Determination of ascorbic acid by flow injection chemiluminescence suppression method

chemiluminescence suppression method for the determination of ascorbic acid based on Luminol-KIO4-H2O2-ascorbic acid system was established. The linear range for ascorbic acid is 1.0 x 10(-7) similar to 1.0 x 10(-5) mol/L and the detection limit is 6.0 x 10(-8) mol/L. The relative standard deviation (n = 11) is 1.0% for 8.0 x 10(-7) mol/L ascorbic acid. The method has been used to determine the content of ascorbic acid in tablets and injections with satisfactory results.

Sol-gel-derived, polishable, 1 : 12-phosphomolybdic acid-modified ceramic-carbon electrode and its electrocatalytic oxidation of ascorbic acid

Novel ceramic-carbon electrodes (CCEs) containing 1:12-phosphomolybdic acid (PMo12) were constructed by homogeneously dispersing PMo12 and graphite powder into methyltrimethoxysilane-derived gel. Peak currents for the PMo12-doped CCE were surface-controlled at lower scan rates but diffusion-controlled at higher scan rates and peak potentials shifted to the negative potential direction with increasing pH. In addition, the electrode exhibited electrocatalytic activity toward the oxidation of ascorbic acid. The PMo12-modified CCE presented good chemical and mechanical stability and good surface renewability (ten successive polishing resulted in less than 5% relative standard deviation). (C) 2000 Elsevier Science B.V. All rights reserved.

Three-dimensional quantitative structure-activity relationship of the opioid antagonist with potent anorectant activity of 3,4-dimethyl-4-(3-hydroxyphenyl) piperidine

A series of 3,4-dimethyl-4-(3-hydroxyphenyl) piperidine opioid antagonists with varying substituents on the nitrogen were evaluated for their effect on food consumption in obese Zucker rats. In developing three-dimensional quantitative structure-activity relationship (3D-QSAR) studies for this series of opioid antagonists, different structure alignments have been tested to predict the anorectant activities. The interaction energies between molecules and the probe atom were then correlated with anorectant activity using partial least squares (PLS) method. The steric and electrostatic features of the 3D-QSAR were presented in the form of standard deviation coefficient contour maps of steric and electrostatic fields. The results showed that 3D-QSAR results are much better than the results obtained by 2D-QSAR.

Anodic voltammetric behavior of medecamycin at a glassy carbon electrode

The anodic voltammetric behavior of medecamycin (MD) in the presence of various electrolytes was studied by linearsweep voltammetry, differential-pulse voltammetry and cyclic voltammetry at a glassy carbon electrode. In phosphate buffer solutions (pH = 9.4), MD is oxidized irreversibly. The peak potential is at about +0.75 V (vs.Ag/AgCl). The height of the peak is linearly increased with the concentration of MD over the range of 5 x 10(-5) similar to 1 x 10(-1) g/L. The method has been used for the direct determination of MD in tablets. The relative standard deviation (n = 10) is 1.8%. The recoveries of MD in urine samples are in the range of 95% similar to 115%.

Laser-time-resolved fluorescence spectroscopy in immunoassays

This paper described a laser-excited time-resolved fluoroimmunoassay set. It made lanthanide ion to couple the anhydrde of diethylenetriaminepentaacetic acid (DTPAA) for labeling antibodies. The experiment used polystyrene tap coated with HCV antigen as the solid phase and a chelate of the rare earth metal europium as fluorescent label. A nitrogen laser beam was used to excite the Eu3+ chelates and after 60 ys delay time,the emission fluorescence was measured. Background fluorescence of short lifetimes caused by serum components and Raman scattering can be eliminated by set the delay rime. In the system condition, fluorescent spectra and fluorescent lifetimes of Eu3+ beta-naphthoyltrifluroacetone (NTA) chelates were measured. The fluorescent lifetime value is 650 mu s. The maximum emssion wavelength is 613 nm. The linear range of europium ion concentration is 1 x 10(-7)- 1 x 10(-11) g.mL(-1) and the detection limit is 1 x 10(-13) g.mL(-1). The relative standard deviation of determination ( n = 12) for samples at 0.01 ng.mL(-1) magnitude is 6.4%. Laser-TRFIA was also found to be suitable for diagnosis of HCV. The sensitvity and specificity were comparable to enzyme immunoassay. The result was obtained with laser-TRFIA for 29 human correlated well with enzyme immunoassay.

