Characterization of metal binding properties of rhamnogalacturonan II from plant cell walls by size-exclusion HPLC/ICP-MS.

The binding properties of metal ions to a pectic polysaccharide, rhamnogalacturonan II (RG-II), from plant cell walls were analyzed by size-exclusion HPLC/ICP-MS. The dimeric RG-II borate complex (dRG-II-B) from sugar beet and red wine contained 0.8 - 1.1 mol/mol of B, 0.8 - 1.1 mol/mol of Ca, 0.1 - 0.3 mol/mol of Sr, and 0.03 - 0.07 mol/mol of Ba. The treatment of dRG-II-B with Sr2+, Ba2+, Pb2+ or La3+ exchanged the originally present Ca, Sr and Ba. In contrast, monomeric RG-II (mRG-II), which contained approximately 0.1 mol/mol of Ca, formed complexes with La3+, Eu3+, and Lu3+ added to the solution, but did not do so with Ca2+, Sr2+, Ba2+ and Pb2+. The HPLC/ICP-MS and HPLC/RI (refractive index detector) analysis of the partially hydrolyzed mRG-II that was treated with La3+ indicated that the side chains and backbone of mRG-II together form a lanthanoid binding site.     

Large-volume injection electrothermal AAS combined with tungsten-treated pyrolytic graphite furnace: determination of cadmium in tap, snow and river water samples with phosphate modifier.

A large-volume (100 microl) injection-ETAAS with W-treated PG furnace combined with a phosphate modifier was applied to the determination of unpolluted levels of Cd in tap, snow and river-water samples. The limit of detection of 1.1 ng l(-1) was observed for a 4 w/v% NH4H2PO4 modifer. Matrix interference studies were tested for major ion species well found in fresh water. The direct determination of Cd in certified river water (12 +/- 2 ng l(-1)) was carried out and the observed value was in agreement with the certified one. The good recoveries of Cd added to real environmental water samples were also observed. This method was applied to the determination of Cd in unpolluted environmental water samples.     

Non-destructive rapid analysis of brominated flame retardants in electrical and electronic equipment using Raman spectroscopy.

Using Raman spectroscopy without any preparation, we analyzed the brominated flame retardant, polybromodiphenyl ethers (PBDEs), which has been prohibited by the European Union. The typical Raman bands of PBDEs, which are clearly different from those of other brominated flame retardants, are from 100 to 300 cm(-1). In our analysis, the detection limit was about 100 ppm, and the analysis took about 1 min, whereas the usual method of solvent extraction using gas chromatography/mass spectroscopy takes 50 h.     

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.     

Photo-Absorption and photochemical decomposition of copper and alkaline-earth ß-diketonates as source gases of high-Tc superconducting films

For low-temperature deposition of oxide films relating to Bi-Sr-Ca-Cu-O superconductors, photo-absorption and -decomposition properties were examined with respect to copper and alkaline-earth ß-diketonates. It was confirmed that all ß-diketonates examined were promising as source materials for photochemical vapour deposition (photo-CVD) using a low-pressure mercury lamp, in view of their large light absorption coefficients at wavelength 254 nm. The light irradiation was effective for the formation of highly crystalline oxide films at temperatures below 600 °C. By combining two sources, Ca₂CuO₃ and SrCuO₂ films were prepared. Photo-CVD of c-axis oriented Bi₂Sr₂CuO_x film was achieved by the irradiation of ternary sources of Bi(C₆H₅)₃ and strontium and copper ß-diketonates at 500 °C.     

Separation of fulvic acid from soil extracts based on ion-pair formation with a cationic surfactant.

