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.     

A precision measurement of the hyperfine structure of87Sr+

The ground state hyperfine splitting of⁸⁷Sr⁺ was measured with a precision of 1×10^–8. The experiments were performed with an RF ion trap connected to an ISOL (isotope separator on-line), where all the possible transitions between Zeeman sublevels were observed by a laser-microwave double resonance method. The magnetic dipole hyperfine constant was determined to beA=–1 000 473.673 (11) kHz.     

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.     

Novel method to control release of lipophilic drugs with high potency from silicone

Silicone has been utilized as a carrier material for sustained release system of lipophilic drugs. Extensive studies revealed that drug release rate is influenced by factors such as physicochemical properties of the drug and additives.(1-5)) When a lipophilic drug is highly potent at low concentrations, the drug release rate should be strictly controlled so as to avoid side effects. In this study, using vitamin D(3) (VD(3)) as an example of such drugs, we investigated novel method to suppress initial burst and to modify drug release rate from silicone matrix. As a result, it was found that (a). addition of human serum albumin (HSA) suppressed initial burst and enhanced release rate in the later stage, resulting constant release of VD(3), (b). covering a matrix formulation with a membrane of low diffusivity (core-rod formulation) suppressed initial burst and released drug in a constant rate, and (3) using materials for which the drug has high affinity as dissolution solvent (reservoir formulation), the drug release rate was reduced.     

Application of an automated synthesis suite to parallel solution-phase peptide synthesis

An in-house developed automated synthesis suite was used to prepare a library of 72 tetrapeptide derivatives, the starting materials for pharmaceutically attractive pentapeptides, employing a convergent strategy. An initial set of 18 dipeptides were synthesized on a large-scale (100-1000 g) using automated synthesis workstations, and then 72 tetrapeptides were synthesized on a medium scale (5-10 g) using an automated system. Each di- or tetrapeptide was prepared in a single operating cycle using a modified methanesulfonic acid method, then a sub-library of 56 pentapeptides were synthesized in parallel, on a small-scale (100 mg-1 g) using a robotic workstation.     

Nuclearg-factors of the 1229 and 2911 keV isomers in143Nd

Nuclearg-factors of the 1229 keV 13⁺/2 and 2911 keV 21⁺/2 level and the half-life of the 1229 keV level have been measured to beg(1229)=0.058(5),g(2911)=0.69(12) andT _1/2 (1229)=6.79(2) ns. The experimental g-factors show that the 1229 keV level has a dominant configuration of (f _7/23^–), and the 2911 keV level has an almost pure (f _7/27^–), configuration.The authors would like to thank the crew of CYRIC for the operation of the cyclotron.     

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.     

Determination of the change of nuclear charge radius of the119Sn Mössbauer transition by internal conversion

Radioactive¹¹⁹Sb was implanted into six host matrices (CaSnO₃, Pt, Y, Au,-Sn, Pb) and internal conversion electrons of the 23.87 keV transition in¹¹⁹Sn were measured with an iron-free magnetic spectrometer as well as Mössbauer spectra. In the analysis of the conversion spectra of outermost electrons, the overlapping K-LM Auger lines were subtracted using the Auger spectrum of tin measured with another source of^117mSn, and the shake-off effect accompanying the conversion process was considered. From the correlation between the Mössbauer isomer shifts and the intensity ratios of O-shell to N₁-shell conversion electrons, the change of the nuclear charge radius of the 23.87 keV transition of¹¹⁹Sn was deduced to be R/R=(0.87 ± 0.25) × 10^–4 for a uniform charge distribution ofR= 1.2 ×A ^1/3 fm or, equivalently, r²>—=(3.6 ± 1.0) ×10^–3 fm².