Dielectric resonator-based resonant structure for sensitive ESR measurements at high-hydrostatic pressures

We present a newly developed microwave probe head that accommodates a gasketed sapphire anvil cell (SAC) for performing sensitive electron spin resonance (ESR) measurements under high-hydrostatic pressures. The system was designed around commercially available dielectric resonators (DRs) having the dielectric permittivity of approximately 30. The microwave resonant structure operates in a wide-stretched double-stacked geometry and resonates in the lowest cylindrical quasi TE(011) mode around 9.2 GHz. The most vital parts of the probe's microwave heart were made of plastic materials, thus making the resonant structure transparent to magnetic field modulation at 100 kHz. The overall ESR sensitivity of the probe was demonstrated for a small speck of 2,2-diphenyl-1-picrylhydrazyl radical (DPPH) positioned in the gasket of the SAC, using water as the pressure-transmitting medium. The system was also used for studying pressure-induced changes in spin-relaxation mechanisms of a quasi-1D-conducting polymer, K(1)C(60). For small samples located in the sample hole of the gasket the probe reveals sensitivity that is only approximately 3 times less than that yielded by regular ESR cavities.     

Polarographische Bestimmung von ?thylendiamin in Gegenwart von Ammoniak

Ohne Zusammenfassung

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Polarographic determination of ethylene diamine in the presence of ammonia

     

Comparison of spectroscopic and electrochemical studies of disproportionation equilibria of 1,3,5-triphenylverdazyl radical inDMF containing carboxylic acids

Summary Stoichiometry and equilibrium constants for the disproportionation of the title radicals in N,N-dimethylformamide containing salicilic, chloroacetic, and phenylacetic acids were determined on the basis of absorption spectra. On the other hand, only apparent equilibrium constants depending on concentrations of an acid and a radical could be obtained from electrochemical measurements at a mercury electrode. Significant differences in reaction stoichiometry and in order of magnitudes of disproportionation constants found under spectroscopic and electrochemical conditions were discussed in terms of an influence of the electric field in the double layer on the distribution of different associates formed by verdazyl species with acids.

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Vergleich spektroskopischer und elektrochemischer Untersuchungen von Disproportionierungsgleichgewichten von 1,3,5-Triphenylverdazylradikalen inDMF/Carbonsäure-Mischungen

Zusammenfassung Die Stöchiometrie und die Gleichgewichtskonstanten für die Disproportionierung der Titelradikale wurden in N,N-Dimethylformamid mit einem Gehalt an Salizyl-, Chloressig- bzw. Phenylessigsäure auf Basis der Absorptionsspektren bestimmt. Andererseits wurden lediglich effektive Gleichgewichtskonstanten — in Abhängigkeit der Konzentration von einer Säure und einem Radikal — aus elektrochemischen Messungen an der Quecksilberelektrode erhalten. Signifikante Unterschiede der Reaktionsstöchiometrie und die Größenordnungen in den Disproportionierungskonstanten, die bei den spektroskopischen bzw. elektrochemischen Bedingungen gefunden wurden, werden im Hinblick auf den Einfluß des elektrischen Feldes in der Doppelschicht auf die Verteilung verschiedener Assoziate von Verdazylspezies mit Säuren diskutiert.

     

Electrochemical studies of ion pairs and triplets formed by alkali metal cations with 1,2-naphthosemiquinone and 1,2-naphthoquinone dianion

The properties of ion associates formed by alkali metal cations with 1,2-naphthosemiquinone radical anions and 1,2-naphthoquinone dianions have been polarographically studied in dimethylsulfoxide solutions. It was established that these radicals and dianions coexist in equilibria with corresponding ion pairs and triple ions. The values of association constants were calculated on the basis of the slightly modified method of De Ford and Hume. Some structural aspects of ion association in the systems investigated are discussed.     

Multifunctionality in Epoxy Resins

Abstract

Epoxy resin will continue to be in the forefront of many thermoset applications due to its versatile properties. However, with advancement in manufacturing, changing societal outlook for the chemical industries and emerging technologies that disrupt conventional approaches to thermoset fabrication, there is a need for a multifunctional epoxy resin that is able to adapt to newer and robust requirements. Epoxy resins that behave both like a thermoplastic and a thermoset resin with better properties are now the norm in research and development. In this paper, we viewed multifunctionality in epoxy resins in terms of other desirable properties such as its toughness and flexibility, rapid curing potential, self-healing ability, reprocessability and recyclability, high temperature stability and conductivity, which other authors failed to recognize. These aspects, when considered in the synthesis and formulation of epoxy resins will be a radical advance for thermosetting polymers, with a lot of applications. Therefore, we present an overview of the recent finding as to pave the way for varied approaches towards multifunctional epoxy resins.     

Interpretation of13C NMR spectra of 7-substituted 9,11-dideoxy-PGF 1 analogues and their synthons

A full interpretation of¹³C NMR spectra of the methyl esters of 7-hydroxy-and 7-oxo-9,11-dideoxy-PGF ₁ analogues and their synthons is reported.

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Interpretation von¹³C-NMR-Spektren von 7-substituierten 9,11-Dideoxy-PGF₁-Analogen und deren Synthonen

Zusammenfassung Es wird eine vollständige Zuordnung der¹³C-NMR-Resonanzen von den Methylestern der 7-Hydroxy- und 7-Oxo-9,11-dideoxy-PGF ₁-Analogen und ihrer Synthone beschrieben.

     

Rates of the halide ion cleavage from halo-9,10-diphenylanthracene anion radicals in DMF

The rate constants k for the cleavage of the carbon-halogen bond in anion radicals of 1- and 2-chloro-9,10-diphenylanthracene, 9,10-dichloroanthracene and 2-bromo-9,10-diphenylanthracene have been determined and compared with the literature data for other anthracenyl halides. There is no significant correlation between log k and the formal potentials of the anion radical formation. However, linear relationships of the experimental RT In k vs. the relative thermodynamic contribution to the activation barrier as well as the relative intrinsic activation energy (calculated on the basis of the recent Savéant model and using the ionic component of the bond enthalpy estimated from the absolute electronegativity and hardness) have been found.