Profiling and biomarker identification in plasma from different Zucker rat strains via high mass accuracy multistage mass spectrometric analysis using liquid chromatography/mass spectrometry with a quadrupole ion trap-time of flight mass spectrometer

High mass accuracy electrospray ionisation multistage tandem mass spectrometry (MS(n)) was applied to metabolite profiling studies on plasma samples derived from two strains of rat (the Zucker (fa/fa) obese strain and the normal wild type). Using a quadrupole ion trap time-of-flight (QIT-TOF) mass spectrometer, metabolite profiling software was applied to locate components of biological significance that could account for the differences between the two strains of rat and a formula prediction software tool was used to help identify individual components. The primary factor discriminating between the two populations was the concentration of endogenous lipids. In the Zucker (fa/fa) obese strain, the dominant ion signals and MS(n) spectra were in agreement with lysoglycerophosphocholine components such as palmitoyllysophosphatidylcholine, 1-oleoylglycerophosphocholine, 1-octadecyl-sn-glycero-3-phosphocholine and 1-stearoylglycerophosphocholine and these were found in relatively higher concentrations compared to the normal wild type. Components were identified using high mass accuracy MS(n) data, formula prediction software and by agreement with published mass spectra through internet databases, rather than using a conventional approach with authentic standards. This application shows that the use of high mass accuracy electrospray ionisation MS(n) together with a software tool can be used effectively to detect and characterise unknown analytes in complex matrices, and represents a promising approach for future profiling studies.     

Photo-activation of Pd-catalyzed Sonogashira coupling using a Ru/bipyridine complex as energy transfer agent

The mixed catalyst system, Pd(CH3CN)2Cl2/P(t-Bu)3/[Ru(2,2'-bipyridine)3].2PF6, promotes the copper-free Sonogashira coupling reaction of aryl bromides at room temperature under irradiation of visible light.     

Reactions of sterically protected phosphaalkenes with some boron reagents

The reactions of sterically protected phosphaalkenes with some boron reagents, such as boron hydrides, were carried out leading to hydroboration products depending on the substrates and boron reagents. © 1999 John Wiley & Sons, Inc. Heteroatom Chem 10: 187–196, 1999     

Influence of Perfluoroarene–Arene Interactions on the Phase Behavior of Liquid Crystalline and Polymeric Materials

A stabilization of the liquid-crystalline mesophase and thus an enlarged temperature range of the mesogenic phase is achieved by adding perfluorotriphenylene to a chiral liquid-crystalline triphenylene. This mesophase is based on 1:1 perfluoroarene–arene interactions (see picture). In a polymer with triphenylenes as mesogens in the side chains, the addition of perfluorotriphenylene led to crystallization.     

Shape/size-controlled syntheses of metal nanoparticles for site-selective modification of carbon nanotubes

Shape- and size-controlled syntheses of metal nanoparticles have been achieved by galvanic displacement reaction between an aqueous solution of metal salt and Cu foil substrate. In particular, cubic and spheric nanoparticles of Pt (Au) with a fairly narrow size distribution were produced by reacting K(2)PtCl(4) (HAuCl(4)) with a Cu foil in an aqueous medium with and without CuCl(2) under different reaction conditions (e.g., different concentrations and reaction times). In conjunction with the substrate-enhanced electroless deposition (SEED) technique (Qu, L.; Dai, L. J. Am. Chem. Soc. 2005, 127, 10806), the shape/size-controlled syntheses have been successfully exploited to site-selectively deposit these metal nanoparticles onto the outerwall, innerwall, or end-tip of carbon nanotubes (CNTs). Asymmetric sidewall modification by attaching the innerwall and outerwall of CNTs with metal nanoparticles of different shapes was also achieved. Furthermore, it was demonstrated that the nanotube-supported Pt nanoparticles could be converted into hollow Au nanoboxes by galvanic displacement of Pt with Au. These CNT-supported metal nanoparticles were shown to possess interesting optical and electrocatalytic properties.     

Aromaticity on the pancake-bonded dimer of neutral phenalenyl radical as studied by MS and NMR spectroscopies and NICS analysis

We have demonstrated the first MS and NMR observation of a face-to-face pi-bonded dimer of an organic radical (pancake-bonded dimer coined by R. S. Mulliken) in solution, using tri-tert-butylated phenalenyl radical 1, a 3-fold symmetric neutral hydrocarbon. In addition to the direct detection of the dimer signal by cold-spray ionization mass spectrometry (CSI-MS), 1H and 13C NMR spectra in solution gave definitive evidence of a well-defined D3d dimer structure with a 12-center-2-electron-long C-C bond formation, which is the same symmetry as seen in the crystalline state. On the basis of the NMR peaks of the dimer in the aromatic region (6.47 ppm for 1H NMR and 120-143 ppm for 13C NMR), we carried out nucleus-independent chemical shift (NICS) analysis, which showed that the ring center of the dimer became more aromatic (-7.1 ppm) than that of the monomer (-3.8 ppm). The trend of aromaticity generation was more pronounced in the interior of the dimer, which has been interpreted by the negative electron density induced in the bonding region as seen in the electrostatic potential surface.     

Effect of Flow Structures on Turbulence Statistics of Taylor-Couette Flow in the Torque Transition State

Direct numerical simulations of Taylor-Couette flow from Re= 8000 to 25000 have been conducted to investigate changes of turbulence statistics in the transition of the Reynolds number dependency of the mean torque near Re= 10000. The velocity fluctuations are decomposed into the contributions of the Taylor vortex and remaining turbulent fluctuations. Significant Reynolds number dependencies of these components are observed in the radial profiles of the Reynolds stress and the transmission of the mean torque. The contributions of Taylor vortex and turbulent components in the net amount of mean torque are evaluated. The Taylor vortex component is overtaken by the turbulent counterpart around Re= 15000 when they are defined as the azimuthally averaged component and the remnants. The results show that the torque transition can be explained by the competition between the contributions of azimuthally averaged Taylor vortex and the remaining turbulent components.