Speciation analysis of aluminium(III) in natural waters and biological fluids by complexing with various catechols followed by differential pulse voltammetry detection

The biological effects of aluminium have received much attention in recent years. Speciation of Al is of basic relevance as it concerns its reactivity and bioavailability. A differential pulse voltammetry (DPV) procedure is proposed for speciation analysis of Al(III) in natural waters and biological fluids using six catechols (L-dopa, dopamine, epinephrine, norepinephrine, caffeic acid and o-benzenediol) as electroactive ligands. The decrease of the DPV anodic peak current for each catechol ligand is linear with the increase of Al concentration. This speciation analysis idea is based on the measurement of the complexation capacity, namely, different affinities of Al(III) for catechols and organic ligands under two pH conditions. The labile monomeric Al fraction (mainly inorganic aluminium) is determined at pH 4.6, while the total monomeric Al fraction is determined at pH 8.5. The principle for Al(III) speciation analysis by an electrochemical method is discussed. This sensitive and simple fractionation method is successfully applied to the speciation analysis of Al in natural waters and the results agree well with those of Driscoll's method. The speciation analysis of Al in biological fluids is also explored and the results are compared with those obtained by ultrafiltration and dialysis. Compared with other speciation protocols the electrochemical method possesses some remarkable advantages: rapidity, high sensitivity, cheap instrumentation and a simple operation procedure.     

Anodic stripping voltammetric determination of bismuth(III) using a Tosflex-coated mercury film electrode

A Tosflex-mercury film electrode (TMFE) was prepared by spin-coating a solution of the perfluorinated anion exchange polymer Tosflex onto a glassy carbon electrode surface followed by electrodeposition of mercury film on this electrode. This electrode was used for the determination of trace bismuth(III) which was preconcentrated onto the TMFE as anionic bismuth(III) complexes with chloride in a chloride medium. The preconcentration was carried out at a potential of-0.2 V, and the preconcentration of the bismuth(III) was enhanced significantly by the anion-exchange feature of Tosflex. The accumulated bismuth(III) was then determined by anodic square-wave stripping voltammetry (SWSV). Various parameters influencing the determination of bismuth(III) were examined in detail. With 2 min accumulation, the analytical signal versus concentration dependence was linear up to 50 ppb, and the detection limit was 0.58 ppb. This modified electrode showed good resistance to the interferences from surface-active compounds and common ions.     

Applications of benzotriazole methodology in heterocycle ring synthesis and substituent introduction and modification

Applications of benzotriazole methodology for the preparation of heterocyclic compounds are reviewed. The characteristic advantages of benzotriazole as a synthetic auxiliary are first briefly considered. This is followed by a summary of its use in ring synthesis in which the construction of small; five-membered; six-membered; and larger heterocyclic rings using benzotriazole methodology are each examined separately. Finally, consideration of the use of benzotriazole in the ring annulation - particularly benzannulation - of heterocycles. Subsequent sections deal with the introduction of substituents into aromatic heterocycles; the ring substitution of saturated heterocycles; and benzotriazole assisted modification of heterocyclic substituents. The present review supplements a recent comprehensive review of benzotriazole chemistry [1] which covers the literature through 1996.     

锑化镓的光助微刻蚀及其表面氧化物的研究

用电化学和光电化学方法研究锑化镓表面的腐蚀以及锑化镓表面氧化膜的生成和溶解，锑化镓电极在一定电势下生成的氧化膜，用俄歇能谱证明，其主要成分为难溶的氧化锑，此氧化膜的存在抑制了锑化镓的进一步腐蚀，同时亦使锑化镓的半导体光电化学性能大为减弱，通过激光微刻蚀及电子显微镜的观察，在刻蚀剂中添加酒石酸，柠檬酸和氢氟酸等试剂，可使刻蚀形得改善，实验研究了锑化镓的平带电势的测定。     

Die Reaktion von Ce(III), Th(IV) und U(VI) mit Chinizaringrün und seinem nichtsulfonierten Grundkörper

The reaction of 1,4-(2-sulpho-4-methylanilino)anthraquinone (quinizarin green,QG) and its non-sulphonated derivative (NSQG) with Ce(III), Th(IV), and U(VI) was investigated. Spectrophotometric and conductometric studies were carried out to investigate the stoichiometry of the complexes formed. The studies revealed the formation of 11 and 12 (ML) complexes. The apparent stability constants of the different complexes were determined. The structure of the ligand in the solid chelates was studied by IR spectrophotometry which showed that the chelate formation takes place through the oxygen of the C=O group and the -imino nitrogen.

