predicted by calculations.     

Ein neuer Photoionisationsdetektor für die Gas-Chromatographie

Zusammenfassung In einem Gas-Chromatographen wird der FID durch einen neuen Photoionisationsdetektor (PID) ersetzt. Der Photoionisationsdetektor wird kurz beschrieben und auf seine operativen Vorteile (einfache Anwendung, Fehlen von Betriebsmitteln wie Brenngase usw.) hingewiesen. Es werden einige Messungen mit dem modifizierten Gerät vorgenommen und die Ergebnisse mit denen des FID verglichen. Bedingt durch systemspezifische Vorteile des Photoionisationsdetektors—verglichen mit dem FID ist der Rauschpegel stark vermindert und wegen des größeren Wirkungsgrades der Photoionisation steht ein höheres Signal zur Verfügung—sowie durch das Fehlen von O₂ und seinen Problemen ist eine erhebliche Empfindlichkeitssteigerung des Gesamtsystems festzustellen. Außerdem ergibt sich, wiederum verglichen mit dem FID, ein weiterer Dynamikbereich. Weiter werden mit Hilfe des Photoionisationsdetektors gewonnene Meßergebnisse mit publizierten Ergebnissen anderer Detektoren verglichen und die Vorteile des PID aufgezeigt.

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A new photoionization detector for gas chromatography

Summary In a commercially available GC the FID was replaced by a newly designed photoionization detector (PID). The PID and its operational advantages (ease of use, no neccessity for combustion gas and the related facilities) are described briefly. Some measurements are made with the such modified GC and the results are compared with those obtained with the FID. Specific advantages of the PID — compared to a FID — the noise level caused by the system is lower and (due to the higher ionization efficiency of the PID) the signal is larger — and due to the lack of oxygen and its altendant problems the overall system sensitivity is strikingly better. In addition, the dynamic range — again compared with the FID — is wider. Further, performance data obtained with the PID are compared with published data of other detectors and the advantages of the PID are shown clearly.

     

Experimental and Computational Study of the Thermal Decomposition of 3‐Methyl‐3‐buten‐1‐ol in m‐Xylene Solution

An experimental study of the thermal decomposition of a β‐hydroxy alkene, 3‐methyl‐3‐buten‐1‐ol, in m‐xylene solution, has been carried out at five different temperatures in the range of 513.15–563.15 K. The temperature dependence of the rate constants for the decomposition of this compound in the corresponding Arrhenius equation is given by ln k (s^?1) = (25.65 ± 1.52) ? (17,944 ± 814) (kJ·mol^?1)·T^?1. A computational study has been carried out at the M05–2X/6–31+G(d,p) level of theory to calculate the rate constants and the activation parameters by the classical transition state theory. There is a good agreement between the experimental and calculated rate constants and activation Gibbs energies. The bonding characteristics of reactant, transition state, and products have been investigated by the natural bond orbital analysis, which provides the natural atomic charges and the Wiberg bond indices. Based on the results obtained, the mechanism proposed is a one‐step process proceeding through a six‐membered cyclic transition state, being a concerted and slightly asynchronous process. The results have been compared with those obtained previously by us (Struct Chem 2013, 24, 1811–1816) for the thermal decomposition of 3‐buten‐1‐ol, in m‐xylene solution. We can conclude that in the compound studied in this work, 3‐methyl‐3‐buten‐1‐ol, the effect of substitution at position 3 by a weakly activating CH₃ group is the stabilization of the transition state formed in the reaction and therefore a small increase in the rate of thermal decomposition.     

Structural and Kinetic Aspects of Blood Plasma Protein Adsorption on the Surface of Hydrophobic Polymers

Abstract

Due to the wide use of polymers in medicine, researchers are required to solve a very important problem–to understand the interaction between materials of nonphysiological origin and the surrounding biological liquids, and tissues, particularly blood.     

Trapped-particle modes and asymmetry-induced transport in single-species plasmas

A new asymmetry-induced transport mechanism in pure electron plasmas is shown to be proportional to the damping rate of the corresponding trapped-particle mode, with simple scalings for all other parameters. This transport occurs when axial particle trapping exists due to variations in the electric or magnetic confinement fields. This new transport is strong for even weak unintentional trapping (deltaB/B approximately 10(-3)), and may be prevalent in transport experiments with magnetic or electrostatic theta asymmetries.