Separation of perfluorocarboxylic acids using capillary electrophoresis with UV detection

A capillary electrophoretic method with UV detection for separation and quantitation of perfluorocarboxylic acids (PFCAs) from C6-PFCA to C12-PFCA has been developed. The optimization of measurement conditions included the choice of the most appropriate type and concentration of buffer in the background electrolyte (BGE), as well as the type and the content of an organic modifier. The optimal separation of investigated PFCAs was achieved with 50 mM phosphate buffer and 40% isopropanol in the BGE using direct UV detection. The optimum wavelength for direct UV detection was optimized at 190 nm. For indirect detection, several chromophores were studied. Five mM 3,5-Dinitrobenzoic acid (3,5-DNBA) in 20 mM phosphate buffer BGE and indirect UV detection at 280 nm gave the optimal detection and separation performance for the investigated PFCAs. The possibility of on-line preconcentration of solutes by stacking has been examined for indirect detection. The detection limits (LODs) determined for direct UV detection ranged from 2 microg/mL for C6-PFCA to 33 microg/mL for C12-PFCA. The LODs obtained for indirect UV detection were comparable to those obtained for direct UV detection.     

Quasi-steady state in the Michaelis–Menten system

We discuss the differential equations derived from the Michaelis–Menten model of an enzyme-catalyzed reaction, with no a priori conditions on parameters or initial concentrations. Using an elementary approach, we derive and investigate inequalities and conditions for the validity of the quasi-stationary approximation, confirming results by Segel and Slemrod, and determine new estimates for the pre-steady state period.     

Atomic quadrupolar photoemission asymmetry parameters from a solid state measurement

A method for measuring the asymmetry parameter gamma arising from dipole-quadrupole interference in core-level photoemission is proposed which is based on condensed thin films and exploits the influence of this asymmetry in photoemission monitoring of x-ray standing wave field absorption. The high density of material in this method offers some advantages over a conventional gas-phase measurement. Results are presented for C, O, and F 1s photoemission at photon energies around 3 keV. The combined nondipole asymmetry factor (delta+gamma/3) for non- s-states can be determined in a similar way.     

Interference of the electrospray voltage on chromatographic separations using porous graphitic carbon columns

The electrospray ionization (ESI) voltage is shown to interfere with liquid chromatographic separations performed with packed porous graphitic carbon (PGC) capillary columns. This interference is ascribed to the presence of an electric field over the conductive column in the absence of an earth point between the column and the ESI emitter. The current evolved alters the chromatographic behavior of the catecholamine metabolite 3-O-methyl-DOPA significantly, as both peak splitting and a dramatic decrease in the retention time were observed. Furthermore, the response from the mass spectrometer was decreased by 33% at the same time. A related compound, tyrosine, exhibited decreased retention times but no peak splitting, whereas no shifts in the retention times (or peak splitting) were seen for the less retained dopamine and noradrenaline. When the current through the PGC column was eliminated by the use of an earth point between the column and the ESI emitter, the chromatographic behavior of the column was found to return slowly to normal after hours of equilibration with 60 : 40 (v/v) methanol-ammonium formate buffer of pH 2.9. The behavior of the PGC column with and without the earth point was found to be highly reproducible during a period of 1 month. We propose that the effect of the ESI voltage on the chromatographic behavior of the PGC column is due to associated redox reactions affecting both the PGC particles and the analytes. It is concluded that (for analytical reasons), care should be taken to ensure that no current is flowing through the chromatographic system when interfacing PGC columns, and conducting parts in general, to ESI mass spectrometry.     

Arsenic complexes in the arsenic hyperaccumulator Pteris vittata (Chinese brake fern)

Pteris vittata (Chinese brake fern), the first reported arsenic (As) hyperaccumulating plant, can be potentially applied in the phytoremediation As-contaminated sites. Understanding the mechanisms of As tolerance and detoxification in this plant is critical to further enhance its capability of As hyperaccumulation. In this study, an unknown As species, other than arsenite (AsIII) or arsenate (AsV) was found in leaflets by using anion-exchange chromatography-hydride generation-atomic fluorescence spectroscopy and size-exclusion chromatography-atomic fluorescence spectrometry. The chromatographic behavior of this unknown As species and its stability suggest that it is likely an As complex. Although phytochelatin with two subunits (PC2) was the only major thiol in P. vittata under As exposure, this unknown As complex was unlikely to be an AsIII-PC2 complex by comparison of their chromatographic behaviors, stability at different pHs and charge states. The complex is sensitive to temperature and metal ions, but relatively insensitive to pH. In buffer solution of pH 5.9, it is present in a neutral form.     

Alkyne Addition and Insertion Reactions of [(Me3Si)3Si]2Ge⋅PMe3

Silylated germylene–PMe₃ adducts exchange their phosphane moiety smoothly for an N‐heterocyclic carbene or isocyanide species to form their respective base adducts. Reaction of the silylated germylene–PMe₃ adducts with monosubstituted alkynes produce germylene adducts with the alkyne inserted into a Ge?Si bond. A computational study of this process provides evidence for the initial formation of a germirene, which rearranges to a vinylgermylene species. The thermodynamic driving force for this reaction is provided by subsequent adduct formation with PMe₃. Reaction of the PMe₃ adduct of bis[(trimethylsilyl)silyl]germylene with disubstituted alkynes leads to the formation of stable germirenes, which can be isomerized further to silagermetes.     

Emergence,Reduction and Supervenience: A Varied Landscape

This is one of two papers about emergence, reduction and supervenience. It expounds these notions and analyses the general relations between them. The companion paper analyses the situation in physics, especially limiting relations between physical theories.