Electron-capture gas chromatographic analysis of beta-phenylethylamine in tissues and body fluids using pentafluorobenzenesulfonyl chloride for derivatization

A gas chromatographic procedure is described for the analysis of beta-phenylethylamine (PEA) in tissues and body fluids. The method involves the use of pentafluorobenzenesulfonyl chloride for extraction and derivatization of PEA. This is followed by separation and analysis of the derivatized amine on a gas chromatograph equipped with a fused-silica capillary column and an electron-capture detector. The procedure is rapid, provides a stable and sensitive derivative, and has been applied to analysis of PEA in brain, heart, kidney, liver, lung, spleen and blood from the rat and urine from human subjects.     

The fragmentation of ortho-methoxyphenyl-2-propanone oximes and related compounds–further examples of an ortho-effect

An [M ? 31]⁺ ion was a prominent fragment in the mass spectra of three ortho-methoxy-phenyl-2-propanone oximes and is shown to be due to the expulsion of a methoxyl radical from the molecular ion as a result of an ortho-effect. In contrast, an [M ? 31]⁺ ion was absent from the spectra of a structurally related ketone and a hydroxylamine, and was not observed in the spectra of meta- and para-methoxyphenyl-2-propanone oximes.     

Systems-based design of bi-ligand inhibitors of oxidoreductases: filling the chemical proteomic toolbox

Genomics-driven growth in the number of enzymes of unknown function has created a need for better strategies to characterize them. Since enzyme inhibitors have traditionally served this purpose, we present here an efficient systems-based inhibitor design strategy, enabled by bioinformatic and NMR structural developments. First, we parse the oxidoreductase gene family into structural subfamilies termed pharmacofamilies, which share pharmacophore features in their cofactor binding sites. Then we identify a ligand for this site and use NMR-based binding site mapping (NMR SOLVE) to determine where to extend a combinatorial library, such that diversity elements are directed into the adjacent substrate site. The cofactor mimic is reused in the library in a manner that parallels the reuse of cofactor domains in the oxidoreductase gene family. A library designed in this manner yielded specific inhibitors for multiple oxidoreductases.     

Synthesis of 2H-1-benzopyrans via palladacycles with a metal-bonded stereogenic carbon

[reaction: see text] Stable oxapalladacycles have been prepared and converted into a series of highly functionalized 2H-1-benzopyrans via regioselective insertion of activated alkynes.     

Three-level operation of a diode-bar-pumped Yb:S-FAP laser

We present an all solid-state Yb:S-FAP laser system running on the three-level laser transition at 985 nm. The pump source was a high fill-factor laser diode bar, with the output reformatted using a two-mirror beamshaping system to produce a rectangular pump beam that focused to a square spot. A nearly on-axis multipassing system was used to obtain four pump passes through a 1.6 mm Yb:S-FAP laser crystal. Gain-switched three-level laser output was achieved with an efficiency of 4.3% with respect to incident pump power. Electro-optic Q-switching produced 0.12 mJ pulses for a pump pulse energy of 11 mJ. Intra-cavity second-harmonic generation yielded a maximum pulse energy at 492.5 nm of 12 μJ.     

Investigation of practical high repetition rate copper vapour lasers with external heating

The characteristics of high repetition rate CVL devices incorporating passive external heating have been investigated. Pre-heating of the CVL plasma tube using external heating has been shown to significantly reduce CVL warm-up time, while supplementary heating of the CVL plasma tube using external heating allows efficient CVL operation with reduced discharge power input without any degradation in output power.     

Motor premium rating

This paper outlines a very simple structure for the practical analysis of motor premiums from a UK point of view. It indicates that it is possible to model different types of claims cost. These results are combined together with some simple economic assumptions, to arrive at premiums. Then the paper develops a ‘points system’ which is similar to a number of premium systems operated by UK Insurance Companies. This ‘points system’ is used to compare different sets of assumptions. Finally, an analysis of surplus is described with an example.     

Structural and electrical properties of granular metal films

Granular metal films (50–200,000 Å thick) were prepared by co-sputtering metals (Ni, Pt, Au) and insulators (SiO₂, Al₂O₃), where the volume fraction of metal, x, was varied from x = 1 to x = 0.05. The materials were characterized by electron micrography, electron and X-ray diffraction, and measurements of composition, density and electrical resistivity at electric fields ε up to 10⁶ V/cm and temperatures T in the range of 1.3 to 291 K. In the metallic regime (isolated insulator particles in a metal continuum) and in the transition regime (metal and insulator particles in a metal continuum) and in the transition regime (metal and insulator labyrinth structure) the conduction is due to percolation with a percolation threshold at x?0.5. Tunnelling measurements on superconductor-insulator-granular metal junctions reveals that the transition from the metallic regime to the dielectric regime (10–50 Å size isolated metal particles in an insulator continuum) is associated with the breaking up of a metal continuum into isolated metal particles. In the dielectric regime the temperature dependence of the low-field resistivity is given by ρL = ρo exp [2√(C/kT)], and the field dependence of the high-field, low-temperature resistivity is given by ρH = ρ∞ exp (εo/ε), where ρo, ρ∞, C, and εo are material constants. A simple theory based on the assumption that the ratio s/d (d-metal particle size and s-separation between particles) is a function only of composition yields expressions for ρ(ε, T) in excellent agreement with experiment. Furthermore, the theory predicts the experimental finding that the resistivity can be expressed in terms of a universal function of the reduced variables kT/C and ε/εo. The inter-relationship between all the important physical properties of granular metals and their structure is also discussed.     

Classification of Convex Ancient Solutions to Curve Shortening Flow on the Sphere

We prove that the only closed, embedded ancient solutions to the curve shortening flow on \(\mathbb {S}^2\) are equators or shrinking circles, starting at an equator at time \(t=-\infty \) and collapsing to the north pole at time \(t=0\). To obtain the result, we first prove a Harnack inequality for the curve shortening flow on the sphere. Then an application of the Gauss–Bonnet, easily allows us to obtain curvature bounds for ancient solutions leading to backwards smooth convergence to an equator. To complete the proof, we use an Aleksandrov reflection argument to show that maximal symmetry is preserved under the flow.     

Developing and applying quantitative skills maps for STEM curricula,with a focus on different modes of learning

Mapping quantitative skills across the science, technology, engineering and mathematics (STEM) curricula will help educators identify gaps and duplication in the teaching, practice and assessment of the necessary skills. This paper describes the development and implementation of quantitative skills mapping tools for courses in STEM at a regional university that offers both on-campus and distance modes of study. Key elements of the mapping project included the identification of key graduate quantitative skills, the development of curriculum mapping tools to record in which unit(s) and at what level of attainment each quantitative skill is taught, practised and assessed, and identification of differences in the way quantitative skills are developed for on-campus and distance students. Particular attention is given to the differences that are associated with intensive schools, which consist of concentrated periods of face-to-face learning over a three-four day period, and are available to distance education students enrolled in STEM units. The detailed quantitative skills mapping process has had an impact on the review of first-year mathematics units, resulted in crucial changes to the curriculum in a number of courses, and contributed to a more integrated approach, and a collective responsibility, to the development of students' quantitative skills for both face-to-face and online modes of learning.