On-line identification of trans-resveratrol in red wine using a sweeping technique combined with capillary electrophoresis/77 K fluorescence spectroscopy

The feasibility of combining the techniques of on-line concentration and capillary electrophoresis/low-temperature fluorescence spectroscopy (CE/LTFS) for the detection and identification of trans-resveratrol in red wine at 77 K is demonstrated for the first time. This technique, involving sweeping-micellar electrokinetic chromatography (sweeping-MEKC), was used for the initial on-line concentration and separation, after which a cryogenic molecular fluorescence experiment was performed at 77 K. In comparison with normal-MEKC mode, a approximately 1500-fold improvement in detection sensitivity could be obtained when the sweeping-MEKC was applied. The proposed method permits not only the separation and detection of trans-resveratrol from red wine extracts but also ensures that the on-line spectrum is readily distinguishable and can be unambiguously assigned at 77 K.     

Increasing throughput of parallel on-line extraction liquid chromatography/electrospray ionization tandem mass spectrometry system for GLP quantitative bioanalysis in drug development

An approach is described with turbulent flow on-line extraction liquid chromatography/electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) for GLP quantitative bioanalysis of a drug candidate. Two systems were built in-house with standard laboratory parts and equipments. One system consisted of one gradient HPLC pump, one isocratic pump, one ten-port valve, two turbulent flow columns, one analytical column, one autosampler and one mass spectrometer. Using this system, an injection-to-injection cycle time of 0.8 min was achieved. By adding an additional valve, another analytical column and an isocratic pump, the injection-to-injection cycle time decreased to 0.4 min. Validation results from the two systems showed that precision and accuracy were acceptable for GLP quantitative analyses. The system was utilized to support sample bioanalysis of a drug candidate in a first-time in-human clinical trial.     

Tetrafluorine‐Containing Ketones and Acetoacetates: Synthesis and Mechanistic Study

Addition of trimethylsilyl trifluoroacetate to the carbanions of α‐fluorobenzyl‐phosphonate ( 3 ) or diisopropyl(fluorocarbethoxymethyl)phosphonate ( 9 ) formed the corresponding intermediates [CF₃C(O)CFPh]^?Li⁺ ( 10 ) and [CF₃C(O)CFCO₂Et]^?Li⁺ ( 11 ), respectively. Subsequent protonation, alkylation or allylation of 10 and 11 afforded trifluoromethyl fluorobenzyl ketones 12 and ethyl 2,4,4,4‐tetra‐fluoroacetoacetates 13 . Based on the results obtained, a plausible mechanism was proposed.     

Cadmium Determination in Human Whole Blood by Electrothermal Atomic Absorption Spectrometry with Magnesium Chloride and Sodium Hydroxide as a Combined Chemical Modifier

In this work, we propose a method to determine trace amounts of Cd in human whole blood samples by electrothermal atomic absorption spectrometry (ETAAS) with the combined chemical modifier including magnesium chloride and sodium hydroxide. Prior to the ETAAS analysis, dissolution of the blood samples is accomplished using a HNO₃-HClO₄double closed-vessel microwave digestion technique followed by drying of the dissolved blood samples by means of an infrared lamp. In using this approach, a MgCl₂ chemical modifier is added to the digested samples, then they are injected into the graphite furnace for detecting the Cd level via atomic absorption spectrometer. Besides we used a NaOH chemical modifier, which removed the matrix major elements through prior ashing at 1200 ° C for 30 s, and the Cd is subsequently volatilized at 2200 °C and determined by AAS. However, the proposed method can be employed to determine the of Cd level in whole blood samples by the calibration technique and the standard-additions method. Its validity is confirmed with two certified reference whole blood materials (Seronorm Trace Elements Whole Blood Batch no. 205052 and Batch no. 203056). By using 10 μL injections, a detection limit of 0.052 ng mL^?1 is achieved.     

Cassette-accelerated rapid rat screen: a systematic procedure for the dosing and liquid chromatography/atmospheric pressure ionization tandem mass spectrometric analysis of new chemical entities as part of new drug discovery

This report addresses the continuing need for increased throughput in the evaluation of new chemical entities (NCEs) in terms of their pharmacokinetic (PK) parameters by describing an alternative procedure for increasing the throughput of the in vivo screening of NCEs in the oral rat PK model. The new approach is called "cassette-accelerated rapid rat screen" (CARRS). In this assay, NCEs are dosed individually (n = 2 rats/compound) in batches of six compounds per set. The assay makes use of a semi-automated protein precipitation procedure for sample preparation in a 96-well plate format. The liquid chromatography/atmospheric pressure ionization tandem mass spectrometry (LC/API-MS/MS) assay is also streamlined by analyzing the samples as "cassettes of six". Using this new approach, a threefold increase in throughput was achieved over the previously reported "rapid rat screen".     

Raman scattering and efficient UV photoluminescence from well-aligned ZnO nanowires epitaxially grown on GaN buffer layer

Optical phonon confinement and efficient UV emission of ZnO nanowires were investigated in use of resonant Raman scattering (RRS) and photoluminescence (PL). The high-quality ZnO nanowires with diameters of 80-100 nm and lengths of several micrometers were epitaxially grown through a simple low-pressure vapor-phase deposition method at temperature 550 degrees C on the precoated GaN(0001) buffer layer. The increasing intensity ratio of n-order longitudinal optical (LO) phonon (A(1)(nLO)/E(1)(nLO)) with increasing scattering order in RRS reveals the phonon quantum confinement as shrinking the diameter of ZnO nanowires. The exciton-related recombination near the band-edge transition dominate the UV emissions at room temperature as well as at low temperature that exhibits almost no other nonstoichiometric defects in the ZnO nanowires.