Preparation of a cyclodextrin dimer linked with a bis(picolinyl)cystine moiety and its intra- and intermolecular inclusion behavior

A novel cyclodextrin (CD) dimer linked with a bis(picolinyl)cystine (Cys) moiety was prepared by the coupling of Boc-protected Cys with amino-modified CDs, followed by deprotection of the Boc groups and bispicolinylation. The dimer showed less affinity to an organic guest molecule compared to that of a native CD monomer. It was attributed to an intramolecular inclusion of the pyridine moiety into CD cavity. The dimer caused significant increase of its organic guest affinity by an addition of a copper ion. The included pyridine group may come out of a CD cavity to bind the copper ion and the two CDs included cooperatively and intermolecularly a guest molecule with high affinity.     

Chemically modified proton‐conducting membranes based on sulfonated polyimides: Improved water stability and fuel‐cell performance

A series of branched/crosslinked sulfonated polyimide (B/C‐SPI) membranes were prepared and evaluated as proton‐conducting ionomers based on the new concept of in situ crosslinking from sulfonated polyimide (SPI) oligomers and triamine monomers. Chemical branching and crosslinking in SPI oligomers with 1,3,5‐tris(4‐aminophenoxy)benzene as a crosslinker gave the polymer membranes very good water stability and mechanical properties under an accelerated aging treatment in water at 130 °C, despite their high ion‐exchange capacity (2.2–2.6 mequiv g^?1). The resulting polymer electrolytes displayed high proton conductivities of 0.2–0.3 S cm^?1 at 120 °C in water and reasonably high conductivities of 0.02–0.03 S cm^?1 at 50% relative humidity. In a single H₂/O₂ fuel‐cell system at 90 °C, they exhibited high fuel‐cell performances comparable to those of Nafion 112. The B/C‐SPI membranes also displayed good performances in a direct methanol fuel cell with methanol concentrations as high as 50 wt % that were superior to those of Nafion 112. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3751–3762, 2006     

The origin of enhanced photocatalytic decomposition of ATP on TiO2 powders as induced by surface modification with lanthanide ions: important roles of ATP adsorption to the modified surface

Surface modification of TiO₂ powders with lanthanide salts (EuCl₃ or YbCl₃) enhanced photocatalytic decomposition of ATP. In comparison with the unmodified catalyst, a 3-fold increase in the ATP decay rate was observed with TiO₂ powders as prepared in 5 mM EuCl₃ (or YbCl₃) solution. The reason was ascribed to enrichment of ATP to TiO₂ powder with the lanthanide ions. Evidence was obtained by adsorption experiments where ATP concentration was monitored after dispersing TiO₂ powders into the solution. The ATP molecules adsorbed faster to TiO₂ powder and strongly stabilized there in the presence of Yb³⁺ than otherwise.     

Evaluation of radioimmunoassay of the blood tobramycin level for the purpose of setting the dosage based on the clinical pharmacokinetic theory and a comparison of radioimmunoassay with other assay methods

With the purpose to use for therapeutic drug monitoring (TDM), blood concentrations of tobramycin (TOB) in each patient were measured by radioimmunoassay (RIA). A RIA kit of TOB (Clinical assay-Japan Travenol) was evaluated for precision and recovery, in that partial improvement of the method was made, in order to measure low level of TOB. The RIA was compared with high-performance-liquid-chromatography (HPLC), bioassay (BA) and 2 kinds of enzyme immunoassay (EIA) (EMIT and SLFIA). The RIA of TOB revealed high precision (1.8-2.4% in C.V.) and high reproducibility (5.0-6.9% in C.V.). It was found that this RIA kit can be used for measuring low level of serum TOB concentrations by a modification of the method. The total range of measurable blood level is from 0.1 to 16.0 micrograms/ml. The nearly one to one correspondence was observed between RIA and other 4 methods, when 154 samples obtained from 18 cases were measured. A representative case of TDM for TOB was demonstrated, in which predicted concentrations agreed fairly well with actual measured values at steady state. It was concluded that the RIA kit is useful for clinical application of TDM for the adequate dosage regimen of TOB. Modification of the method for rapid assay of a small number of samples will increase the clinical usefulness.     

Simple and rapid spectrophotometric determination of iron after preconcentration as its 1,10-phenanthroline complex on the natural polymer "chitin"

Preconcentration by collection of metal complexes on chitin has been applied to the spectrophotometric determination of iron in water. The iron is collected as its 1,10-phenanthroline (phen) complex on a column of chitin in the presence of tetraphenylborate as counter-ion. The iron(II)-phen complex retained on the chitin is eluted with an acetone-1M acetic acid mixture (8:2 v/v), and the absorbance of the eluate is measured at 512 nm. Beer's law is obeyed over the concentration range 1.1-11.2 mug of iron in 10 ml of eluate. In the presence of EDTA as masking agent, Ca, Mg, Al, Mn, Zn, Cd and Pb do not interfere in concentrations up to 100 times that of iron(II) and Co, Ni and Cu do not interfere in concentrations up to 20 times that of iron(II). Common inorganic anions do not interfere in concentrations up to 10,000 times that of iron(II). The proposed method has been applied to determination of iron in tap water.     

External validation of the biodegradability prediction model CATABOL using data sets of existing and new chemicals under the Japanese Chemical Substances Control Law

External validation of the biodegradability prediction model CATABOL was conducted using test data of 338 existing chemicals and 1123 new chemicals under the Japanese Chemical Substances Control Law. CATABOL predicts that 1089 chemicals will have a BOD < 60% while 925 (85%) actually have an observed BOD<60%. The percentage of chemicals with an observed BOD value <60% tends to increase as the predicted BOD values decrease. In contrast, 340 chemicals were predicted to have a BOD > or = 60% and 234 (69%) actually had an observed BOD > or = 60%. The prediction of poor biodegradability was more accurate than the predictions of high biodegradability. The features of chemical structures affecting CATABOL predictability were also investigated.     

Constituents of holothuroidea.9. Isolation and structure of a new ganglioside molecular species from the sea cucumber Holothuria pervicax

A new ganglioside molecular species, HPG-7 (1) was obtained from the polar fraction of the chloroform/methanol extract of the sea cucumber, Holothuria pervicax. On the basis of chemical and spectroscopic evidence, the structure of 1 was determined, and the major component was 1-O-[alpha-L-fucopyranosyl-(1-->4)-(N-acetyl-alpha-D-neuraminosyl) - (2-->11)-(N-glycolyl-alpha-D-neuraminosyl)-(2-->4)-(N-acetyl -alpha-D- neuraminosyl)-(2-->6)-beta-D-glucopyranosyl]-(2S,3S,4R)-2-[(2R)-2- hydroxytetracosanoylamino]-14-methyl-hexadecane-1,3,4-triol. This is the first report on the isolation and structure elucidation of trisialo-ganglioside from sea cucumber. 1 showed neuritogenic activity toward the rat pheochromocytoma cell line, PC-12 cell.