Rapid solution and solid phase synthesis of monodisperse oligo[(1,4-phenyleneethynylene)-alt-(2,5-thiopheneethynylene)]s

Monodisperse oligo[(1,4-phenyleneethynylene)-alt-(2,5-thiopheneethynylene)]s, new candidates for molecular wires, were rapidly synthesized via an iterative divergent/convergent doubling strategy in solution as well as on Merrifield's resin.

A rapid solid-phase synthesis to soluble oligothiophene molecular wires

A novel method for the preparation of oligothiophene molecular wires is described via a bi-directional solid-phase synthesis. Using an alternating sequence of bromination and Stille coupling reactions, oligomers were obtained up to the heptamer in excellent yield and purity.

Capillary electrophoresis with amperometric detection of curcumin in Chinese herbal medicine pretreated by solid-phase extraction

In the present study, curcumin from Chinese herbal medicine turmeric was determined by capillary electrophoresis with amperometric detection (CE-AD) pretreated by a self-designed, simple, inexpensive solid-phase extraction (SPE) cartridge based on the material of tributyl phosphate resin. An average concentration factor of 9 with the recovery of >80% was achieved when applied to the analysis of curcumin in extracts of turmeric. Under the optimized CE-AD conditions: a running buffer composed of 15 mM phosphate buffer at a pH 9.7, separation voltage at 16 W, injection for 6 s at 9 W and detection at 1.20 V, CE-AD with SPE exhibited low detection limit as 3 - 10(-8) mol/l (SIN = 3), high efficiency of 1.0(.)10(5) N, linear range of 7(.)10(-4) -3(.)10(-6) mol/l (r = 0.9986) for curcumin extracted from light petroleum. The method developed resulted in enhancement of the detection sensitivity and reduction of interference from sample matrix in complicated samples and exhibited the potential application for routine analysis, especially in food, because a relatively complete process of sample treatment and analysis was described.

Preparation of Pt/C catalyst with solid phase reaction method

The PVC catalyst was prepared with solid phase reaction method (Pt/C(S)) for the first time. Its performances were compared with that prepared by the traditional liquid phase reaction method. The results demonstrate that the electrocatalytic activity of PVC catalyst with solid phase reaction method for methanol oxidation is higher than that with liquid phase reaction method. XRD and TEM measurements indicate that the Pt/C(S) possesses low crystalline extent and small particle size.

Y-Ba-Cu-O mixed oxides for production of diphenols in liquid-solid phase

Superconductor mixed oxides were often used as catalysts at higher temperature in gas phase oxidations, and considered not suitable for lower temperature reactions in the liquid-solid phase; here the catalysis of YBa2Cu3O7+/-x and Y2BaCuO5+/-x in the phenol hydroxylation at lower temperature with H2O2 as oxygen donor was studied, and found that the superconductor YBa2Cu3O7+/-x, has no catalytic activity for phenol hydroxylation, but Y2BaCuO5+/-x does, even has better catalytic activity and stability than most previously reported ones. With the studies of catalysis of other simple metal oxides and perovskite-like mixed oxides, a radical substitution mechanism is proposed and the experimental facts are explained clearly, and draw a conclusion that the perovskite-like mixed oxides with (AO)(ABO(3)) and (AO)2(ABO(3)) structure have better catalytic activity than the simple perovskite oxides with (ABO(3))(3) structure alone, and (AO) structure unit is the key for the mixed oxides to have the phenol hydroxylation activity. No pollution of this process is very important for its further industrial application.

Superconductor mixed oxides La2-xSrxCuO4+/-lambda for catalytic hydroxylation of phenol in the liquid-solid phase

Superconductor mixed oxides are often used as catalysts at high temperature in gas-solid phase oxidations and considered not suitable for lower temperature reactions in the liquid-solid phase; here the catalysis of La2-xSrxCuO4+/-lambda (x = 0, 0.1, 0.7, 1) mixed oxides in phenol hydroxylation at lower temperatures are studied, and we find that the value of x has a significant effect on catalytic activity: the lower its value, the higher the catalytic activity; a mechanism is proposed to explain the experimental phenomena.