Electrochemiluminescent determination of peroxydisulfate with Cr(bpy)(3)(3+) in purely aqueous solution

A novel method for the sensitive and selective determination of peroxydisulfate was proposed. It was based on an electrochemiluminescent method with Cr(bpy)(3)(3+). The applied potential was set at -0.5 V in Cr(bpy)(3)(3+) system which was much more positive than those in Ru(bpz)(3)(2+) and Ru(bpy)(3)(2+) systems. A linear calibration was obtained over the range of 7-100 mu mol l(-1) with a correlation coefficient of 0.993. The relative standard deviation was 2% for 10 replicate injections of 0.01 mol l(-1) S2O82- solution. The detection limit (S/N=3) was 1 mu mol l(-1). The method was successfully applied to determination of peroxydisulfate in phase transfer catalysis. (C) 2000 Elsevier Science B.V. All rights reserved.

Electrochemiluminescent determination of perchlorate by solvent extraction in the presence of Ru(bpy)(3)(2+)

A novel method for the highly sensitive determination of perchlorate was proposed. It was based on solvent extraction in the presence of Ru(bpy)(3)(2+) followed by Ru(bpy)(3)(2+) electrochemiluminescent determination. A linear calibration was obtained over the range of 0.1 to 10 mu mol l(-1) with a correlation coefficient of 0.998. The detection limit (S/N = 3) was 5.0 x 10(-8) mol l(-1). The relative standard deviation for 10 replicates of 1 mu mol l(-1) perchlorate was 1.6%. Interference studies suggest that this method is selective for the determination of perchlorate. Application of this method to the highly sensitive determination of other anions is suggested. (C) 1999 Elsevier Science S.A. All rights reserved.

Determination of 14 rare earth impurities in Y2O3 by petroleum sulfoxide extraction chromatography

Petroleum sulfoxide-NH4SCN extraction chromatography was developed for the separation of Y from other rare earth elements. Some chromatographic parameters were chosen and separation factors between Y and other rare earth elements were determined. A column of resin coated with petroleum sulfoxide was used. The Y in the sample was eluted with NH4SCN, then titrated with EDTA. The recovery was 67%-120% and relative standard deviation +/-4.0%-19.4%. This method can be applied to the determination of trace amounts of rare earth impurities in Y2O3 with a purity of 99.999 9%-99. 999 99%.

Evaluation of luminol-H2O2-KIO4 chemiluminescence system and its application to hydrogen peroxide, glucose and ascorbic acid assays

(A) novel chemiluminescence (CL) system was evaluated for the determination of hydrogen peroxide, glucose and ascorbic acid based on hydrogen peroxide, which has a catalytic-cooxidative effect on the oxidation of luminol by KIO4. Hydrogen peroxide can be directly determined by luminol-KIO4 -H2O2 CL system. The detection limit was 3.0 x 10(-8) mol l(-1) and the calibration graph was linear over the range of 2.0 x 10(-7)-6.0 x 10(-4) mol l(-1). The relative standard deviation of H2O2 was 1.1% for 2.0 x 10(-6) mol l(-1) (N = 11). Glucose was indirectly determined through measuring the H2O2 generated by the oxidation of glucose in the presence of glucose oxidase at pH 7.6. The present method provides a source for H2O2, which, in turn, coupled with the luminol-KIO4-H2O2 CL reaction system. The CL was linearly correlated with glucose concentration of 0.6-110 mu g ml(-1). The relative standard deviation was 2.1% for 10 mu g ml(-1) (N = 11). Detection limit of glucose was 0.08 mu g ml(-1). Ascorbic acid was also indirectly determined by the suppression of luminol-KIO4-H2O2 CL system. The calibration curve was linear over the range of 1.0 x 10(-7)-1.0 x 10(-5) mol l(-1) of ascorbic acid. The relative standard deviation was 1.0% for 8.0 x 10(-7) mol l(-1) (N = 11). Detection limit of ascorbic acid was 6.0 x 10(=8) mol l(-1). These proposed methods have been applied to determine glucose, ascorbic acid in tablets and injection. (C) 1999 Elsevier Science B.V. All rights reserved.

