Determination of TNT and its metabolites in water samples by voltammetric techniques

Square-wave voltammetry with the hanging drop mercury electrode as the working electrode was used for the determination of ultratraces of explosives in aqueous solution. It was shown that the strong pressure dependence of the pneumatically controlled multimode electrode system of a conventional Metrohm apparatus could be compensated by an additional pressure regulation, through which the pressure variations could be decreased when switching from deaeration to the static measurements. By using square-wave voltammetry with this electrode system after this modification the limits of detection for 2,4,6-trinitrotoluene (TNT) and other TNT-metabolites could be decreased down to 0.2 μg L⁻¹ when using a measurement time of 6 min. Also a simultaneous determination of TNT and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) was shown to be possible over a wide linear range and the detection limits then were 2.2 μg L⁻¹ for TNT and 25 μg L⁻¹ for RDX. By applying the highly stable and adjustable pressure as mentioned before, the calibrations could be kept stable over a period of up to 1 week.     

Acid catalyzed hydrolysis of brotizolam,a thienotriazolodiazepine: Spectroscopic study

The acid catalyzed hydrolysis of the thienotriazolodiazepine, Brotizolam, 2-bromo-4-(2-chlorophenyl)-9-methyl-6H-thieno[3,2-f][1,2,4]triazolo[4,3-a][1,4]diazepine ( 1 ), has been studied spectrometrically (ir, pmr, cmr, and ms). The cleavage reaction of the azomethine bond is reversible and the open-ring compound is in equilibrium with the ring closed compound (protonated form of the parent drug).     

Spectrophotometric study of bismuth with N-(2-acetamido)iminodiacetic acid (ADA): Determination of bismuth in pharmaceutical formulations

A new method for the Spectrophotometric determination of bismuth using N-(2-acetamido)iminodiacetic acid as complexometric agent is proposed. The complex is formed in a wide pH range, 5.5–7.5, and has a maximum absorption at 265 nm. Beer's law is obeyed in the interval 3.8–17.9 μg of bismuth(III)/ml, with a minimum photometric error of 2.3. The molar absorptivity is 9.1 × 10³ liters/cm mol. The stoichiometry of the reaction takes place in the metal-to-ligand ratio 1:2. The interferences produced by the more common ions are studied. The method has been successfully applied to the determination of bismuth in pharmaceutical formulations.     

Laser-Induced Fluorescence (LIF) Probe for <Emphasis Type="Italic">In-situ</Emphasis> Nitric Oxide Concentration Measurement in a Non-thermal Pulsed Corona Discharge Plasma Reactor

Laser-induced fluorescence (LIF) is an effective in-situ probe for NO concentrations below 300 ppm in a non-thermal plasma reactor. A new method has been developed to measure in-situ NO concentration in the reactor discharge region using a long-time—on the order of seconds—averaged fluorescence detection. This method, for quantifying NO concentration in a nonthermal plasma reactor, is simpler than a short-time—on the order of nanoseconds—fluorescence detection. For accurate measurement based on the new method, the LIF intensity must be close to the corona-induced fluorescence (CIF) intensity; the CIF intensity serves as a guide in selecting the LIF intensity. We find that a kinetic model proposed earlier works for two-tube reactors and represents the NO concentration in the middle of the reactor, which verifies the assumption of gas plug flow.     

Development and validation of a capillary electrophoresis method for the determination of phenothiazines in human urine in the low nanogram per milliliter concentration range using field-amplified sample injection

A capillary zone electrophoresis (CZE) method with ultraviolet-visible detection has been established and validated for the determination of five phenothiazines: thiazinamium methylsulfate, promazine hydrochloride, chlorpromazine hydrochloride, thioridazine hydrochloride, and promethazine hydrochloride in human urine. Optimum separation was obtained on a 64.5 cm x 75 microm bubble cell capillary using a buffer containing 150 mM tris(hydroxymethyl)aminomethane and 25% acetonitrile at pH 8.2, with temperature and voltage of 25 degrees C and 20 kV, respectively. Naphazoline hydrochloride was used as an internal standard. Field-amplified sample injection (FASI) has been applied to improve the sensitivity of the detection. Considering the influence of parameters affecting the on-line preconcentration (nature of preinjection plug, sample solvent composition, injection times, and injection voltage) and due to the significant interactions among them, in this paper we propose for the first time the application of a multivariate approach to carry out the study. The optimized conditions were as follows: preinjection plug of water for 7 s at 50 mbar, electrokinetic injection for 40 s at 6.2 kV, and 32 microm of H3PO4 in the sample solvent. Also, a solid-phase extraction (SPE) procedure is developed to obtain low detection limits and an adequate selectivity for urine samples. The combination of SPE and FASI-CZE-UV allows adequate linearities and recoveries, low detection limits (from 2 to 5 ng/mL), and satisfactory precisions (3.0-7.2% for an intermediate RSD %).     

