Esterification of perfluorinated carboxylic acids with bromomethyl aromatic compounds for gas chromatography combined with laser ionization mass spectrometry.

Perfluorinated carboxylic acids (PFCAs) were derivatized with two types of aromatic compounds that contained a bromomethyl group, i.e., 2-(bromomethyl)naphthalene (BMN) and benzyl bromide (BB). The conditions for derivatization were optimized in terms of reaction temperature and time and the concentration of derivatizing reagent. Using these optimal conditions, the PFCAs-MN and PFCAs-B derivatives were measured by gas chromatography (GC) combined with mass spectrometry using an ultraviolet femtosecond laser (267 nm) as the ionization source. The efficiency of derivatization for PFCAs-B was higher than that for PFCAs-MN because of the smaller size of the chromophore (benzene). The ionization efficiency of PFCAs-MN, however, was better than PFCAs-B, since a larger sized chromophore (naphthalene) and then a larger molar absorptivity was preferable for resonance-enhanced two-photon ionization. Due to superior GC separation, BB was successfully used as the derivatizing agent for the trace analysis of PFCAs, with detection limits of 6.0, 8.4, and 9.5 ng/mL for perfluoroheptanoic, perfluorooctanoic, and perfluorononanoic acids, respectively. The other bromomethyl aromatic compounds were evaluated for use as a derivatization reagent in future studies.

Atomic PdAu Interlayer Sandwiched into Pd/Pt Core/Shell Nanowires Achieves Superstable Oxygen Reduction Catalysis.

Rationally designing the core/shell architecture of Pt-based electrocatalysts has been demonstrated as an effective way to induce a surface strain effect for promoting the sluggish kinetics of the oxygen reduction reaction (ORR) at the cathode of fuel cells. However, unstable core dissolution and structural collapse usually occur in Pt-based core/shell catalysts during the long-term cycling operation, greatly impacting actual fuel cell applications. Impeding the dissolution of cores beneath the Pt shells is the key to enhancing the catalytic stability of materials. Herein, a method for sandwiching atomic PdAu interlayers into one-dimensional (1D) Pd/Pt core/shell nanowires (NWs) is developed to greatly boost the catalytic stability of subnanometer Pt shells for ORR. The Pd/PdAu/Pt core/shell/shell NWs display only 7.80% degradation of ORR mass activity over 80 000 potential cycles with no dissolution of Pd cores and good preservation of the holistic sandwich core/shell nanostructures. This is a significant improvement of electrocatalytic stability compared with the Pd/Pt core/shell NWs, which deformed and inactivated over 80 000 potential cycles. The density functional theory (DFT) calculations further demonstrate that the electron-transfer bridge Pd and electron reservoir Au, serving in the PdAu atomic interlayer, both guarantee the preservation of the high electroactivity of surface Pt sites during the long-term ORR stability test. In addition, the Pd/PdAu/Pt NWs show a 1.7-fold higher mass activity (MA) for ORR than the conventional Pd/Pt NWs. The enhanced activity can be attributed to the strong interaction between PdAu interlayers and subnanometer-Pt shells, which suppresses the competitive Pd-4d bands and boosts the surface Pt-5d bands toward the Fermi level for higher electroactivity, proved from DFT.

Determination of tandospirone in human plasma by a liquid chromatography-tandem mass spectrometry method.

A rapid, sensitive, and selective liquid chromatography-tandem mass spectrometry method for the detection of tandospirone in human plasma is described. It was employed in a pharmacokinetic study. The analyte and internal standard diphenhydramine were extracted from plasma using liquid-liquid extraction, then separated on a Zorbax XDB C(18) column using a mobile phase of methanol-water-formic acid (80:20:0.5, v/v/v). The detection was performed with a tandem mass spectrometer equipped with an electrospray ionization source. Linearity was established in the concentration range of 10.0-5,000 pg/ml. The lower limit of quantification was 10.0 pg/ml. The intraday and interday relative standard deviation across three validation runs over the entire concentration range was less than 13%. Accuracy determined at three concentrations (25.0, 200, and 4,000 pg/ml for tandospirone) ranged from 94.4 to 102.1%. Each plasma sample was chromatographed within 3.4 min. The method proved to be highly selective and suitable for bioequivalence evaluation of different formulations containing tandospirone and clinical pharmacokinetic investigation of tandospirone.

