Facilitated sulfate transfer across the nitrobenzene-water interface as mediated by hydrogen-bonding ionophores.

Facilitated SO4(2-) transfers by hydrogen bond-forming ionophores are investigated across the nitrobenzene (NB)-water interface by using polarography with a dropping electrolyte electrode. Bis-thiourea 1, alpha,alpha'-bis(N'-p-nitrophenylthioureylene)-m-xylene, is found to significantly facilitate the transfer of the highly hydrophilic SO4(2-) whereas its counterpart, N-(p-nitrophenyl)-N'-propylthiourea (ionophore 2), cannot. In contrast to the predominant formation of a 1:1 complex with SO4(2-) in the bulk NB phase, the SO4(2-) transfer assisted by 1 is indeed based on the formation of a 1:2 complex between SO4(2-) and ionophore, even under the condition of [SO4(2-)]aq > [1]org. Such an exclusive formation of the 1:2 (SO4(2-) to ionophore) complex at the NB-water interface is not observed with structurally similar bis-thiourea 3, alpha,alpha'-bis(N'-phenylthioureylene)-m-xylene, where p-nitrophenyl moietes of bis-thiourea 1 are simply replaced by phenyl groups. The facilitated transfer of SO4(2-) with bis-thiourea 1 is further compared to that of HPO4(2-) and H2PO4- across the NB-water interface, which was previously shown to be assisted by 1 through the formation of the 1:1 and 2:1 (anion to ionophore) complexes, respectively. On the basis of these examinations, unique binding behaviors of hydrogen bond-forming ionophores at the NB-water interface are discussed, with a view towards development of ionophore-based anion-selective chemical sensors.     

Syntheses and characterization of 16‐arm star and star diblock copolymer and AB8 9‐miktoarm star copolymer via NMRP and ROP from dendritic multifunctional macroinitiators

A dendritic macroinitiator having 16 TEMPO‐based alkoxyamines, Star‐16 , was prepared by the reaction of a dendritic macroinitiator having eight TEMPO‐based alkoxyamines, [G‐3]‐OH , with 4,4′‐bis(chlorocarbonyl)biphenyl. The nitroxide‐mediated radical polymerization (NMRP) of styrene (St) from Star‐16 gave 16‐arm star polymers with PDI of 1.19–1.47, and NMPR of 4‐vinylpyridine from the 16‐arm star polymer gave 16‐arm star diblock copolymers with PDI of 1.30–1.43. The ring‐opening polymerization of ε‐caprolactone from [G‐3]‐OH and the subsequent NMRP of St gave AB₈ 9‐miktoarm star copolymers with PDI of 1.30–1.38. The benzyl ether linkages of the 16‐arm star polymers and the AB₈ 9‐miktoarm star copolymers were cleaved by treating with Me₃SiI, and the resultant poly(St) arms were investigated by size exclusion chromatography (SEC). The SEC results showed PDIs of 1.23–1.28 and 1.18–1.22 for the star polymers and miktoarm stars copolymers, respectively, showing that they have well‐controlled poly(St) arms. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1159–1169, 2007.     

Validation of a method for predicting the precision, limit of detection and range of quantitation in competitive ELISA.

The mathematical model for predicting the precision, limit of detection (LOD) and range of quantitation (ROQ) in a competitive enzyme-linked immunosorbent assay (ELISA) proposed by Hayashi et al. (Anal. Chem., 2004, 76, 1295) was validated. The model describes the relative standard deviation (RSD) of concentration estimates by the RSDs of pipetting volumes of analyte, enzyme-conjugated antigen, antibody and substrate solutions, and the standard deviation (SD) of inherent absorbances between the wells in an ELISA plate. For 6 kinds of direct competitive ELISA kits, the LOD and ROQ predicted by the model agreed well with those obtained by experiments with real samples. It was also confirmed that the model is applicable to the prediction of uncertainty that depends on the pipetting error of the viscous antiserum solution. The model was demonstrated to be useful for estimating the LOD and ROQ of competitive ELISA.     