A novel method for separating fulvic acid (FA) from soil extracts is proposed. The FA, defined as the acid-soluble fraction of an alkaline extract of soil, was separated based on the precipitation of an ion-pair with a cationic surfactant, such as domiphen bromide. The precipitate was dissolved in aqueous HCl to produce H+ -type FA and a surfactant chloride (SUR-Cl). SUR-Cl, in the aqueous solution, was removed by extraction with CHCl3. After the aqueous phase was passed through a cation-exchanger (H+ -type), H+ -type FA (FA-SUR) was obtained as a powder by lyophylization. The chemical characteristics of FA-SUR were compared with an FA sample separated according to the method of the International Humic Substances Society using a DAX-8 resin (FA-DAX). The oxygen content, O/C atomic ratio and total acidity of the FA-SUR were significantly larger than the corresponding values for FA-DAX. The solid-state CPMS 13C NMR spectra indicated that the higher oxygen content of the FA-SUR could be due to alcoholic hydroxyl groups and polysaccharides as well as carboxylic groups. These results show that FA-SUR is more polar and hydrophilic than FA-DAX.     

Viscoelasticity and birefringence of polyisoprene

The complex Young's modulus, E^*(ω), and the complex strain-optical coefficient, O^*(ω), which is the ratio of the birefringence to the strain, were measured for polyisoprene (PIP) over a frequency range of 1 ～ 130 Hz and a temperature range of 22 ～ ?100°C. The imaginary part of O^*, O″, was positive at low frequencies and negative at high frequencies. The real part, O′, was always positive and showed a maximum. The complicated behavior of O^* could be understood by the assumption that E^* = E_R^* + E_G^* and O^* = C_RE_R^* + C_GE_G^*, where E_R^* and E_G^* were complex quantities and C_R and C_G were constants. The C_R value, equal to the ordinary stress-optical coefficient measured in the rubbery plateau zone, was 2.0 × 10^?9 Pa^?1. The C_G value, defined as the ratio O″/E″ in the glassy zone, was ?1.1 × 10^?11 Pa^?1. The E_G^*, which was the major component of E^* in the glassy zone, showed almost the same frequency dependence as that of polystyrene and polycarbonate. The E_R^*, which was dominant in the rubbery zone, was described well by the bead-spring theory. The temperature dependence of the E_G^* was stronger than that of the E_R^*. This difference caused the breakdown of the thermorheological simplicity for E^* and O^* around the glass-to-rubber transition zone. © 1995 John Wiley & Sons, Inc.     

Mass spectral study on thiazolo[3,2-a]benzimidazoles. Studies on heterocyclic compounds. IV

Condensation of α-halocarbonyl compounds and 2-mercaptobenzimidazole gives thiazolo-[3,2-a]benzimidazoles. This condensation occurred at the mercapto group of the benzimidazole followed by cyclization to form the thiazole ring. This was confirmed by the examination of the mass spectra of 2- and 3-methylthiazolo[3,2-a]benzimidazoles, 2- and 3-phenylthiazolo[3,2-a]-benzimidazoles, and their derivatives.     

Enzymatic sulfation of polyphenols related to tannins by arylsulfotransferase.

This report discusses a novel type of arylsulfotransferase (AST) which was derived from human intestinal bacterium sulfated polyphenolic compounds when p-nitrophenyl sulfate (PNS) was taken as a donor substrate. (+)-Catechin, (+/-)-catechin, (-)-epicatechin and (-)-epicatechin gallate were better substrates than tyramine. (-)-Epigallocatechin and (-)-epigallocatechin gallate were slightly worse substrates than tyramine. Although gallic acid was a bad substrate, alkyl gallate esters were better substrates than tyramine. The degree of acceptor specificity increased in proportion to the length of the alkyl group up to the carbon number of five. Pedunculagin, geraniin and corilagin were less effective than tyramine. Rosmarinic acid and penta-O-galloyl-beta-D-glucose were similarly well sulfated. Two products, 4'-monosulfate and 4',5-disulfate of (+)-catechin, were detected at a two-fold molar excess of PNS over (+)-catechin. When (+)-catechin-4'-monosulfate as an acceptor was enzymatically sulfated with PNS as a donor, only the 4',5-disulfate was produced. Thus, arylsulfotransferase was useful for the convenient preparation of sulfate esters of polyphenols at their specific hydroxyl groups.