Study of a fluorescence quenching mechanism of enoxacin and its determination in human serum and urine samples

The maximum emission wavelength of dopamine is 317 nm with excitation at 290 nm. The relative fluorescence intensity of dopamine decreased in the presence of enoxacin, which showed that fluorescence quenching occurred. The Stern-Volmer (S-V) plot showed a nonlinear relationship between the relative fluorescence intensity of dopamine and the concentration of enoxain. The quenching mechanism was studied and the results suggested that both dynamic and static quenching processes were responsible for the observed positive deviation in the S-V plot. When the S-V plot was modified by logarithm, the linear relationship was obtained between logF ₀/F and C in the range of 0.10 to 13.0 μg/mL (where F ₀ is the relative fluorescence intensity of dopamine, F is the relative fluorescence intensity of dopamine in the presence of enoxacin, and C is the concentration of enoxacin). The fluorescence quenching method for the determination of enoxacin was developed. The linear regression equation of the calibration graph of enoxacin was C = 13.70 (logF ₀/F) − 0.5836, with the correlation coefficient 0.9984. The detection limit was 2.0 ng/mL and the relative standard deviation was 2.52%. The effects of pH, the stability of dopamine in the presence of enoxacin, and foreign ions on the determination of enoxacin have been examined. The recovery of enoxacin was from 94.9 to 103.0% in a human serum sample and from 94.9 to 108.0% in a urine sample. The method is simple, rapid, and can be used for the determination of enoxacin in human serum and urine samples with satisfactory results. The text was submitted by the authors in English.     

LC-ESI-MS Determination of Bilobalide and Ginkgolides in Canine Plasma

A sensitive and selective method using liquid chromatography with electrospray ionization mass spectrometric detection was developed for the quantification of bilobalide and ginkgolides in canine plasma. The analytes were extracted with diethyl ether-dichloromethane-isopropanol (6:3:1, v/v) after spiking the samples with daidzein (internal standard). The lower limit of quantification (LLOQ) of the method was 2.5 μg L⁻¹ for ginkgolide B and 10.0 μg L⁻¹ for bilabolide, ginkgolide A and ginkgolide C. The accuracy of the method was within 15% of the actual values over a wide range of plasma concentrations. The intra-day and inter-day precision was better than 15% (R.S.D.). Finally, the LC-ESI-MS method was successfully applied to study the pharmacokinetics of ginkgolides and bilabolide after administration of Ginkgo biloba extracts to dogs.     

Reactivity of Ar'GeGeAr' (Ar' = C6H3-2,6-Dipp2, Dipp = C6H3-2,6-iPr2) toward alkynes: isolation of a stable digermacyclobutadiene

The first reactions of the "digermyne" Ar'GeGeAr' (1, Ar' = C6H3-2,6-Dipp2, Dipp = C6H3-2,6-iPr2) with alkynes are reported. 1 reacts with 1 equiv of H5C6CCC6H5 to afford the 1,2-digermacyclobutadiene 2 in high yield, while it reacts with 2 equiv of the less hindered alkyne Me3SiCCH to yield an unexpected bicyclic compound 3. Molecular structures of 2 and 3 were determined by X-ray crystallography. A possible mechanism for the formation of 3 is discussed. The high reactivity of 1, even at room temperature, emphasizes the fundamental differences between the GeGe and CC multiple bonds.     

Capillary electrophoresis with wavelength-resolved laser-induced fluorescence detection

Capillary electrophoresis (CE) enables rapid separations with high separation efficiency and compatibility with small sample volumes. Laser-induced fluorescence detection can result in extremely low limits of detection in CE. Single-channel fluorescence detection, however, furnishes little qualitative information about a species being detected, except for its CE migration time. Use of multidimensional information often enables unambiguous identification of analytes. Combination of CE with information-rich wavelength-resolved fluorescence detection is analogous with ultraviolet-visible diode-array detection and furnishes both qualitative and quantitative chemical information about target species. This review discusses recent advances in wavelength-resolved laser-induced fluorescence detection coupled with CE, with an emphasis on instrument design.     