Carbon nanotubes as adsorbent of solid-phase extraction and matrix for laser desorption/ionization mass spectrometry

A method with carbon nanotubes functioning both as the adsorbent of solid-phase extraction (SPE) and the matrix for matrix assisted laser desorption/ ionization mass spectrometry (MALDI-MS) to analyze small molecules in solution has been developed. In this method, 10 muL suspensions of carbon nanotubes in 50% (vol/vol) methanol were added to the sample solution to extract analytes onto surface of carbon nanotubes because of their dramatic hydrophobicity. Carbon nanotubes in solution are deposited onto the bottom of tube with centrifugation. After removing the supernatant fluid, carbon nanotubes are suspended again with dispersant and pipetted directly onto the sample target of the MALDI-MS to perform a mass spectrometric analysis. It was demonstrated by analysis of a variety of small molecules that the resolution of peaks and the efficiency of desorption/ ionization on the carbon nanotubes are better than those on the activated carbon. It is found that with the addition of glycerol and sucrose to the dispersant, the intensity, the ratio of signal to noise (S/N), and the resolution of peaks for analytes by mass spectrometry increased greatly. Compared with the previously reported method by depositing sample solution onto thin layer of carbon nanotubes, it is observed that the detection limit for analytes can be enhanced about 10 to 100 times due to solid-phase extraction of analytes in solution by carbon nanotubes. An acceptable result of simultaneously quantitative analysis of three analytes in solution has been achieved. The application in determining drugs spiked into urine has also been realized. (C) 2004 American Society for Mass Spectrometry.

The kinetic-theory for dilute solid liquid 2-phase flow

On the basis of a brief review of the continuum theory for macroscopic descriptions and the kinetic theory for microscopic descriptions in solid/liquid two-phase flows, some suggestions are presented, i.e. the solid phase may be described by the Boltzmann equation and the liquid phase still be described by conservation laws in the continuum theory. Among them the action force on the particles by the liquid fluid is a coupling factor which connects the phases. For dilute steady solid/liquid two-phase flows, the particle velocity distribution function can be derived by analogy with the procedures in the kinetic theory of gas molecules for the equilibrium state instead of being assumed, as previous investigators did. This done, more detailed information, such as the velocity probability density distribution, mean velocity distribution and fluctuating intensity etc. can be obtained directly from the particle velocity distribution function or from its integration. Experiments have been performed for dilute solid/liquid two-phase flow in a 4 x 6 cm2 sized circulating square pipe system by means of laser Doppler anemometry so that the theories can be examined. The comparisons show that the theories agree very well with all the measured data.

Pharmacokinetics of sifuvirtide, a novel anti-HIV-1 peptide, in monkeys and its inhibitory concentration in vitro

Aim: To study the pharmacokinetics of sifuvirtide, a novel anti-human immunodeficiency virus (HIV) peptide, in monkeys and to compare the inhibitory concentrations of sifuvirtide and enfuvirtide on HIV-1-infected-cell fusion. Methods: Monkeys received 1.2 mg/kg iv or sc of sifuvirtide. An on-line solid-phase extraction procedure combined with liquid chromatography tandem mass spectrometry (SPELC/MS/MS) was established and applied to determine the concentration of sifuvirtide in monkey plasma. A four-I-127 iodinated peptide was used as an internal standard. Fifty percent inhibitory concentration (IC50) of sifuvirtide on cell fusion was determined by co-cultivation assay. Results: The assay was validated with good precision and accuracy. The calibration curve for sifuvirtide in plasma was linear over a range of 4.88-5000 mu g/L, with correlation coefficients above 0.9923. After iv or sc administration, the observed peak concentrations of sifuvirtide were 10626 +/- 2886 mu g/L and 528 +/- 191 mu g/L, and the terminal elimination half-lives (T,12) were 6.3 +/- 0.9 h and 5.5 +/- 1.0 h, respectively. After sc, T-max was 0.25-2 h, and the absolute bioavailability was 49% +/- 13%. Sifuvirtide inhibited the syncytium formation between HIV-1 chronically infected cells and uninfected cells with an IC50 of 0.33 mu g/L. Conclusion: An on-line SPE-LC/MS/MS approach was established for peptide pharmacokinetic studies. Sifuvirtide was rapidly absorbed subcutaneously into the blood circulation. The T-1/2 of sifuvirtide was remarkably longer than that of its analog, enfuvirtide, reported in healthy monkeys and it conferred a long-term plasma concentration level which was higher than its IC50 in vitro.

