Structural characterization of polypyrrole in the solid state by high resolution 15N NMR spectroscopy [II]

The solid-state ¹⁵N CP/MAS NMR spectra and ¹⁵N spin-lattice relaxation times (T₁) of doped and dedoped ¹⁵N-labeled polypyrroles prepared by electrochemical polymerization, have been measured by means of high-resolution solid-state ¹⁵N NMR. The ¹⁵N signal of polypyrrole consists of four peaks decomposed by line shape analysis. The four peaks obtained have been assigned to the various structures of polypyrrole. Further, the half-width of the ¹⁵N NMR spectra of polypyrroles is discussed as related to the electrical conductivity. © 1995 John Wiley & Sons, Inc.     

Uniqueness of form factors for the reduced sine-Gordon model

Using certain asymptotic conditions, we prove the uniqueness of the form factors of the energy-momentum tensor for the reduced sine-Gordon model (2/3) (RSG(2/3)). Bibliography: 5 titles. Translated fromZapiski Nauchnykh Seminarov POMI, Vol. 199, 1992, pp. 177–181. Translated by I. A. Izergina.     

High paraoxon-hydrolyzing activity in organophosphorus insecticide-resistant mosquitoes.

We found a strong paraoxon-hydrolyzing activity (23.4 +/- 8.50 nmol/h/individual and 137 +/- 86.2 nmol/h/mg protein) in the crude extract from larvae of Culex tritaeniorhynchus Toyama 89, which is markedly resistant to organophosphorous insecticides. The activity was higher than those from Cx. tritaeniorhynchus re-e-ae (0.175 +/- 0.0336 and 1.83 +/- 0.651), Anopheles omorii (0.112 +/- 0.0301 and 1.86 +/- 0.746) and An. stephensi (0.0651 +/- 0.0713 and 0.789 +/- 0.910), which are susceptible to organophosphorous insecticides. These facts suggest that the high paraoxon-hydrolyzing activity plays a role in the development of organophosphorous resistance in Cx. tritaeniorhynchus. The enzyme preparation obtained from Toyama 89 showed higher activity in the alkaline pH range and its Km values to paraoxon were 0.67 mM in larvae and 0.50 mM in adults. A calcium ion was strictly required for the hydrolysis of paraoxon. Fenitroxon was also hydrolyzed, in addition to paraoxon. However, it did not degradate parathion and fenitrothion at all. Dichlorvos and phenyl acetate competitively inhibited the enzyme. The phenyl acetate-hydrolyzing activity in the preparation of Toyama 89 was significantly (p less than 0.01) lower than those in susceptible strains, and was irreversibly inhibited by paraoxon. Therefore, the paraoxon-hydrolyzing activity belongs to the class of organophosphate compound hydrolases; it must be thus distinguished from bacterial phosphotriesterase.     

Accelerated glycosylation under frozen conditions

O-Glycosylations using thiomethyl glycosides as donors were compared under both frozen and unfrozen conditions. In the presence of MeOTf as a promoter, enormous rate acceleration was observed when the glycosylation was conducted in p-xylene below its freezing point.     

Hyperbolic-parabolic singular perturbation for quasilinear equations of Kirchhoff type

We consider a hyperbolic-parabolic singular perturbation problem for a quasilinear equation of Kirchhoff type, and obtain parameter-dependent time decay estimates of the difference between the solutions of a quasilinear dissipative hyperbolic equation of Kirchhoff type and the corresponding quasilinear parabolic equation. For this purpose we show time decay estimates for hyperbolic-parabolic singular perturbation problem for linear equations with a time-dependent coefficient.     

HPLC determination of (+)-pseudoephedrine and (-)-ephedrine in Japanese herbal medicines containing Ephedra herb using solid-phase extraction

We developed a rapid and simple HPLC method combined with solid-phase extraction (SPE) for quantitative analysis of (+)-pseudoephedrine (PEP) and (-)-ephedrine (EP) in Japanese herbal (Kampo) medicines such as Kakkon-to, Sho-seiryu-to, Goshaku-san and Bofu-tsusho-san. SPE was performed on TOYOPAK IC-SP M containing propylsulfonic groups. Determination of PEP and EP was carried out using ion-pair reversed-phase HPLC with sodium dodecyl sulfate. N-Benzyldiethylamine was used as an internal standard. The analytical procedure was validated with regard to specificity, linearity, accuracy, and precision. These data suggest that the analytical method developed in this study is useful for quantitative analysis of PEP and EP in various formulations of Kampo medicine containing Ephedra herb.     

Quasi-classical limit of Toda hierarchy andW-infinity symmetries

Previous results on quasi-classical limit of the KP hierarchy and itsW-infinity symmetries are extended to the Toda hierarchy. The Planck constant now emerges as the spacing unit of difference operators in the Lax formalism. Basic notions, such as dressing operators, Baker-Akhiezer functions, and tau function, are redefined.W _{1 +} symmetries of the Toda hierarchy are realized by suitable rescaling of the Date-Jimbo-Kashiara-Miwa vertex operators. These symmetries are contracted tow _{1 +} symmetries of the dispersionless hierarchy through their action on the tau function.     

A lithiation approach to cordycepin analogues variously substituted at the C-8 position

Several 8-substituted cordycepins were prepared via LDA lithiation of 2′,5′-bis-O-(t-butyldimethylsilyl)-cordycepin and successive reactions of its C-8 lithiated species with various types of electrophiles. Wittig reaction of the 8-formyl derivative was also examined.     

A practical synthesis of 4′-thioribonucleosides

A practical synthesis of 4′-thioribonucleosides starting from inexpensive l-arabinose is described. 1,4-Anhydro-2,3-O-isopropylidene-4-thioribitol, which was prepared by using a novel reductive ring-contraction reaction, was converted to the 5-O-silylated sulfoxides. The Pummerer-type thioglycosylation of the sulfoxides gave the 4′-thioribonucleosides stereoselectively.     

Synthesis, structure, and reactivity of novel 3,4-diphosphacyclobutenes bearing silyl groups

[reaction: see text] Copper-mediated homocoupling of sterically hindered 2-(2,4,6-tri-tert-butylphenyl)-1-trialkylsilyl-2-phosphaethenyllithiums afforded 1,2-bis(trialkylsilyl)-3,4-diphosphacyclobutenes (1,2-dihydrodiphosphetenes) through a formal electrocyclic [2+2] cyclization in the P=C-C=P skeleton as well as 2-trimethylsilyl-1,4-diphosphabuta-1,3-diene. Reduction of 1,2-bis(trimethylsilyl)-3,4-diphosphacyclobutenes followed by quenching with electrophiles afforded ring-opened products, (E)-1,2-bis(phosphino)-1,2-bis(trimethylsilyl)ethene and (Z)-2,3-bis(trimethylsilyl)-1,4-diphosphabut-1-ene. The structures of the ring-opened products indicated E/Z isomerization around the C=C bond after P-P bond cleavage of 5, and the isomerization of the P-C=C skeleton. Ring opening of 1,2-bis(trimethylsilyl)-3,4-diphosphacyclobutenes affording (E,E)- and (Z,Z)-1,4-diphosphabuta-1,3-dienes was observed upon desilylation.