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.     

Direct determination of benzamides in serum by column-switching high-performance liquid chromatography.

A column-switching high-performance liquid chromatographic method with fluorescence detection was developed for the simultaneous determination of four benzamide-type anti-psychotic drugs: sulpiride, tiapride, sultopride and metoclopramide in human serum. In this method, a TSKgel Super-ODS column was used as an analytical column, and a TSKgel G 2000SW was prepared as a pretreatment column. Under the optimized analytical conditions, four benzamide-type anti-psychotic drugs were eluted within 18 min. The detection limits (S/N = 3) for sulpiride, tiapride, sultopride and metoclopramide are 1 ng/ml, 4 ng/ml, 2 ng/ml and 0.5 ng/ml, respectively. Finally, the method was applied to the determination of sulpiride in human serum samples obtained after a single oral dose of sulpiride.     

Simple and rapid determination of trace amounts of gold(III), palladium(II), and platinum(IV) in industrial waste solutions after recovery of noble metals by combined use of GFAAS and anion-exchange separation.

A simple and rapid method for the analysis of trace amounts of gold(III), palladium(II), and platinum(IV) by the combined use of graphite furnace atomic absorption spectrometry and anion-exchange separation was proposed, and successfully applied to the rapid determination of metals in industrial waste solutions obtained from the final process of noble-metal recovery factories, because noble metals can be selectively and quantitatively separated to a high degree by using a small column containing only a 0.7 g-portion of a common anion-exchange resin and a dilute thiourea solution.     

Solid-State polymerization of the binary mixture of methacrylate and liquid-crystalline compound by electron beam

Solid-state polymerization of a binary mixture of nonliquid-crystalline monomer and liquidcrystalline compound was carried out using electron beam. The monomers were benzoic acid containing 4-[ω-(meth)acryloyloxyalkyloxy] benzoic acids, in which the alkylene spacer was ethylene, hexamethylene, or undecamethylene. The conversion yield of monomer to polymer to a large extent increased with increasing content of a liquid-crystalline compound with a terminal carboxylic group, such as 4-n-alkyloxybenzoic acid, while the addition of a liquid-crystalline compound without terminal carboxylic group did not affect polymerization of the monomer. Phase diagrams of the mixture of monomer and liquid-crystalline compound were examined using cross-polarizing microscopy and differential scanning calorimetry (DSC). All mixtures of monomer and 4-n-alkyloxybenzoic acid or liquid-crystalline compound without terminal carboxylic group showed liquid-crystallinity in a broad composition range. It was concluded that liquid-crystalline compounds with terminal carboxylic acid may form hydrogen bondings with methacrylate or acrylate monomer having terminal carboxylic acid which enhance polymerizability of the mixture. The stereoregularity of polymers determined by NMR depended on increasing irradiation dose and temperature rather than the content of the added liquid-crystalline 4-n-decanoxybenzoic acid.     

Novel quinazoline ring synthesis by cycloaddition of N-arylketenimines with N,N-disubstituted cyanamides

The reaction of N-aryl-substituted ketenimines with N,N-disubstituted cyanamides or (MeS)2C=N-CN under high pressure afforded 4-(N,N-disubstituted amino) or 4-(MeS)2C=N-substituted quinazoline derivatives, respectively. These products were formed by [4+2] cycloaddition between the aza-diene moieties of the N-arylsubstituted ketenimines and cyano groups. A 4-(unsubstituted amino)quinazoline derivative was synthesized by hydrolysis of the latter product.     

Control of viscoelasticity using redox reaction

The viscoelasticity of a fluid was tuned with the Faradaic reaction of (11-ferrocenylundecyl)trimethylammonium bromide (FTMA), a "redox-switchable" surfactant. An aqueous solution of the reduced form of FTMA exhibited a remarkable viscoelasticity in the presence of sodium salicylate (NaSal) because of the formation of three-dimensional entanglement of wormlike micelles. Electrolytic oxidation of FTMA caused the viscosity of the system to dramatically decrease and the elasticity to disappear. This drastic decrease in viscoelasticity arose from the disruption of wormlike micelles. This novel electrorheological phenomenon is expected to be applicable to ink for inkjet printers, the electrochemically controlled release of substances entrapped in wormlike micelles of FTMA, and fluid flow rate control using electric signals.     

Electrochemical control of CO/NO ligand exchange in a triruthenium cluster monolayer assembled on a gold electrode surface

A highly selective ligand exchange reaction is realized in the self-assembled monolayer (SAM) of a triruthenium cluster on a gold electrode surface under precise electrochemical potential control. CO as well as NO molecules, which are known to play key roles in many chemical, biological, and environmental systems, can be efficiently introduced into the SAM by electrochemically tuning the electronic state of the Ru site. These unique surface reactions are more convenient and efficient than conventional ligand exchange reactions in solution and could be used for the elucidation of the electron-transfer mechanism in a biological system as well as in the development of molecular sensors and devices.     

Hydroxylation of ionized aromatics including carboxylic acid or amine using recombinant Streptomyces lividans cells expressing modified biphenyl dioxygenase genes

The bphA1(2072)A2A3A4 gene cluster codes for a shuffled biphenyl dioxygenase holoenzyme with broad substrate specificity. These bphA1(2072)A2A3A4 genes were expressed in the actinomycetes Streptomyces lividans using a thiostrepton-inducible promoter P_tipA. Biotransformation experiments of various aromatics including carboxylic acid or amine in their molecular structure, such as 1-naphthoic acid, 2-(1-naphthyl)acetic acid, diphenylamine, and 1-benzyl-4-piperidone, were performed using the recombinant S. lividans cells. These ionized aromatics were converted to the corresponding 1,2-dihydrodiol, mono- or tri-hydroxy forms in 48 h. The structure of the converted products was determined by their EI-MS, ¹H- and ¹³C NMR analysis, and several products were found to be novel compounds.     

Synthesis, properties, and crystal structure of a novel anthracene-bridged molybdenum-zinc porphyrin dimer

The synthesis and properties of novel anthracene-bridged porphyrin dimers having an oxomolybdenum(V) porphyrin unit, H(2)(DPA)[Mo(V)O(OMe)] (1) and (DPA)[Mo(V)O(OMe)][Zn(II)(MeOH)] (2), and the relevant monomer porphyrin complexes Mo(V)O(MPP)OMe (3) and Zn(II)(MPP) (4) are presented. An oxomolybdenum(V) unit was introduced into one of the two porphyrins in DPA to give 1, which has a free-base porphyrin unit. By introducing a zinc(II) ion to the free-base part, a mixed-metal complex of 2 was prepared and isolated. The structure of 2 was analyzed by X-ray crystallography (2.(7)/(6)CH(2)Cl(2), triclinic, P(-)1 (no. 2), a = 15.2854(12) A, b = 19.9640(15) A, c = 13.6915(12) A, alpha = 90.968(3), beta = 113.108(4), gamma = 96.501(4), Z = 2, R1 = 9.9, wR2 = 19.2). The structure of 2 demonstrated that a methanol is stably coordinated to the Zn(II) ion with the aid of a hydrogen bond to the methoxo ligand on the Mo(V) ion in the binding pocket of DPA. The electrochemical measurements of 2 suggested that the methanol was kept in the pocket of DPA in solution even at the reduced state of the molybdenum ion.