非离子型表面活性剂组成的微乳液热力学性质 (IV) 烷烃的碳原子数影响

由表面活性剂、醇、油和水所组成的微乳液,油相的烷烃长度会影响到微乳液的性质,主要表现在界面相组成和界面张力.Birdi 用加溶法研究以十六烷、硬脂酸钠、水和醇(从C_5到C_9)所组成的微乳液,醇的碳原子数n_a 与标准自由能△G(?)有以下关系:△G(?),醇=1563-839.5n_a(J·mol~(-1)在同样体系内,戊醇和不同烷烃则:     

Preparation and characterization of nitrogen-doped titanium dioxides

A type of high visible-light active titanium oxinitride(TiO2-xNx) powder was prepared by a simple proc-ess:the calcination of the hydrated titanium dioxide at the atmosphere of ammonia-argon using a tu-bular electric furnace at high temperatures. The hydrated titanium dioxide was synthesized as the precursor of TiO2-xNx using titanic acid as raw material,which came from sulfate technique of produc-ing titanium white. The effects of temperature and reaction time on the nitrogen content,grain size and crystal structure were studied. The visible-light activity and photocatalysis capability of the powder were also investigated.     

便携式温度计校验仪的研制

介绍便携式温度计校验仪的工作原理及研制过程。对该仪器的恒温槽体机械结构、制冷器和散热器的设计、恒温槽体温度测量及控制等进行了详细叙述。该仪器提供的温度场稳定、均匀，在-20～100℃范围内可任意设定温度。解决了温度计现场快速校准的问题。     

Nitrosation of Phenolic Compounds: Effects of Alkyl Substituents and Solvent

Summary.  Nitrosation reactions of phenol, o-cresol, 2,6-dimethylphenol, o-tert-butylphenol, 2-hydroxyacetophenone, and 2-allylphenol in water and water/acetonitrile were studied. Kinetic monitoring of the reactions was accomplished by spectrophotometric analysis of the nitrosated products at 345 nm. The dominant reaction was C-nitrosation via a mechanism consisting of an attack on the nitrosatable substrate by NO⁺/NO₂H₂ ⁺ followed by a slow proton transfer. The values of the rate constants of phenolic C-nitrosation were increased by electron donating substituents, and a good Hammett correlation was observed with ρ = −6.1. The results also revealed the strong effect of pH and the permitivity of the reaction medium on the rate constant, whose maximum values were observed for pH ≈ 3, decreasing strongly for higher pH values. The study in water/acetonitrile with up to 25% acetonitrile showed that it is possible to inhibit the reaction strongly by increasing the percentage of the organic component. The conclusions drawn show that (i) it is possible to predict the rate of nitrosation of phenolics as a function of the meta-substituents on the phenol ring and (ii) the nitrosation of phenolics can be strongly inhibited by increasing the pH of the reaction medium as well as by lowering its dielectric constant. Received July 13, 2001. Accepted (revised) September 18, 2001     

Direct observation of cations and polynucleotides explains polyion adsorption to like-charged surfaces

We show an experimental approach for directly observing the condensation of polynucleotides and their electrolyte counterions at a liquid/solid interface. X-ray standing waves (XSW) generated by Bragg diffraction from a d = 20 nm Si/Mo multilayer substrate are used to measure the distinct distribution profiles of the polyanions and simple cations along the surface normal direction with subnanometer resolution. The 1D spatial sensitivity of this approach is enhanced by observing the XSW induced fluorescence modulations over multiple orders of Bragg peaks. We study the interesting divalent cation driven adsorption of anionic polynucleotides to anionic surfaces by exposing a hydroxyl-terminated silica surface to an aqueous solution with ZnCl2 and mercurated poly-uridylic acid (a synthetic RNA molecule). The in situ long-period XSW measurements are used to follow the evolution of both the Zn and Hg distribution profiles during the adsorption process. The conditions and physical mechanisms that govern the observed divalent cation adsorption and subsequent polynucleotide adsorption to an anionic surface are explained by a thermodynamic model that incorporates nonlinear electrostatic effects.     

Preparation and characterization of Co(II), Ni(II) and Cu(II) complexes of a ligand containing 1,3,4-thiadiazole groups

(1R,2R)-1,2-bis-(5-amino-1,3,4-thiadiazole-2-yl)ethane-1,2-diol (L) has been prepared by the reaction of thiosemicarbazide with (2R,3R)-(+)-tartaric acid (I) and phosphorous oxychloride, and its complexes with Co(II), Ni(II) and Cu(II) have been obtained. The structures of the ligand and its complexes have been established by i. r., ¹H- and ¹³C-n.m.r. spectra, u.v.–vis–nir spectroscopy, elemental analyses, T.g.-D.t.a. and magnetic susceptibility measurements.