Electrochemical reduction of pyrethroid insecticides based on esters of α-cyano-3-phenoxybenzyl alcohol at glassy carbon and mercury electrodes in acetonitrile

The electrochemical reduction of eight commercially important pyrethroid insecticides which are esters of either α-cyano-3-phenoxybenzyl alcohol (cycloprothrin, cyphenothrin, cyhalothrin, deltamethrin, esfenvalerate and cypermethrin) or 4-fluro-α-cyano-3-phenoxybenzyl alcohol (cyfluthrin and flumethrin) has been studied under conditions of voltammetry and bulk electrolysis at both glassy carbon and mercury electrodes in acetonitrile. In general, the peak potential of the initial reduction process observed at very negative potentials at both electrode surfaces shifts to a more positive value under conditions of consecutive potential cycling. At the hanging mercury drop electrode the reduction occurs at even more negative potentials than at a glassy carbon electrode because a blocking mechanism appears to be operative. Despite this major difference in the primary reduction step, common voltammetric features are observed at less negative potentials on second and subsequent cycles of the electrode potential at either electrode surface. For example, the initial reduction process always results in the formation of a species which is reversibly reduced at less negative applied potentials. Furthermore, despite the definition of the voltammetric response being highly sensitive to the individual pyrethroid structure, long time-scale bulk electrolysis experiments at glassy carbon or mercury pool electrodes led to the formation of analogous final products. The fact that pyrethroids with a widely varying range of acid moieties exhibit similar voltammetric behaviour suggests that the acid moiety is not directly involved in the initial electron transfer process. Controlled potential electrolysis studies at both electrode surfaces coupled with HPLC and mass spectral identification of products obtained after ethylation with ethyl iodide showed that the reduction mechanism on the longer time-scale involves cleavage of the ester with liberation of free cyanide ion. The major reduction product identified was the anion of either 3-phenoxybenzoic acid or 4-fluoro-3-phenoxybenzoic acid in yields ranging from 31 to 66%.     

High energy electronic neutrino (ve) and antineutrino (ve) interactions

The total cross-sections for $\text{v}{}_{\mathrm{<mtext>e</mtext>}}\text{(}\text{v}{}_{\mathrm{<mtext>e</mtext>}}\text{)}$-nucleon scattering have been measured. A test has been made of the muon number conservation law. A limit of 2.4 GeV is found the mass of the “Georgi-Glashow type” heavy lepton     

Observation of inclusive η production in ee annihilation at CM energies of 34 GeV

The inclusive production of η mesons at CM energies around 34 GeV has been studied for e⁺e⁻ annihilation into hadrons. The average number of η-mesons per event is found to be 0.72 ± 0.10 (stat.) ± 0.18 (syst.). The abundance of η's is studied as a function of event shape parameters and it is compared to the corresponding π⁰ rates.     

Stereoselective synthesis of four stereoisomers of beta-methoxytyrosine, a component of callipeltin A

Callipeltin A is a novel cyclic depsipeptide that selectively inhibits the cardiac sodium/calcium exchanger and is therefore of interest as a regulator of myocardial contractility. The stereochemistry of beta-methoxytyrosine, one of the amino acids contained within the marine natural product, could not be determined. In an effort to elucidate the stereochemistry of this moiety, a stereoselective synthesis of four stereoisomers of beta-methoxytyrosine from (S)- and (R)-serine was accomplished.     

Micro-eta3:eta4-Lithiocene and eta3:eta3-zincocene incorporating 1,2-diaza-3,5-diborolyl, a cyclopentadienyl analog

A heterocyclic cyclopentadienyl analog containing only one carbon atom in the ring was prepared and a polymeric lithiocene and a monomeric zincocene containing this novel ligand have been isolated and crystallographically characterized.     

Statistical analysis of the autoregressive modeling of reverberant speech

Hands-free speech input is required in many modern telecommunication applications that employ autoregressive (AR) techniques such as linear predictive coding. When the hands-free input is obtained in enclosed reverberant spaces such as typical office rooms, the speech signal is distorted by the room transfer function. This paper utilizes theoretical results from statistical room acoustics to analyze the AR modeling of speech under these reverberant conditions. Three cases are considered: (i) AR coefficients calculated from a single observation; (ii) AR coefficients calculated jointly from an M-channel observation (M > 1); and (iii) AR coefficients calculated from the output of a delay-and sum beamformer. The statistical analysis, with supporting simulations, shows that the spatial expectation of the AR coefficients for cases (i) and (ii) are approximately equal to those from the original speech, while for case (iii) there is a discrepancy due to spatial correlation between the microphones which can be significant. It is subsequently demonstrated that at each individual source-microphone position (without spatial expectation), the M-channel AR coefficients from case (ii) provide the best approximation to the clean speech coefficients when microphones are closely spaced (<0.3m).     

Direct enantio- and diastereoselective Mannich reactions of malonate and beta-keto esters with N-Boc and N-Cbz aldimines catalysed by a bifunctional cinchonine derivative

A highly enantioselective Mannich reaction between malonate esters and N-Boc and N-Cbz aldimines, catalysed by a bifunctional cinchonine derivative, has been developed; extension of this methodology to encompass the use of 2-substituted-1,3-dicarbonyl nucleophiles allows the formation of adjacent stereocentres, one of which is quaternary, in high relative and absolute stereocontrol.     

Counting arithmetical structures on paths and cycles

Let $G$ be a finite, connected graph. An arithmetical structure on $G$ is a pair of positive integer vectors $\mathbf{d},\mathbf{r}$ such that $(diag\left(\mathbf{d}\right)?A)\mathbf{r}=0$, where $A$ is the adjacency matrix of $G$. We investigate the combinatorics of arithmetical structures on path and cycle graphs, as well as the associated critical groups (the torsion part of the cokernels of the matrices $(diag\left(\mathbf{d}\right)?A)$). For paths, we prove that arithmetical structures are enumerated by the Catalan numbers, and we obtain refined enumeration results related to ballot sequences. For cycles, we prove that arithmetical structures are enumerated by the binomial coefficients $\left(\genfrac{}{}{0ex}{}{2n?1}{n?1}\right)$, and we obtain refined enumeration results related to multisets. In addition, we determine the critical groups for all arithmetical structures on paths and cycles.