Differential pulse voltammetric determination of P(V) following adsorptive accumulation of alpha-[PMo(12)O(40)](3-) on a polypyrrole-modified glassy carbon electrode

On the basis of the formation and pre-concentration of an α-Keggin-type [PMo₁₂O₄₀]³⁻ complex, a novel voltammetric method was developed for the determination of trace levels of P(V). The α-[PMo₁₂O₄₀]³⁻ complex was formed by heating a 5×10⁻⁴ M Mo(VI)-0.2 M HCl-40% (v/v) CH₃CN system containing a trace amount of P(V) at 70 °C for 30 min. During the electrochemical polymerization of pyrrole in the α-[PMo₁₂O₄₀]³⁻ solution, the α-[PMo₁₂O₄₀]³⁻ complex was accumulated into the polypyrrole film on a glassy carbon electrode. The differential pulse voltammetric peak current due to the α-[PMo₁₂O₄₀]³⁻ complex incorporated in the polypyrrole film was linearly dependent on the P(V) concentration in the range of 5×10⁻⁹-5×10⁻⁷ M; a detection limit of 2×10⁻⁹ M was achieved.     

Preparation of light-stable micelles with azo dyes from a nonamphiphilic random block copolymer

Light-stable micelles with azo dyes were prepared by micelle formation of a nonamphiphilic diblock copolymer containing azobenzene and UV absorbent at ca. 1 mol% as the unit ratios. The nonamphiphilic block copolymer consists of two different kinds of random copolymer blocks: poly[4-(phenylazophenoxymethyl)styrene-co-vinylphenol] (P(AS-co-VPh)) and poly[4-(2-hydroxybenzophenoxymethyl)styrene-co-styrene] (P(HBS-co-St)). This random block copolymer, P(AS-co-VPh)-b-P(HBS-co-St) formed the micelles in the presence of 1,4-butanediamine (BDA) through hydrogen bond cross-linking between the VPh units via BDA. The micelles had the azobenzene moieties at the cores and the UV absorbents at the coronas. The micelles showed a small color difference in color fading experiments, in comparison with the unimers and with micelles having no UV absorbent at the coronas. It is significant that the diblock copolymer forms the micelles and has the UV absorbents at the coronas to suppress the color fading. Furthermore, the chain length of ,-diamines had no effect on the hydrodynamic radius of the micelles, but affected the aggregation number and the cmc.     

A New Synthesis of 3-Deoxy-D-Manno-Octulosonic Acid (KDO) From D-Mannose Via Condensation of Dioxene

Abstract

The title compound has long been known as an essential component of lipopolysaccharides (LPS) and capsular polysaccharides which exist in the outer membrane of Gram-negative bacteria. KDO has attracted additional attention as a consequence of some remarkable discoveries; i) mutants unable to produce KDO are non-viable.¹ ii) KDO is not present in mammalian cells,² iii) the 2-deoxy analog of β-KDO represents a new class of synthetic antimicrobial agent.^3,4 Although syntheses of KDO have been reported by many groups,^5–8 a more efficient synthetic method endowed with the potential for synthesis of not only complex glycoconjugates but also biologically significant analogs is required.     

Permselective monolayer membrane based on two-dimensional cross-linked polysiloxane LB films for hydrogen peroxide detecting glucose sensors

Novel two-dimensional (2D) cross-linked polysiloxane LB films were prepared and applied for glucose sensing as H2O2-permselective films in order to block other electroactive interferences, such as L-ascorbic acid, L-cysteine, uric acid and acetaminophen; the 2D cross-linked polysiloxane monolayers were remarkably effective in eliminating interfering responses and had a rapid response for glucose, even though the films were only a monolayer thick.     

Direct detection of formate ligation in cytochrome c oxidase by ATR-FTIR spectroscopy

The IR signature of binding of formate to the heme a(3-)Cu(B) binuclear site of bovine cytochrome c oxidase has been obtained by perfusion ATR-FTIR spectroscopy. The data show unequivocally that formate binds in its anionic form despite its binding being electroneutral overall. The bound formate can be distinguished from free ligand by the binding-induced sharpening and downshifting of vibrational bands. Formate ligation also causes shifts of vibrational modes of heme a(3) and its substituents and perturbation of histidine residues. The association of the accompanying protonation change with a carboxylate or tyrosine can be ruled out and may involve a histidine metal ligand or, more likely, a simple displacement into the bulk phase of a hydroxide ligand to heme a(3) or CU(B), a reaction which would account for stoichiometric proton uptake and maintenance of net charge within the binuclear center domain.     

Reliability tests for Weibull distribution with variational shape parameter based on sudden death lifetime data

In the traditional design of reliability tests for assuring the mean time to failure (MTTF) in Weibull distribution with shape and scale parameters, it has been assumed that the shape parameter in the acceptable and rejectable populations is the same fixed number. For the purpose of expanding applicability of the reliability testing, Hisada and Arizono have developed a reliability sampling scheme for assuring MTTF in the Weibull distribution under the conditions that shape parameters in the both populations do not necessarily coincide, and are specified as interval values, respectively. Then, their reliability test is designed using the complete lifetime data. In general, the reliability testing based on the complete lifetime data requires the long testing time. As a consequence, the testing cost becomes sometimes expensive. In this paper, for the purpose of an economical plan of the reliability test, we consider the sudden death procedure for assuring MTTF in Weibull distribution with variational shape parameter.     

