Spectrofluorometric determination of certain quinolone antibacterials using metal chelation

Simple, rapid, reliable, and sensitive spectrofluorometric methods were developed for the determination of eight quinolone antibacterials namely ciprofloxacin, norfloxacin, lomefloxacin, difloxacin, amifloxacin, pefloxacin, ofloxacin, and nalidixic acid. The methods depend on the chelation of each of the studied drugs with zirconium, molybdenum, vanadium or tungsten to produce fluorescent chelates. Different factors affecting the relative fluorescence intensity of the resulting chelates were studied and optimised. At the optimum reaction conditions, the drug-metal chelates showed excitation maxima ranging from 274 to 295 nm and emission maxima ranging from 409 to 495 nm. The chelates were found to be stable at room temperature for 2 days and show good stability upon increasing temperature to 50 °C for about 1 h. Rectilinear calibration graphs were obtained in the range of 10-60 ng ml⁻¹ for each of the investigated drugs and the limits of detection and quantitation ranged from 1.214 to 2.046 and from 4.047 to 6.819 ng ml⁻¹, respectively. The molar ratios of the formed chelates were determined by Job's method and their association constants were also calculated. The developed methods were applied successfully for the determination of the studied drugs in their pharmaceutical dosage forms with a good precision and accuracy compared to official and reported methods as revealed by t- and F-tests. They were also applied for the determination of studied drugs in spiked urine and plasma samples.     

TPSR STUDIES OF THE ACTIVATION OF METHANE ON SUPPORTED PLATINUM CATALYSTS

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New approaches in radical carbonylation chemistry: fluorous applications and designed tandem processes by species-hybridization with anions and transition metal species

New approaches in radical carbonylation chemistry are described. We have successfully integrated tin mediated radical carbonylation chemistry into modern fluorous applications and separation techniques. We revealed that radical carbonylation reactions can be performed using fluorous tin mediators, such as fluorous tin hydride and fluorous allyltin reagents. Fine tuning of the reaction conditions resulted in a good efficiency equivalent to conventional tin mediators. The tedious procedure of removing organotin byproducts can be circumvented through the use of fluorous/organic liquid-liquid extraction or fluorous liquid-solid phase extraction with fluorous reverse phase silica (FRPS). Also described are newly developed tandem carbonylation reactions that are based on species hybridization approaches. Using a radical/anionic hybrid system based on zinc-induced one-electron reduction, we achieved a three-component coupling reaction consisting of 4-alkenyl iodides, carbon monoxide, and electron-deficient alkenes. We observed two types of annulations processes, namely [4 + 1](radical)/[3 + 2](anionic) and [5 + 1](radical)/[3 + 2](anionic), which lead to the production of bicyclo[3.3.0]octanols and bicyclo[3.2.1]octanols, respectively. We found a radical/palladium hybrid system to be useful in the construction of new cyclic systems that incorporate two or three molecules of carbon monoxide.     

Polymer-protected palladium nanoparticles. Morphologies and catalytic selectivities

Colloidal palladium nanocatalysts prepared by in situ reductions of palladium chloride were immobilized and protected by either of two water-soluble polymers. The particle sizes and size distributions of the palladium colloids were determined by transmission electron microscopy. Their selectivities as catalysts were determined by comparing the extents of hydrogenation of carefully chosen pairs of small-molecule olefins. There was found to be high hydrogenation selectivity with regard to cyclic vs. noncyclic olefins. Selectivity was relatively low, however, among olefins that differed only in size (such as hexene vs. octene), or olefins differing only with regard to the positions of the double bonds (such as 1-octene vs. 3-octene). Selectivity could be improved by careful choice of the immobilizing polymer, and by its use at relatively high concentrations.     

Organoelement Compounds with Al?Al,Ga?Ga,and In?In Bonds

In the attempt to synthesize compounds with aluminum in a low oxidation state and an Al Al bond, by the reduction of alkylaluminum halides with alkali metals, analogous to a Wurtz coupling, in general the deposition of elemental aluminum and the formation of the corresponding trialkylaluminum compounds is observed. Thus, tetrasubstituted dialuminum compounds R₂Al AlR₂, apart from a few poorly characterized examples, were for a long time considered part of an unverified class of substances. Only with the sterically very highly shielded tetrakis[bis(trimethylsilyl)methyl]dialuminum did we achieve the synthesis of the first completely characterized organoelement compound with unlimited stability, which shows aluminum in the oxidation state + II and has an Al Al bond. In the meantime, corresponding compounds for the elements gallium and indium have been obtained. With the simple access to tetrasubstituted dimetal compounds, a fascinating new research area has opened for preparative chemistry, in which the particular interest will naturally lie in the reactive properties of the metal-metal bond.     

化学形态分析

本文综述了金属元素的化学形态分析,包括:形态分析的方法与技术,形态分析在水、土壤、空气和生物样品中的应用,样品的处理方法等。     

Effect of cooperativity on the O-H stretching force constant in associated water species

CNDO/force calculations have been employed to calculate the O-H stretching force constants for various structures of associated water species such as water-dimethylether, water-acetonitrile, water-lithium fluoride, linear and cyclic water polymers. The variation in the O-H stretching force constant in A_m… O-H… D_n species where A_m and D_n represent, respectively,m number of electron-acceptor andn number of electron-donor molecules, is explained on the basis of the cooperativity effect. With increasing electron-acceptor power of A and electron-donor power of D, the hydrogen-bonded O-H stretching force constant is significantly reduced. The results obtained in these studies are in general agreement with experimental observations reported earlier.     

Synthese und Struktur von Li3RhH6, einem ternären Hydrid mit isolierten [RhH6]3−-Oktaedern

Synthesis and Structure of Li₃RhH₆ — a Ternary Hydride with Isolated [RhH₆]^3? Octahedra The ternary rhodium hydride Li₃RhH₆ was synthesized by the reaction of lithium hydride with rhodium under a hydrogen pressure of 80 bar. X-ray investigations on powdered samples and an elastic neutron diffraction experiment on the deuterated compound led to the complete structure determination (space group: Pnma, Z = 4). The atomic arrangement is isotypic to the Na₃RhH₆ structure type. The crystal structure contains isolated [RhH₆]^3? octahedra, which are separated by the lithium ions.     

Trends in Preconcentration Procedures for Metal Determination Using Atomic Spectrometry Techniques

 Methods for metal preconcentration are often described in the literature. However, purposes are often different, depending on whether the methods are applied in environmental, clinical or technological fields. The respective method needs to be efficient, give high sensitivity, and ideally also is selective which is useful when used in combination with atomic spectroscopy. This review presents the actual tendencies in metal preconcentration using techniques such as Flame Atomic Absorption Spectrometry (FAAS), Electrothermal Atomic Absorption Spectrometry (ETAAS), Hydride Generation Atomic Absorption Spectrometry (HGAAS), Inductively Coupled Plasma Optical Emission Spectrometry (ICP OES) and Inductively Coupled Plasma Mass Spectrometry (ICP-MS). Procedures based on related to electrochemical, coprecipitation/precipitation, liquid–liquid and solid–liquid extraction and atom trapping mechanisms are presented. Correspondence: Department of Analytical Chemistry, Universidade Estadual de Campinas – UNICAMP, P.O. Box 6154, 13083-970 Campinas, Brazil. e-mail: zezzi@iqm.unicamp.br Received December 20, 2001; accepted October 11, 2002