He I (584 Å) photoelectron spectra and photoionization cross sections of atomic chlorine and bromine

Well-resolved He I photoelectron spectra of atomic chlorine and bromine have been obtained without serious background electrons, giving rise to relative photoelectron intensities associated with differential photoionization cross sections at an angle of 90° with respect to the incident 584 Å radiation.     

Anti-inflammatory activity of new guaiane type sesquiterpene from Wikstroemia indica

In our investigation of in vitro anti-allergic screening of medicinal herbal extracts, the ethyl acetate extract of the root of Wikstroemia indica was observed to inhibit nitric oxide (NO) production in a lipopolysaccharide (LPS) and recombinant mouse interferon-gamma (IFN-gamma) activated murine macrophage-like cell line, RAW 264.7. Fractionation of the active extract led to the isolation of one new guaiane type sesquiterpene, indicanone (1), and two known biflavonoids, sikokianin B (2) and sikokianin C (3). 1 inhibited NO production with IC50 values at 9.3 microM and also inhibit the inducible nitric oxide synhase (iNOS) gene expression. This is the first report of NO production inhibitory activity of Wikstroemia indica and supports the pharmacological use of it, which has been employed as an herbal medicine for the treatment of inflammation.     

The electrochemical behavior of Os(II) complexes with α,α′-bipyridine and o-phenanthroline in non-aqueous solvents

The electrode reactions of Os(II) complexes with α,α′-bipyridine and o-phenanthroline have been studied in non aqueous solvents. Tris bipyridine and tris phenanthroline complexes of Os(II) give one-step oxidation waves and three-step reduction waves, while bis bipyridine complexes of Os(II) containing py₂, en, CN₂, Cl₂ and Br₂ as mixed ligands give one-step oxidation waves and two-step reduction waves. Most of these waves correspond to reversible single electron transfers. It is noticed that the half-wave potentials or the peak potentials of bis bipyridine complexes are shifted to more negative direction than those of the tris complex in both oxidation and reduction processes. This is attributable to less electron with drawing nature of substituted ligands than bipyridine. These potential data, the shifts of E_1/2 or E_p from those of tris complexes, and δE*, the potential difference between two consecutive single electron waves, are discussed in terms of molecular orbital scheme.     

Role of the nature of copper sites in the activity of copper-based catalysts for no conversion

The activities of the copper-based catalysts, Cu²⁺ /SiO²,Cu²⁺ /Vycor and Cu²⁺/ZSM-5, and V²O⁵/TiO² for NO conversion to N² in the presence or absence of NH³ and/or O² have been investigated. The Cu²⁺ /ZSM-5 catalyst exhibited the highest activity, even higher than that of V²O⁵/TiO². Photoluminescence studies of the dehydrated copper-based catalysts have suggested that the copper ions anchored onto ZSM-5 locate as isolated copper species near Brönsted sites in the zeolite channels while the copper ions anchored onto Vycor and SiO² locate mainly as copper dimer forms. These results suggest the role of copper ions which are stabilized with near-lying oxygen vacancies created by dehydroxylation of the zeolite, in NO conversion. As a result, it may be concluded that the isolated copper ions near Brönsted sites play a significant role in NO conversion but dimeric or polynuclear copper species are less effective for the reaction.     

Application of 28Mg to the kinetic study of Mg uptake by rice plants

The time course of Mg uptake and release using intact rice plants and ²⁸Mg as a tracer is presented. Since there is no conventional Mg tracer available, ²⁸Mg was produced via ²⁷Al(α, 3p)²⁸Mg reaction using a cyclotron. Using the purified ²⁸Mg tracer, it was found that the uptake amount of ²⁸Mg by the rice plants increased linearly during 30 min of application. After ²⁸Mg treatment for 90 min, the roots were sequentially washed with iced solution for 120 min. Within about 10 min, almost all of the ²⁸Mg, that was thought to be weakly bound to the apoplast, was washed away.