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Structure and properties of a novel 3D straight-channel polyoxovanadate and an unexpected trimeric barbiturate obtained by hydrothermal reactions

The hydrothermal reaction of NaVO(3).H(2)O, barbituric acid, NH(2)NH(2).2HCl, H(3)PO(4), and H(2)O gave a novel heteropolyoxovanadate Na(6)[(P(V)O(4))V(V)(6)V(IV)(12)O(39)](2).H(3)PO(4).31H(2)O (1) and an unexpected phase Na(2)[C(12)H(6)N(6)O(9)].7H(2)O (2). The basic building blocks in 1 are the six-capped sphere-shaped heteropoly anion [(P(V)O(4))V(V)(6)V(IV)(12)O(39)](3-) with framework similar to that of the reported polyoxovanadates possessing [V(18)O(42)] clusters encapsulating VO(4) or other ions. These heterpoly anionic units are linked via V[bond]O[bond]V bridges into an interesting 3D straight-channel structure. The structure of 2 consists of novel organic anions ([C(12)H(6)N(6)O(9)](2-), 5,5-bis(2',4',6'-trioxopyrimidyl)barbital, representing the first oxidized barbituric acid trimer) linked via sodium ions into 1D hollow tubes with diameter of 4.49 x 6.86 A and further connected into a three-dimensional framework via hydrogen bonds.     

Capillary electrophoresis with amperometric detection of curcumin in Chinese herbal medicine pretreated by solid-phase extraction

In the present study, curcumin from Chinese herbal medicine turmeric was determined by capillary electrophoresis with amperometric detection (CE-AD) pretreated by a self-designed, simple, inexpensive solid-phase extraction (SPE) cartridge based on the material of tributyl phosphate resin. An average concentration factor of 9 with the recovery of > 80% was achieved when applied to the analysis of curcumin in extracts of tumeric. Under the optimized CE-AD conditions: a running buffer composed of 15 mM phosphate buffer at a pH 9.7, separation voltage at 16 kV, injection for 6 s at 9 kV and detection at 1.20 V, CE-AD with SPE exhibited low detection limit as 3 x 10(-8) mol/l (S/N = 3), high efficiency of 1.0 x 10(5) N, linear range of 7 x 10(-4) -3 x 10(-6) mol/l (r = 0.9986) for curcumin extracted from light petroleum. The method developed resulted in enhancement of the detection sensitivity and reduction of interference from sample matrix in complicated samples and exhibited the potential application for routine analysis, especially in food, because a relatively complete process of sample treatment and analysis was described.     

Luminescent organoboron quinolate polymers

The synthesis of well-defined luminescent organoboron polymers via a novel three-step procedure starting from silylated polystyrene is reported. Highly selective borylation of poly(4-trimethylsilylstyrene) (PS-Si), followed by replacement of the bromine substituents in poly(4-dibromoborylstyrene) (PS-BBr) with substituted thienyl groups (R = H, 3-hexyl, 5-hexyl), and final introduction of the 8-hydroxyquinolato moiety yields a series of new organoboron quinolate polymers in 67-83% isolated yield. The hexyl-substituted polymers are highly soluble and solution-processable yielding thin films that efficiently emit light at 513-514 nm upon excitation at 395 nm.     

Theoretical analysis and computer simulation of fluorescence lifetime measurements. I. Kinetic regimes and experimental time scales

The configuration-controlled regime and the diffusion-controlled regime of conformation-modulated fluorescence emission are systematically studied for Markovian and non-Markovian dynamics of the reaction coordinate. A path integral simulation is used to model fluorescence quenching processes on a semiflexible chain. First-order inhomogeneous cumulant expansion in the configuration-controlled regime defines a lower bound for the survival probability, while the Wilemski-Fixman approximation in the diffusion-controlled regime defines an upper bound. Inclusion of the experimental time window of the fluorescence measurement adds another dimension to the two kinetic regimes and provides a unified perspective for theoretical analysis and experimental investigation. We derive a rigorous generalization of the Wilemski-Fixman approximation [G. Wilemski and M. Fixman, J. Chem. Phys. 60, 866 (1974)] and recover the 1/D expansion of the average lifetime derived by Weiss [G. H. Weiss, J. Chem. Phys. 80, 2880 (1984)].     

A Novel Environmentally Benign Method for the Selective Oxidation of Alcohols to Aldehydes and Ketones

In the presence of [Ru(terpyridine)(2,6‐pyridinedicarboxylate)], aliphatic and benzylic alcohols are oxidized to the corresponding aldehydes or ketones with high selectivity by using hydrogen peroxide as the oxidant. There is no need for the addition of co‐catalysts or organic solvents. By applying an optimized reaction protocol, high catalyst productivity (turnover number>10 000) and activity (turnover frequency up to 14 800 h^?1) has been achieved.