Quinones for redox flow batteries

Quinones are electroactive species that have shown great promise for redox flow batteries due to the ability to tune their properties and to act as both negative and positive electrolytes. The following review outlines highlights of work in the last couple of years working to provide materials with higher stability, solubility, and performance. Developments toward stable negolytes have provided opportunities for potential commercial opportunities when paired with alternate chemistries. However, the stability of quinones in high potential electrolytes is still not sufficient and the number of potential quinones limited.     

Crystallization of Arthrobacter sp. strain 1C N-(1-D-carboxyethyl)-L-norvaline dehydrogenase and its complex with NAD+

The novel NAD+-linked opine dehydrogenase from a soil isolate Arthrobacter sp. strain 1C belongs to an enzyme superfamily whose members exhibit quite diverse substrate specificites. Crystals of this opine dehydrogenase, obtained in the presence or absence of co-factor and substrates, have been shown to diffract to beyond 1.8 ? resolution. X-ray precession photographs have established that the crystals belong to space group P21212, with cell parameters a = 104.9, b = 80.0, c = 45.5 ? and a single subunit in the asymmetric unit. The elucidation of the three-dimensional structure of this enzyme will provide a structural framework for this novel class of dehydrogenases to enable a comparison to be made with other enzyme families and also as the basis for mutagenesis experiments directed towards the production of natural and synthetic opine-type compounds containing two chiral centres.     

High-p T αα andαp interactions

Properties of secondaries associated with a high-p _T charged trigger particle (3<p _T <5 GeV/c) were studied for αp and αα interactions at c.m. energies \(\sqrt s = 88\) GeV and 125 GeV, respectively. Thep _T distributions of secondaries in the away-jet and trigger-jet regions were compared with those for high-p _{T pp} interactions. No statistically significant differences were seen, except at lowp _T . Momentum and angular distributions of spectator and leading protons were studied as a function of charge and rapidity of the trigger hadron. The observed correlations between trigger charge and number of spectator protons provide evidence of valence quark contributions to the trigger jet.     

Interactions in water-alcohol mixtures studied by NMR and infrared spectroscopy

By using low temperatures and largely deuterated solvents, the rate of OH proton exchange for aqueous solutions of alcohols is reduced sufficiently to give separate NMR signals from water and alcohol OH protons. The limiting shifts for dilute alcohols in water are down-field of both the water resonance and those of the pure alcohols. This contrasts with the limiting shift for water in the alcohols, which is to high field of the bulk water resonance. The resonance shifts initially to low fields as [ROH] increases, the rate of shift being greatest for t-butyl alcohol. For dilute aqueous solutions, all the alcohols reduce the total concentration of free OH groups, as judged by the overtone infrared spectra. Some of these results are interpreted in terms of a scavenging of free OH groups by the excess lone-pairs of the alcohol molecules. An extra, temperature dependent, down-field shift in the water proton resonance induced by t-butyl alcohol is assigned to a clathrate cage effect.     

Oxygen-hydrogen stretching frequencies for water and methanol in the primary solvent shells of cations and anions

Since the band for OH stretching of HOD molecules solvating perchlorate ions is clearly resolved, the remaining band can be analysed to give values for the OH absorption for the cation solvation shell: these are closely correlated with NMR shift data.     

Analysis of the results of calibrating meteoritic olivine crystals with238U nuclei at the Bevalac accelerator

The results are presented of calibrating the sensitivity of olivine crystals from meteorites by the²³⁸U nuclei produced at the Bevalac accelerator. The comparative studies of the spectra of the etchable track lengths due to the²³⁸U nuclei and to fossil tracks in these olivines have shown that the group of the 210 m fossil tracks observed in 1980 at the LNR, JINR is due to the galactic cosmic-ray nuclei of the Th-U group. As regards the origin of the 340–360 m group of fossil tracks which were considered in [2] to be candidates for superheavy nuclei in cosmic rays the presence of the track with a length of up to 360 m in the calibrating²³⁸U track length spectra indicates that the above interpretation has to be questioned. The possible ways of the unambiguous identification of the group of the abnormally long fossil tracks are discussed.In conclusion the authors express their deep gratitude to Academician G.N. Flerov for thoughtful guidance and permanent attention to this study. The authors wish to thank Dr. G.M. Ter-Akopian for very useful discussions and advice and also for his help during the calibrations on Bevalac, Dr. R.I. Petrova for her help in preparing olivine crystal mounts and for their subsequent annealing and etching, and Mrs. G.G. Bankova and G.P. Knyazeva for the thorough microscopic measurements of the²³⁸U track spectra.     

Electron spin resonance studies of the radiolysis of bi-π-cyclopentadienylalkyls of molybdenum and tungsten

Exposure of (C₅H₅)₂MO(CH₃)₂ and (C₅H₅)₂W(CH₃)₂, prepared from the corresponding dichlorides, to ²⁰Co γ-rays at 77 K gave H₂C.CML₃ carbene species characterised by their ESR spectra, together with a central feature possibly due to the parent cations. Dilute solutions in CD₃OD gave features assigned to the parent anions which were converted on bleaching with visible light into methyl radicals, and H₂C.ML₃ radicals. From the magnitude of the ¹H and ¹⁸³W hyperfine coupling constants, it is deduced that the SOMO for H₂C.WL₃ radicals is strongly localised on carbon.Dilute solutions in aqueous sulphuric acid also gave species with A(2H) = 20 G, identified as the carbene derivatives, H₂C.Ml₃. These were formed on annealing, as signals assigned to HSO₄ · radicals were lost.     

An electron spin resonance study of dimeric,trimeric, and tetrameric paramagnetic silver atom clusters

The low temperature γ-irradiation of frozen benzene solutions containing AgClO₄ leads directly to the formation of the paramagnetic species Ag₂ ⁺, no Ag⁰ centre being detected. When benzene or toluene solutions containing AgBF₄ were similarly treated and the matrix carefully annealed, well-resolved E.S.R. spectra attributed to paramagnetic clusters containing three and four equivalent silver atoms were detected. The lack of resolved anisotropy in the spectrum of the trimer and tetramer are thought to argue in favour of a triangular and tetrahedral geometry respectively rather than linear chains.