Determination of zolmitriptan in human plasma by liquid chromatography-tandem mass spectrometry method: application to a pharmacokinetic study.

A sensitive and selective liquid chromatography-tandem spectrometry method for the determination of zolmitriptan was developed and validated over the linearity range 0.05-30 ng/ml with 0.5 ml of plasma using diphenhydramine as the internal standard. Liquid-liquid extraction using a mixture of diethyl ether and dichloromethane was used to extract the drug and the internal standard from plasma. The mass spectrometer was operated under the selected reaction monitoring (SRM) mode using the atmospheric pressure chemical ionization (APCI) technique. The instrument parameters were optimized to obtain 3.0 min run time. The mobile phase consisted of acetonitrile-water-formic acid (70:30:0.5), at a flow rate of 0.5 ml/min. In positive mode, zolmitriptan produced a protonated precursor ion at m/z 288 and a corresponding product ion at m/z 58. And internal standard produced a protonated precursor ion at m/z 256 and a corresponding product ion at m/z 167. The inter- and intra-day precision (%R.S.D.) were less than 8.5% and accuracy (%error) was less than -2.5%. The method had a lower limit of quantification of 0.05 ng/ml for zolmitriptan, which offered increased sensitivity and selectivity of analysis, compared with existing methods. The method was successfully applied to a pharmacokinetic study of zolmitriptan after an oral administration of 5 mg zolmitriptan to 20 healthy volunteers.

Simultaneous determination of pantoprazole and its two metabolites in dog plasma by HPLC.

A simple and sensitive high-performance liquid chromatography (HPLC) method is developed and validated for simultaneous determination of pantoprazole and its two metabolites (pantoprazole sulfone and pantoprazole thioether) in dog plasma and applied to a pharmacokinetic study in Beagle dogs. Following a protein precipitation procedure, the samples are separated using reversed-phase HPLC (C18) by a gradient of acetonitrile and ammonium acetate (pH 6.0) at a flow rate of 1.0 mL/min and quantitated using UV detection at 290 nm. Omeprazole is selected as the internal standard. The method has a lower limit of quantitation of 0.025 microg/mL for pantoprazole and its two metabolites, using 0.1-mL aliquots of plasma. The linear calibration curves are obtained in the concentration range of 0.025-10.0 microg/mL for three analytes. The intra- and interrun precision (relative standard deviation), calculated from quality control (QC) samples, is less than 13% for three analytes. The accuracy determined from QC samples is between -6.4% and 12%.

Determination of glufosfamide in rat plasma by liquid chromatography/tandem mass spectrometry.

A sensitive and selective high-performance analytical method based on liquid chromatography with tandem mass spectrometric detection (LC/MS/MS) was developed for the quantification of glufosfamide in rat plasma. Zidovudine was employed as internal standard. Glufosfamide was determined after methanol-mediated plasma protein precipitation using LC/MS/MS with an electrospray ionization interface in negative ion mode. Two sets of standard curves were developed, from 0.005 to 1.0 microg/mL and from 1.0 to 50.0 microg/mL. The assay was accurate (% deviations from nominal concentrations < 5%), precise and reproducible (intra- and inter-day coefficients of variation < 10%). Glufosfamide in rat plasma was stable over three freeze/thaw cycles, and at ambient temperatures, for at least 2 h. The validated method was successfully applied to the determination of glufosfamide plasma concentrations in rats for 24 h following an intravenous administration of 25 mg/kg.