Quantitative determination of glutathione in single human erythrocytes by capillary zone electrophoresis with electrochemical detection

Glutathione (GSH) in single human erythrocytes is determined by capillary zone electrophoresis with end-column amperometric detection at a gold/mercury amalgam microelectrode. A capillary of 10 microm inner diameter is suitable for determination of GSH in an individual erythrocyte with a good signal-to-noise ratio. The limit of detection is 1 x 10(-7) mol/L or 26 amol and the linear dynamic range is 2 x 10(-7) to 2 X 10(-5) mol/L for the capillary. In this method, the calibration line is obtained with a capillary adsorbed before a certain amount of hemoglobin can be used for the quantification of GSH in the external standardization. The whole cell injection and the lack of necessity of a derivatization reaction lead to more accurate and precise results, which are closer to the macroscopic values of glutathione in human red blood cell (i.e., hemolysate) than those determined by indirect laser-induced fluorescence detection.     

Sorption of 241Am by Aspergillus nigerspore and hyphae

Biosorption of ²⁴¹Am by a fungus A. niger, including the spore and hyphae, was investigated. The preliminary results showed that the adsorption of ²⁴¹Am by the microorganism was efficient. More than 96% of the total ²⁴¹Am could be removed from ²⁴¹Am solutions of 5.6-111 MBq/l (C _o) by spore and hyphaeof A. niger, with adsorbed ²⁴¹Am metal (Q) of 7.2-142.4 MBq/g biomass, and 5.2-106.5 MBq/g, respectively. The biosorption equilibrium was achieved within 1 hour and the optimum pH range was pH 1-3. No obvious effects on ²⁴¹Am adsorption by the fungus were observed at 10-45 °C, or in solutions containing Au³⁺ or Ag⁺, even 2000 times above the ²⁴¹Am concentration. The ²⁴¹Am biosorption by the fungus obeys the Freundlich adsorption equation. There was no significant difference between the adsorption behavior of A. nigerspore and hyphae. This revised version was published online in July 2006 with corrections to the Cover Date.     

Dispersion state of CuO on CeO2

XRD and XPS are used to study the dispersion state of CuO on ceria surface. The dispersion capacity values of CuO measured by the two methods are consistent, which are of 1.20 mmol CuO/100 m² CeO₂. In addition, the results reveal that highly dispersed Cu²⁺ ions are formed at low CuO loadings and that increasing the CuO content to a value higher than its dispersion capacity produces crystalline CuO after the surface vacant sites on CeO₂ are filled. The atomic composition of the outermost layer of the CuO/CeO₂ samples has been probed by using static secondary ion mass spectroscopy (SSIMS), and the ratim of Cu/Ce are found to be 0.93 and 0.46 for the 1.22 and 0.61 mmol CuO/CeO₂ samples respectively. Temperature-programmed reduction (TPR) profile with two reduction peaks at 156 and 165°C suggests that the reduction of highly dispersed Cu²⁺ ions consists of two steps and is easier than that of CuO crystallites, in which the TPR profile has only one reduction peak at about 249°C. The above experimental results are in good agreement with the prediction of the incorporation model. Project supported by the National Natural Science Foundation of China.     

Biosorption of americium-241 by Saccharomyces cerevisiae

The biosorption of radionuclide ²⁴¹Am from solution by Saccharomyces cerevisiae (S. cerevisiae), and the effects of experimental conditions on the adsorption were investigated. The preliminary results showed thatS. cerevisiae is a very efficient biosorbent. An average of more than 99% of the total ²⁴¹Am could be removed by S. cerevisiae of 2.1 g/l (dry weight) from ²⁴¹Am solutions of 17.54–4386.0 mg/l (2.22 MBq/l–555 MBq/l) with adsorption capacities of 7.45–1880.0 mg/g biomass (dry weight) (0.94 MBq/g–237.9 MBq/g). The adsorption equilibrium was achieved within 1 hour and the optimum pH ranged 1–3. No significant differences on ²⁴¹Am adsorption were observed at 10–45 °C, or in solutions containing Au³⁺ or Ag⁺, even 2000 times above ²⁴¹Am concentration. The relationship between concentrations and adsorption capacities of ²⁴¹Am indicated the biosorption process should be described by the Freundlich adsorption isotherm.     