The fabrication and performance of an Ag/AgCl reference electrode in human serum

A simple set of electric circuits was used to assemble a pulse generator. With pulse potentials and under galvanostatical control, a clean silver wire was anodized electrochemically for 0.2-0.5 min in 1.0 moll(-1) HCl with a pulse current density of 20 mA cm(-2), and the pulse wave parameters of t(a)/t(c) = 1 and a cycle of 4 s forming an Ag/AgCl reference electrode. Even though the AgCl layer was consumed during the working period when the Ag/AgCl electrode was used as a cathode, the AgCl layer could be in situ recovered electrochemically in serum used when a reversed potential was applied to the electrode system immediately after the measuring program was finished. The current response curve of the anode indicated that an AgCl layer in high density was basically accomplished during the first 6 pulse cycles in human serum. In order to keep a stable and uniform AgCl layer on the reference electrode after each measuring cycle, the ratio of the recovery time (t(r)) to the working time (t(w)) was measured and the smallest value was obtained at 0.03. The open-circuit potential of the Ag/AgCl electrode with respect to a SCE in 0.1 moll(-1) KCl was monitored over a period of 14 days and the mean value was 40.09 mV vs SCE with a standard deviation of 2.55 mV. The potential of the Ag/AgCl reference electrode did remain constant when the measurements were repeated more than 600 times in undiluted human serum with a standard deviation of 1.89 mV. This study indicated that the Ag/AgCl reference electrode could been rapidly fabricated with a pulse potential and could be used as a reference electrode with long-term stable properties in human serum samples.

STUDY OF THE ELECTRODE PROCESS OF HEMOGLOBIN AT A POLYMERIZED AZURE A FILM ELECTRODE

The electrochemically polymerized azure A film electrode is reported. The resulting film on a platinum electrode surface was analyzed with electron spectroscopy for chemical analysis (ESCA). The heterogeneous electron transfer processes of hemoglobin at the polymerized azure A film electrode have been investigated using in situ UV-visible spectroelectrochemistry. The formal potential (E-degrees') and electron transfer number (n) of hemoglobin were calculated as E = 0.088 V versus NHE (standard deviation +/- 0.5, N = 4) and n = 1.8 (standard deviation +/- 0.5, N = 4). Exhaustive reduction and oxidation electrolysis are achieved in 80 and 380 seconds, respectively, during a potential step between -0.3 and +0.3 V. A formal heterogeneous electron-transfer rate constant (k(sh)) of 3.54(+/- 0.12) X 10(-6) cm/s and a transfer coefficient (alpha) of 0.28(+/- 0.01) were obtained by cyclic voltabsorptometry, which indicated that the poly-azure A film electrode is able to catalyze the direct reduction and oxidation of hemoglobin.

Simultaneous determination of four phases of copper in geological samples

According to the specific property of respective phases in copper ore, optimal extracting condition for, tour phases of copper with five infusion was examined. After a series of experiments, for example, different weight Of sample, artificial mixed single phases sample and repeated experiment, the extracting ratio constants foil all phases in different infusions were obtained. The mathematical model which is on the basis of the stable extracting constant is established. Based on the purpose-control genetic algorithms, we only need to determine the total copper in the sample in different infusions under the selected condition, then the value of respective phase could be calculated. The-relative standard deviation are (%) free oxidized copper phase:1.5, conjunction oxidized copper phase: 17.6,, secondary copper sulfide phase: 1.9, primary copper sulfide phase : 2.7,total copper: 0.8.

