Analysis of aromatic compounds in gasoline with flow-switching comprehensive two-dimensional gas chromatography

A comprehensive two-dimensional gas chromatography (GC x GC) instrument has been created by coupling a flow-switching modulator and a standard gas chromatograph. The instrument was used to characterize the aromatic composition of gasoline. The high-resolution separation produced by flow-switching GC x GC allowed gasoline aromatics to be fully resolved from saturated components. The aromatic compounds were further separated into groups having the same carbon number. A standard gasoline sample was analyzed to evaluate the quantitative accuracy and precision of this technique. The data show that flow-switching GC x GC produces results that are comparable to gas chromatography-mass spectrometry (GC-MS) and thermal modulation GC x GC. The simple, low-cost, and robust nature of flow-switching GC x GC makes it an ideal technique for the routine analysis of aromatic compounds in gasoline.     

Delamination of layered double hydroxides in polar monomers: new LDH-acrylate nanocomposites

The layered double hydroxide Mg2Al(OH)6(C12H25SO4) was delaminated to give high levels of inclusion in acrylate monomers; subsequent polymerisation of the monomers containing the LDH dispersion gave polyacrylates with the inorganic component still in the delaminated form.     

Structural basis for thrombin activation of a protease-activated receptor: inhibition of intramolecular liganding

Protease-activated G protein-coupled receptors (PAR1-4) are tethered-ligand receptors that are activated by proteolytic cleavage of the extracellular domain (exodomain) of the receptor. PAR1, the prototypic member of the PAR family, is the high-affinity thrombin receptor of platelets and vascular endothelium and plays a critical role in blood coagulation, thrombosis, and inflammation. Here, we describe the solution structure of the thrombin-cleaved exodomain of PAR1. The side chains of a hydrophobic hirudin-like (Hir) sequence and adjacent anionic motif project into solution. Docking of the exodomain Hir sequence to exosite I of thrombin reveals that the tethered ligand in the cleaved exodomain bends away from thrombin, leaving its active site available to another large macromolecular substrate. The N-terminal ligand is longer than anticipated and forms an intramolecular complex with a region located in the C terminus of the exodomain. Mutational analysis confirmed that this C-terminal region is a ligand binding site for both intra- and intermolecular ligands. A lipidated-ligand binding site peptide was found to be an effective inhibitor of thrombin-induced platelet aggregation.     

Resonance Energy Transfer in a Genetically Engineered Polypeptide Results in Unanticipated Fluorescence Intensity

The fluorescence intensity of a C-terminal acceptor chromophore, N-(7-dimethylamino-4-methyl coumarin (DACM), increased proportionally with 280 nm irradiation of an increasing number of donor tryptophan residues located on a β-sheet forming polypeptide. The fluorescence intensity of the acceptor chromophore increased even as the length of the β-sheet edge approached 256 Å, well beyond the Förster radius for the tryptophan–acceptor chromophore pair. The folding of the peptides under investigation was verified by circular dichroism (CD) and deep UV resonance Raman experiments. Control experiments showed that the enhancement of DACM fluorescence occurred concomitantly with peptide folding. In other control experiments, the DACM fluorescence intensity of the solutions of tryptophan and DACM did not show any enhancement of DACM fluorescence with increasing tryptophan concentrations. Formation of fibrillar aggregates of the substrate peptides prepared for the fluorescence studies was undetectable by thioflavin T (ThT) fluorescence.     

High pressure fast-flow technique for gas phase kinetics studies

A fast-flow technique suitable for measuring elementary rate constants over a wide range of pressures has been developed. The method operates under turbulent flow conditions, in contrast to laminar flow which characterizes the conventional low pressure technique. Flow visualization, velocity profile measurements, and tracer pulse studies have been carried out in a flow tube reactor to investigate the dynamics of both laminar and turbulent flow for chemical kinetics purposes. Furthermore, the wall collision frequency for the reactants has been determined: at the higher pressures it is greatly reduced in comparison with the frequency characteristic of the conventional low pressure laminar flow technique. Also, to test and validate the technique the bimolecular rate constants for the reactions H+Cl₂ and H+O₃ have been measured at total pressures in the 3–300 torr range; at pressures below 5 torr, as well as above 50 torr in the turbulent flow regime the agreement with the recommended literature values is excellent. © 1993 John Wiley & Sons, Inc.     