In Situ Amperometric Detection of Vesicles and Microgel Phases in an Aggregating System: Calcium Alginate

In situ amperometric characterization of an aggregating system in terms of molecular adsorption and single microparticle interactions at the electrode interface is demonstrated using a model system: alginate/Ca(II) in an aqueous electrolyte solution. Recording of chronoamperometric curves of oxygen reduction at the dropping mercury electrode is designed for detection of dip‐shaped signals of individual gel microparticles. By addition of Ca(II) decrease of alginate adsorption is accompanied by appearance of signals indicating vesicle type association of alginate molecules and microparticles of gel phase. AFM imaging provided evidence of initial stage in calcium alginate gel formation.     

Cadmium speciation in Arabidopsis thaliana as a strategy to study metal accumulation system in plants

The strategy to identify cadmium deactivation mechanism in Arabidopsis thaliana has been developed using selective and sensitive hyphenated techniques. Cadmium concentrations, in main parts of the plant, were determined by ICP-MS and total amount was found as 0.43-0.44 μg g⁻¹ in leaves and 3.3-3.4 μg g⁻¹ in roots. Speciation of the metal complexes in cells was investigated by SEC-ICP-MS in order to estimate the accumulation process. Phytochelatins, desglycyl-phytochelatins and phytochelatins homologues lacking the N-terminal γ-linked glutamic acid were extracted from plant and were identified by RPLC-ESI-MS. Two-dimensional chromatography allowed to link the metal complexes separated by SEC with isoforms of phytochelatins analyzed by high resolution RPLC and confirm their significant responsibility for metal accumulation. The potential of the cadmium complexes speciation indicates that obtained results could be reliable source of knowledge to confirm the information coming from the well-known genomic sequence of Arabidopsis and to estimate the role of γ-glutamyl transpeptidase in metabolism of glutathione.     

Biosensors for environmental pollutants and food contaminants

This review article provides an overview of the most recent literature on biosensors for environmental pollutants and food contaminants. Due to the large number of publications, only papers published between 2000 and January 2003 were considered. Also, while not all of the published literature could be reviewed here, over 200 references are cited to provide a good overview of research undertaken in the last two years. Older publications are covered by a number of earlier review articles. This article provides an introduction into the field including specific consideration of the application areas, describes the typical biosensor assay format used, and is subsequently structured according to the biorecognition elements used (i.e., nucleic acids, enzymes, whole cells, tissue and whole organisms, antibodies and receptors, and biomimetic materials). In addition, a section on microbiosensing systems is provided. Since only very few microbiosensors with applications in environmental and food systems have been published, enabling technology is also covered in this article.Abbreviations BOD biological oxygen demand - cfu colony forming units - DNP dinitrophenol - GFP green fluorescent protein - NASBA nucleic acid sequence-based amplification - PCR polymerase chain reaction - ppt parts per trillion - QCM quartz crystal microbalance - SPR surface plasmon resonance     

原子氧在Ru低指数面及(110),(111)台阶面上的吸附

利用原子与表面簇合物相互作用的5参数Morse势方法(简称5-MP)系统地研究了O-Ru低指数面及Ru(1120),(1121)台阶面体系,获得了吸附几何、结合能、振动频率等临界点特性,所得相关数据与实验结果非常吻合.并且通过理论计算及原子吸附态振动指纹的遗传、遗变特性预言了氧原子在Ru(1121)台阶面的吸附.本文认为氧原子在HCP晶格的金属表面上的吸附倾向于三重位.     

超声波辐射下金属锰引发芳香醛的偶联反应

超声波引发下Mn-H2O-HOAc体系中进行的一系列芳香醛的偶联反应,室温反应3 h得到45%～71%的邻二醇产品.