Mechanism of oxidation of organic substrates by the rhenium(VI) dithiolate complex in nonaqueous media as determined by EPR using the spin trap method

The mechanism of the reaction of the rhenium(VI) dithiolate complex Re^IV(TDT)₃ with some electron-donating organic reagents in nonaqueous solvents is studied by the spin trap method combined with electron paramagnetic resonance. The reaction products are stable complex rhenium(V) anions, Re^V(TDT)₃-, and short-lived radicals forming long-lived adducts with spin traps as probed by EPR. The possibility of using the radical processes for analytical purposes is discussed.     

Reactions of 5-cyano-1,4,6,9-trioxathia-5-phosphaspiro[4,4]nonanes with compounds containing a labile hydrogen atom

All the investigated reactions of 5-cyano-1,4,6,9-trioxathia-5-phosphaspiro[4,4]nonanes with compounds containing a labile hydrogen atom proceed with the loss of HCN, predominant opening of the oxathiophospholane ring, and formation of 2-oxo-1,3,2-dioxaphospholane derivatives.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Science Center, Russian Academy of Sciences, 420083 Kazan. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 11, p. 2670–2673, November, 1992.     

On the minimal time function for distributed control systems in Banach spaces

In this paper, it is shown that the minimal time function is locally Lipschitz continuous for the control systemx=Ax+u in a Banach spadeE, under either of two conditions:A is linear and generates aC ₀-semigroup of bounded linear operators; orA is nonlinear, possibly multivalued, and dissipative. The main tool used for the nonlinear case is a result of Barbu concerning the null controllability of the system.     

On the role of collective and local molecular fluctuations in the relaxation of proton intrapair dipolar order in nematic 5CB

We investigate the role that local motions and slow cooperative fluctuations have on the relaxation of the intrapair dipolar order in the nematic 5CB. With this purpose we present a theoretical and experimental systematic study which allow us to quantify the contribution from each type of molecular fluctuation to the intrapair dipolar order relaxation time, T(1D). The experimental work includes measurements of Zeeman and intrapair dipolar order relaxation times (T(1Z) and T(1D)) as a function of temperature at conventional NMR frequencies, in three complementary samples: normal and chain deuterated 4-n-pentyl-4(')-cyanobiphenyl (5CB and 5CB(d11)) and a mixture of normal 5CB and fully deuterated 4-n-pentyl-4'-cyanobiphenyl (5CB(d19)), 50% in weight. Additionally we perform T(1Z) field-cycling Larmor frequency-dependent measurements to obtain the spectral density of the cooperative fluctuations. The obtained results are as follows. (a) The cooperative molecular fluctuations have a strong relative weight in the relaxation of the intrapair dipolar order state, even at Larmor frequencies in the range of conventional NMR. (b) Alkyl chain rotations are an important relaxation mechanism of the intrapair dipolar order at megahertz frequencies. (c) Intermolecular fluctuations mediated by translational self-diffusion of the molecules is not an efficient mechanism of relaxation of the intrapair dipolar order.     

Crystal structure and ionic conductivity of solid electrolytes M5RESi4O12, where M=Na,Ag, RE=Sm→Lu

Conductivity measurements of the crystals of the N₅RESi₄O₁₂ family, where RE=Sm→Lu, have been made. A reversible phase transition R32

R$\text{3}$c has been established. The conductive channels have been determined using a high temperature X-ray structural analysis of the Na₅RESi₄O₁₂ crystals, as well as the ion exchanged Ag phase.     

Neutral strange particle production inK + p interactions at 32 GeV/c

The production properties ofK _s ⁰ , \(\bar \Lambda\) andK ⁺ p interactions at 32 GeV/c are investigated using the final statistics of the experiment. We present total and semi-inclusive cross sections and aver-age multiplicities. Estimates are given of the diffractive dissociation contributions to total and differential cross sections. Thex-,p _T ^?, and transverse mass dependence of inclusive and semi-inclusive distributions is discussed as well as properties of “prompt”K _s ⁰ 's. The ratio of “prompt”K ₈₉₀ ⁺ (K ₈₉₀ ⁰ ) to “prompt”K ⁰ cross sections is measured to be 1.03±0.12 (0.98±0.17). From a comparison of \(\bar \Lambda\) production inK ^± p interactions at 32 GeV/c, we estimate a strange sea-quark suppression of 0.26 ±0.02. The double differential cross sections ofK _s ⁰ 's is studied as a function of Feynman-x andp _T ² , and a Triple-Regge fit performed. The data are compared in detail to versions of the Lund-model for low-p _T hadronic collisions.     

Mobility of muons in Cu below 2 K

We have performed transverse fieldSR experiments on several different samples of copper in the temperature range below 2 K, including isotope separated Cu and impurity doped polycrystalline Cu.We do not observe any strong effect of the isotope composition of the sample. A⁶³Cu and a natural Cu sample of identical purity both yield 0.16s^–1 for the low-temperature plateau, while an increased linewidth in the⁶⁵Cu case may be related to the strong effects of Fe impurities.Careful transverse field measurements on large single crystals at 0.08 K reveal non-Gaussian lineshapes in accordance with the picture of diffusing muons at this temperature. This allows us to reject several of the existing models for muon behaviour in copper below 2 K.     

Novel laccase redox mediators: spectral, electrochemical, and kinetic properties

The screening of potential redox mediators for laccase was performed using homogeneous enzyme preparations from Coriolus hirsutus and Coriolus zonatus. It was discovered that derivatives of 1-phenyl-3-methyl-pyrazolones were efficient substrates for the laccases. The characterization of two representatives of the 1-phenyl-pyrazolone class, sodium 1-phenyl-3-methyl-4- methylamino-pyrazolone-5-N(4)-methanesulfonate and 1-(3'-sulfophenyl)-3- methylpyrazolone-5, in the reaction catalyzed by laccase was carried out using spectral, electrochemical, and enzyme kinetics methods. The kinetic parameters for the oxidation of the newly discovered substrates were comparable with those for 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulfonate) (ABTS) oxidation by laccase. Electrochemical experiments demonstrated that oxidation of these compounds yielded two high-potential intermediates capable of oxidizing veratryl alcohol, which was used as a lignin model substrate, to the corresponding aldehyde and acid. 1-(3'-Sulfophenyl)-3- methylpyrazolone-5 was about 30-40% as effective in degrading veratryl alcohol compared to ABTS as judged from high-performance liquid chromatography kinetic studies. 1-Phenyl-3-methyl-pyrazolones may be of commercial interest for oxidoreductase-catalyzed biodegradation of organic compounds.     

Synthesis and properties of functional derivatives ofN′-phosphoryl- andN′-phosphonoyldiazeneN-oxides; molecular structure ofN-(2,2-dimethyl-5-nitro-1,3-dioxan-5-yl)-N′-[methoxy(phenyl)phosphoryl]diazeneN-oxide

Methods for the synthesis of polyfunctionalN-phosphoryl- andN-phosphonoyldiazeneN-oxides containing hydroxyl, acetoxyl, and nitrate groups, and dibromoallyl and dibromopropyl fragments have been developed. The molecular structure ofN-(2,2-dimethyl-5-nitro-1,3-dioxan-5-yl)-N-[methoxy(phenyl)phosphoryl)diazeneN-oxide was established by X-ray structural analysis.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1284–1289, July, 1994.