Synthesis of 2‐Dihydrooxadiazolinyl Chromones

Reactions of the substituted 2‐formyl chromones with aroylhydrazines gave corresponding 2‐(aroylhydrazonomethylidyne) chromones. Then 2‐(3′‐acetyl‐5′‐aryl‐2′,3′‐dihydro‐1′,3′,4′‐oxadiazol‐2′‐yl) chromones were prepared by these 2‐(aroylhydrazonomethylidyne) chromones under refluxing with Ac₂O. All target compounds were characterized through elemental analysis and IR, ¹H NMR, MS.     

1.5-Diaza-3.7-diphospha-cyclooctane

The alkyl (aryl)-bishydroxymethylphosphines react with primary amines to give the title compounds. With optically active amines optically active phosphines are formed.     

Stationary phase evaluations of quantum rate constants

We compute the quantum rate constant based on two extended stationary phase approximations to the imaginary-time formulation of the quantum rate theory. The optimized stationary phase approximation to the imaginary-time flux-flux correlation function employs the optimized quadratic reference system to overcome the inaccuracy of the quadratic expansion in the standard stationary phase approximation, and yields favorable agreements with instanton results for both adiabatic and nonadiabatic processes in dissipative and nondissipative systems. The integrated stationary phase approximation to the two-dimensional barrier free energy is particularly useful for adiabatic processes and demonstrates consistent results with the imaginary-time flux-flux correlation function approach. Our stationary phase methods do not require calculation of tunneling paths or stability matrices, and work equally well in the high-temperature and the low-temperature regimes. The numerical results suggest their general applicability for calibration of imaginary-time methods and for the calculation of quantum rate constants in systems with a large number of degrees of freedom.     

A convenient and efficient preparation of β-substituted α-haloenones from diazodicarbonyl compounds

Rhodium(II)-catalyzed reactions of cyclic diazodicarbonyl compounds with a variety of halides have been examined. With acid halides, β-acyloxy α-haloenones are produced in good yields. With benzyl halides, β-benzyloxy α-haloenones are obtained in good yields. Reactions with methylene halides yield β-halomethoxy α-haloenones in good yields, whereas reactions with ethyl halides and ethylene dihalides result in β-hydroxy α-haloenones in high yields. These reactions provide a useful and rapid entry to β-substituted α-haloenones. The mechanistic pathway for the formation of these products has been also described in terms of halonium ylides.     

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.     

An HPLC and EPR investigation on the stability of DMPO and DMPO spin adducts in vivo

Application of the spin trapping technique in intact animals requires an understanding of the stability and distribution of the spin traps and their spin adducts in vivo. We studied the stability of DMPO in vivo in mice using HPLC and the stability of spin adducts of DMPO by EPR in plasma, whole blood, peritoneal fluid, and homogenized heart tissue of the rat. At 15 minutes after intraperitoneal injection DMPO had similar concentrations in the liver, heart, and blood of the mice and 40% remained in the organs 2 hours after the injection. In contrast, the spin adduct DMPO-OH was short lived, with a half-life of 3.0 minutes in plasma, and was not detectable 1 minute after formation in whole blood and homogenized heart tissue. The carbon centered spin adduct DMPO-CH(OH)CH₃ was more stable, having half-lives of 16, 11, 3.6, and 0.79 minutes in plasma, peritoneal fluid, whole blood, and homogenized heart tissue, respectively. The spin adduct DMPO-SO₃ was sufficiently stable for the adduct to be observed directly from living mice.