Enhancement of protein sensitivity for MALDI imaging mass spectrometry after chemical treatment of tissue sections

MALDI imaging mass spectrometry (IMS) has become a valuable tool for the investigation of the content and distribution of molecular species in tissue specimens. Numerous methodological improvements have been made to optimize tissue section preparation and matrix deposition protocols, as well as MS data acquisition and processing. In particular for proteomic analyses, washing the tissue sections before matrix deposition has proven useful to improve spectral qualities by increasing ion yields and the number of signals observed. We systematically explore here the effects of several solvent combinations for washing tissue sections. To minimize experimental variability, all of the measurements were performed on serial sections cut from a single mouse liver tissue block. Several other key steps of the process such as matrix deposition and MS data acquisition and processing have also been automated or standardized. To assess efficacy, after each washing procedure the total ion current and number of peaks were counted from the resulting protein profiles. These results were correlated to on-tissue measurements obtained for lipids. Using similar approaches, several selected washing procedures were also tested for their ability to extend the lifetime as well as revive previously cut tissue sections. The effects of these washes on automated matrix deposition and crystallization behavior as well as their ability to preserve tissue histology were also studied. Finally, in a full-scale IMS study, these washing procedures were tested on a human renal cell carcinoma biopsy.     

Analysis of biodiesel/petroleum diesel blends with comprehensive two-dimensional gas chromatography

Comprehensive two-dimensional gas chromatography (GCxGC) is used to analyze petroleum diesel, biodiesel, and biodiesel/petroleum diesel blends. The GCxGC instrument is assembled from a conventional gas chromatograph fitted with a simple, in-line fluidic modulator. A 5% phenyl polydimethylsiloxane primary column is coupled to a polyethylene glycol secondary column. This column combination generates chromatograms where the fatty acid methyl esters (FAMEs) found in biodiesel occupy a region that is also populated by numerous cyclic alkanes and monoaromatics found in petroleum. Fortunately, the intensities of the petroleum hydrocarbon peaks are far lower than the intensities of the FAME peaks, even for blends with low biodiesel content. This allows the FAMEs to be accurately quantitated by direct integration. The method is calibrated by analyzing standard mixtures of soybean biodiesel in petroleum diesel with concentrations ranging from 1 to 20% v/v. The resulting calibration curve displays excellent linearity. This curve is used to determine the concentration of a B20 biodiesel/petroleum diesel blend obtained from a local retailer. Excellent precision and accuracy are obtained.     

Reactions of small negative ions with O2(a Δg) and O2(X Σg)

The rate constants and product ion branching ratios were measured for the reactions of various small negative ions with O₂(X ³Σ_g⁻) and O₂(a ¹Δ_g) in a selected ion flow tube (SIFT). Only NH₂⁻ and CH₃O⁻ were found to react with O₂(X) and both reactions were slow. CH₃O⁻ reacted by hydride transfer, both with and without electron detachment. NH₂⁻ formed both OH⁻, as observed previously, and O₂⁻, the latter via endothermic charge transfer. A temperature study revealed a negative temperature dependence for the former channel and Arrhenius behavior for the endothermic channel, resulting in an overall rate constant with a minimum at 500 K. SF₆⁻, SF₄⁻, SO₃⁻ and CO₃⁻ were found to react with O₂(a ¹Δ_g) with rate constants less than 10⁻¹¹ cm³ s⁻¹. NH₂⁻ reacted rapidly with O₂(a ¹Δ_g) by charge transfer. The reactions of HO₂⁻ and SO₂⁻ proceeded moderately with competition between Penning detachment and charge transfer. SO₂⁻ produced a SO₄⁻ cluster product in 2% of reactions and HO₂⁻ produced O₃⁻ in 13% of the reactions. CH₃O⁻ proceeded essentially at the collision rate by hydride transfer, again both with and without electron detachment. These results show that charge transfer to O₂(a ¹Δ_g) occurs readily if the there are no restrictions on the ion beyond the reaction thermodynamics. The SO₂⁻ and HO₂⁻ reactions with O₂(a) are the only known reactions involving Penning detachment besides the reaction with O₂⁻ studied previously [R.S. Berry, Phys. Chem. Chem. Phys., 7 (2005) 289–290].