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.     

Thickness decrease of a grafted polyelectrolyte membrane exposed to shear flow

The effect of the shear flow on the thickness change of a polyelectrolyte membrane grafted onto a glass substrate was directly investigated with a flow cell combined with a confocal laser scanning microscope. The membrane thickness decreased proportionally to an increase in the shear stress of the flow when the shear rate exceeded a critical value of 1 s^?1. The higher the ionic strength was of the fluid, the greater the thinning effect was. The correlation between the critical shear rate and the relaxation of the polymer in the gel membrane was examined. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2808–2815, 2003     

Novel ring transformation of thiazolidine to oxazolidine: acyl halide-promoted intramolecular rearrangement of 4(R)-hydroxymethyl-3-methyl-1,3-thiazolidine

An interesting transformation occurs during acylation of 4(R)-hydroxymethyl-3-methyl-1,3-thiazolidine when 4(R)-acylthiomethyl-3-methyl-1,3-oxazolidines are yielded: the reaction competing with O-acylation is controlled by the bulkiness of the acyl group.     

Synthesis and metal-ion binding properties of monoazathiacrown ethers

Synthetic procedures for monoazathiacrown ethers were explored, and monoazatrithia-12-crown-4, monoazatetrathia-15-crown-5, and monoazapentathia-18-crown-6 were obtained in moderate yields by the reaction of bis(2-chloroethyl)amine with the appropriate dithiols in the presence of lithium hydroxide in THF. To evaluate metal-ion binding properties of the monoazathiacrown ethers by solvent extraction, lipophilic dodecyl and dodecanoyl groups were incorporated onto the monoazathiacrown ethers. The solvent extraction experiments suggested that monoazathiacrown ethers have Ag(+) and Hg(2+) selectivities and that the relative selectivity between Ag(+) and Hg(2+) depends on their nitrogen atom properties and numbers of sulfur atoms reflecting the respective affinities of nitrogen and sulfur atoms to Hg(2+) and Ag(+). An interesting ability to bind Mg(2+) was observed in the case of N-dodecyl monoazatrithia-12-crown-4.     

High-performance liquid chromatographic assay for glucuronidation activity of 7-ethyl-10-hydroxycamptothecin (SN-38), the active metabolite of irinotecan (CPT-11), in human liver microsomes

A simple and sensitive assay for glucuronidation activity of 7-ethyl-10-hydroxycamptothecin (SN-38), the active metabolite of irinotecan (CPT-11), in human liver microsomes by high-performance liquid chromatography (HPLC) with fluorescence detection is reported. The method was validated for the determination of SN-38 glucuronide (SN-38G) with respect to specificity, linearity, recovery, stability, precision, accuracy, and limits of detection and quantitation. There was no interference from matrix and non-enzymatic reactions. The calibration curve for SN-38G was linear from 5 to 500 nM. Average recoveries ranged from 98 to 100% in spiked human liver microsome samples, and the SN-38G was stable at 4 degrees C for at least 72 h. The newly developed method was found to be more sensitive and selective than previous methods using thin layer chromatography and HPLC. The limit of quantitation for SN-38G was 5 nM (2.5 pmol/assay). The intra- and inter-day precision and accuracy were less than 7 and 4%, respectively. The intra- and inter-day precision of enzyme assay for UDP-glucuronosyltransferase (UGT) activity toward SN-38 in human liver microsomes was less than 4%. With this improved sensitivity, the kinetics of SN-38 glucuronidation in human liver microsomes could be determined more precisely. Therefore, this method is applicable to in vitro study on the side effects and drug interactions of CPT-11 using small amounts of biological sample.     

Measurement of acid-catalyzed isomerization of unsaturated aldehyde-2,4-dinitrophenylhydrazone derivatives by high-performance liquid chromatography analysis

Aldehyde-2,4-dinitrophenylhydrazones exist as (E)- and (Z)-geometrical isomers, and adventitious isomerization during sample preparation can cause analytical errors. Purified alkenal-2,4-dinitrophenylhydrazone derivatives comprise only the (E)-isomer. However, partial isomerization to the (Z)-isomer occurs upon addition of acid to attain an equilibrium isomer ratio. The UV-visible spectral properties of the isomers differ; the (Z)-isomer exhibiting a 6-10 nm lower absorption maximum compared to the (E)-isomer. Alkenal-2,4-dinitrophenylhydrazones having a CC double bond at the 2- or 3-position of the alkenal exhibited similar absorption maxima with an equilibrium isomer ratio (0.035) that was much lower than those of other alkenals. The CC double bond at the 3-position migrates to a position of conjugation with the CN double bond during hydrazone synthesis to form a stabilized molecular structure. Alkenal-2,4-dinitrophenylhydrazones having a double bond at the 4-position or greater exhibited a similar absorption maxima equilibrium isomer ratio (0.14) to alkanal-2,4-dinitrophenylhydrazones. The quantitative analysis of carbonyl compounds in air or water using DNPH is usually conducted in the presence of an acid catalyst. Consequently, the solution of the direct extract prepared for HPLC or GC analysis contains both (E)- and (Z)-isomers.     

A theoretical study of the dielectric solvent effect on vicinal spin coupling constants

The dielectric solvent effect on HCCH, HCNH and HCNC spin coupling constants in ethane, tetrachloroethane and trans N-methylformamide has been calculated by finite perturbation theory based on the INDO and CNDO/2 approximations incorporating solvaton theory. The available experimental data are interpreted using the calculated variations of spin coupling constants. The effect of dielectric constant on the general form of the Karplus relation is included in the finite perturbation calculations.