Relation between drug-induced taste disorder and chelating behavior with zinc ion; statistical approach to the drug-induced taste disorder, part II

There are many reports that the drug-induced taste disorder is ascribable to the chelate reaction of a drug with zinc ion and the following zinc deficiency. As a quantitative measure of the chelating ability of drugs with zinc ions, the chelating ability was estimated from the electrode potential change of the Zn2+/Zn(Hg) system during the addition of a drug. The electrode potential was measured in a water-N,N-dimethylformamide mixed solution and in an aqueous solution depending on the solubility of the drugs. The observed electrode potential change showed a positive correlation to the frequency of the drug-induced taste disorder that was supplied from the manufacturer of the original drug. The regression analysis was carried out assuming that the frequency of the taste disorder and the electrode potential change was linear. The F-values, p-values, and R2-values were 4.29, 0.13, 0.589, and 4.15, 0.13, 0.580, respectively. The positive correlation between the drug-induced taste disorder and the electrode potential change appeared evident if the uncertainty in the frequency of the taste disorder was taken into consideration. Thus the assumption of the zinc ion chelating mechanism on the drug-induced disorder was also evident except for cisplatin. The frequency of the drug-induced taste disorder of bezafibrate was estimated to be 0.4--0.5 from the regression analysis.     

Metabolomic investigation of cholestasis in a rat model using ultra-performance liquid chromatography/tandem mass spectrometry

Metabolomics follows the changes in concentrations of endogenous metabolites, which may reflect various disease states as well as systemic responses to environmental, therapeutic, or genetic interventions. In this study, we applied metabolomic approaches to monitor dynamic changes in plasma and urine metabolites, and compared these metabolite profiles in Eisai hyperbilirubinemic rats (EHBR, an animal model of cholestasis) with those in the parent strain of EHBR - Sprague-Dawley (SD) rats - in order to characterize cholestasis pathophysiologically. Ultra-performance liquid chromatography/tandem mass spectrometry-based analytical methods were used to assay metabolite levels. More than 250 metabolites were detected in both plasma and urine, and metabolite profiles of EHBR differed from those of SD rats. The levels of antioxidative and cytoprotective metabolites, taurine and hypotaurine, were markedly increased in urine of EHBR. The levels of many bile acids were also elevated in plasma and urine of EHBR, but the extent of elevation depended on the particular bile acid. The levels of cytoprotective ursodeoxycholic acid and its conjugates were markedly elevated, while that of cytotoxic chenodeoxycholic acid remained unchanged, suggesting the balance of bile acids had shifted resulting in decreased toxicity. In EHBR, reduced biliary excretion leads to increased systemic exposure to harmful compounds including some endogenous metabolites. Our metabolomic data suggest that mechanisms exist in EHBR that compensate for cholestasis-related damage.     

Lithium chloride: an active and simple catalyst for cyanosilylation of aldehydes and ketones

LiCl acts as a highly effective catalyst for cyanosilylation of various aldehydes and ketones to the corresponding silylated cyanohydrins. The reaction proceeds smoothly with a substrate/catalyst molar ratio of 100-100,000 at 20-25 degrees C under solvent-free conditions. alpha,beta-Unsaturated aldehydes are completely converted to the 1,2-adducts. The cyanation products can be isolated by direct distillation of the reaction mixture.     

Selective removal of DNA from protein solution with copolymer particles derived from N,N-dimethylaminopropylacrylamide

To remove nucleic acids from cellular products as drugs, cross-linked N,N-dimethylaminopropylacrylamide (DMP) particles with cationic functional groups were prepared. The particle's hydrophobicity and its anion-exchange capacity were easily adjusted by changing the cross-linking agent and the DMP ratio in the cross-linking, respectively. When divinylbenzene (DVB) was used as a cross-linking agent and the DMP ratio (in the cross-linking) was adjusted to 90 mol%, the particles (DMP-DVB, 90:10) showed the highest adsorbing activity of DNA (salmon spermary). Its adsorption capacity was 54 mg/ml adsorbent. On the other hand, the adsorption of bovine serum albumin (BSA) to the DMP-DVB extremely increased with increase in the adsorbent's pore size (molecular mass exclusions; M(lim)) from 2 x 10(3) to 1 x 10(4), but decreased with increase in the buffer's ionic strength (mu) to 0.2 or stronger. As a result, when the DMP-DVB (80:20) with M(lim) 2 x 10(3) was used as adsorbent by a column method at pH, 7.2 and mu = 0.17, it only selectively removed DNA from a BSA solution, including 1000 microg/ml of BSA and 10 microg/ml of DNA. The adsorbent decreased the concentration of DNA in the BSA solution to < 10 ng/ml, and the recovery rate of BSA was more 98%.