Simultaneous determination of microcystin-LR and its glutathione conjugate in fish tissues by liquid chromatography-tandem mass spectrometry

A sensitive and selective liquid chromatography-tandem mass spectrometry method was developed and validated for the simultaneous quantitative determination of microcystin-LR (MC-LR) and its glutathione conjugate (MC-LR-GSH) in fish tissues. The analytes were extracted from fish liver and kidney using 0.01 M EDTA-Na-2-5% acetic acid, followed by a solid-phase extraction (SPE) on Oasis HLB and silica cartridges. High-performance liquid chromatography (HPLC) with electrospray ionization mass spectrometry, operating in selected reaction monitoring (SRM) mode, was used to quantify MC-LR and its glutathione conjugate in fish liver and kidney. Recoveries of analytes were assessed at three concentrations (0.2, 1.0, and 5 mu g g(-1) dry weight [DW]) and ranged from 91 to 103% for MC-LR, and from 65.0 to 75.7% for MC-LR-GSH. The assay was linear within the range from 0.02 to 5.0 mu g g(-1) DW, with a limit of quantification (LOQ) of 0.02 mu g g(-1) DW. The limit of detection (LOD) of the method was 0.007 mu g g(-1) DW in both fish liver and kidney. The overall precision was determined on three different days. The values for within- and between-day precision in liver and kidney were within 15%. This method was applied to the identification and quantification of MC-LR and its glutathione conjugate in liver and kidney of fish with acute exposure of MC-LR. (c) 2007 Elsevier B.V. All rights reserved.

Sol-gel synthesis and properties of Ce1-xGdxO2-x/2 solid solutions

A series of solid electrolytes Ce1-xGdxO2-x/2(x=0 similar to0.6) was prepared by sol-gel method. The structure, thermal expansion coefficient and electrical properties of the solid solutions were systematically studied. XRD data showed that a complete cubic fluorite structure was formed at 160 degreesC. The purity of the product prepared by the sol-gel method is higher, the grain size is uniformly smaller. They were easily sintered into highly dense ceramic pellets at 1 300 degreesC. The sintering temperature was significantly lower than that by traditionally high temperature solid phase reaction method. The thermal expansion coefficient of Ce0.8Gd0.2O1.9, determined from high- temperature XRD data, is 8. 125 X 10(-6) K-1. Impedance spectra analyses showed that the grain-boundary resistance of the solid electrolyte prepared by sol-gel method was reduced or even eliminated. The conductivity of Ce0.8Gd0.2O1.9 is 5.26 X 10(-3) S/cm at 600 degreesC. The activation energy (E-a) is 0.82 eV.

Low temperature preparation and fuel cell properties of rare earth doped barium cerate solid electrolytes

The solid electrolytes, BaCe(0.8)Ln(0.2)O(2.9) (Ln: Gd, Sm, Eu), were prepared by the sol-gel method. XRD indicated that a pure orthorhombic phase was formed at 900 degrees C. The synthesis temperature by the sol-gel method was about 600 degrees C: lower than the high temperature solid phase reaction method. The electrical conductivity and impedance spectra were measured and the conduction mechanism was studied. The grain-boundary resistance of the solid electrolyte could be reduced or eliminated by the sol-gel method. The conductivity of BaCe0.8Gd0.2O2.9 is 7.87 x 10(-2) S.cm(-1) at 800 degrees C. The open-circuit voltage of hydrogen-oxygen fuel cell using BaCe0.8Gd0.2O2.9 as electrolyte was near to 1 V and its maximum power density was 30 mW.cm(-2).