Grain-size records at ODP site 1146 from the northern South China sea: Implications on the east Asian monsoon evolution since 20 Ma

273 samples from Ocean Drilling Program (ODP) Site 1146 in the northern South China Sea (SCS) were analyzed for grain-size distributions using grain-size class vs. standard deviation method and end-member modeling algorithm (EMMA) in order to investigate the evolution of the East Asian mon-soon since about 20 Ma. 10-19 mu m/1.3-2.4 mu m, the ratio of two grain-size populations with the highest variability through time was used to indicate East Asian winter monsoon intensity relative to summer monsoon. The mass accumulation rate of the coarsest end member EM1 (eolian), resulting from EMMA, can be used as a proxy of winter monsoon strength and Asian inland aridity, and the ratio of EM1/(EM2+EM3) as a proxy of winter monsoon intensity relative to summer monsoon. The combined proxies show that a profound enhancement of East Asian winter monsoon strength and winter monsoon intensity relative to summer monsoon occurred at about 8 Ma, and it is possible that the summer monsoon simultaneously intensified with winter monsoon at 3 Ma. Our results are well consistent with the previous studies in loess, eolian deposion in the Pacifc, radiolarians and planktonic foraminifera in the SCS. The phased uplift of the Himalaya-Tibetan Plateau may have played a significant role in strengthening the Asian monsoon at 8 Ma and 3 Ma.

Generation and evolution of magma beneath the East Pacific Rise: Constraints from U-series disequilibrium and plagioclase-hosted melt inclusions

Mid-ocean ridge basalt (MORB) samples from the East Pacific Rise (EPR 12 degrees 50'N) were analyzed for U-series isotopes and compositions of plagioclase-hosted melt inclusions. The Ra-226 and Th-230 excesses are negatively correlated; the Ra-226 excess is positively correlated with Mg# and Sm/Nd, and is negatively correlated with La/Sm and Fe-8; the Th-230 excess is positively correlated with Fe-8 and La/Sm and is negatively correlated with Mg# and Sm/Nd. Interpretation of these correlations is critical for understanding the magmatic process. There are two models (the dynamic model and the "two-porosity" model) for interpreting these correlations, however, some crucial parameters used in these models are not ascertained. We propose instead a model to explain the U-series isotopic compositions based on the control of melt density variation. For melting either peridotite or the "marble-cake" mantle, the FeOt content, Th-230 excess and La/Sm ratio increases and Sm/Nd decreases with increasing pressure. A deep melt will evolve to a higher density and lower Mg# than a shallow melt, the former corresponds to a long residence time, which lowers the Ra-226 excess significantly. This model is supported by the existence of low Ra-226 excesses and high Th-230 excesses in MORBs having a high Fe-8 content and high density. The positive correlation of Ra-226 excess and magma liquidus temperature implies that the shallow melt is cooled less than the deep melt due to its low density and short residence time. The correlations among Fe-8, Ti-8 and Ca-8/Al-8 in plagioclase-hosted melt inclusions further prove that MORBs are formed from melts having a negative correlation in melting depths and degrees. The negative correlation of Ra-226 excess vs. chemical diversity index (standard deviation of Fe-8, Ti-8 and Ca-8/Al-8) of the melt inclusions is in accordance with the influence of a density-controlled magma residence time. We conclude that the magma density variation exerts significant control on residence time and U-series isotopic compositions. (c) 2010 Elsevier B.V. All rights reserved.

Mean sea surface heights of the South and East China Seas from ocean circulation model and geodetic leveling

The mean sea surface heights (sea surface topography) of the South China, East China, Yellow and Bohai Seas are derived from an ocean general circulation model and surface air pressure. The circulation model covers the global oceans, with fine grid (1/6degrees) covering the East Asian marginal seas and coarse grid (31) covering the rest part of the global oceans. The result shows that the China 1985 National Altitude Datum is 24.7 cm above the me-an sea surface height of the world oceans. The mean sea surface in the coastal ocean adjacent to China is higher in the south than in the north. Intercomparison of the model results with the geodetic leveling measurements at 28 coastal tidal stations shows a standard deviation of 4.8 cm and a fitting coefficient of 95.3%. After correction through linear regression, the standard deviation is reduced to 4.5 cm. This indicates that the accuracy of model results is sufficient for practical application. Based on the model results, the mean sea surface heights for the study area with a resolution of 1/6 degree are given. This result also links the mean sea levels at islands with those on the mainland coast and gives the mean sea surface heights at tidal stations in the Taiwan Island, the Dongsha Islands, the Yisha Islands and the Nansha Islands relative to the China 1985 National Altitude Datum.