Amine-functionalised SBA-15 of tailored pore size for heavy metal adsorption

This study examines the synthesis of SBA-15 with tailored pore sizes through controlled thermal treatment for the adsorption of Pb and Cd ions. The aim is to produce a material that can adsorb heavy metals at both high and low concentrations. The materials were characterised by means of N(2) physisorption, powder X-ray diffraction (PXRD), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), microanalysis and transmission electron microscopy (TEM). The surface areas ranged from 410 to 871 m(2)g(-1), and pore diameter was increased from 5.9 to 10.8 nm. This method allows for maximum adsorption of metal ions at very low concentrations. Metal ion adsorption was determined using an Atomic Absorption Spectrophotometer. The effects of pH were found to play a major role in the precipitation and, therefore, adsorption of metal ions. This method proved to be efficient at adsorbing large quantities of both metals (39 and 41 mg g(-1) for Pb and Cd, respectively).     

Quantitative Acoustic Microscopy for Determination of Properties of Hard Coatings

 For quantitative assessment of the properties of hard coatings there is an increasing demand for testing methods with high reliability of the test results, especially concerning the independence of the method and the comparability between different laboratories. This includes the knowledge about all the factors which influence the test procedure itself, determination of best testing conditions, testing of these conditions in round-robins to get a view of the comparability of results, and formulation of guidelines for standardization. In a European project several test methods for hard coatings on steel were investigated for this purpose and the elastic moduli of the coating and coating thickness were determined non-destructively by means of quantitative acoustic microscopy. This method and the instruments available had not yet been certified in the fields of coatings simply owing to the absence of standardised signal processing, followed by the determination of sound velocities and materials parameter extraction. For this purpose four laboratories carried out investigations and measurements on reference samples and on two types of hard coatings (titanium nitride and C-doped chromium) on M2 tool steel.     

Efficient pairing computation on supersingular Abelian varieties

We present a general technique for the efficient computation of pairings on Jacobians of supersingular curves. This formulation, which we call the eta pairing, generalizes results of Duursma and Lee for computing the Tate pairing on supersingular elliptic curves in characteristic 3. We then show how our general technique leads to a new algorithm which is about twice as fast as the Duursma–Lee method. These ideas are applied to elliptic and hyperelliptic curves in characteristic 2 with very efficient results. In particular, the hyperelliptic case is faster than all previously known pairing algorithms.      

Distorted-wave Born approximation calculations of (e, 2e) reactions

The distorted-wave Born approximation (DW-BA) is discussed and samples of calculations are presented for ionization of the 2p inner shell of Ar, the 5p, 5s and 4d shells of Xe, and for ionization of He in asymmetric perpendicular plane geometry. Agreement with measurements of inner shell ionization of Ar is excellent. It is pointed out that triple differential cross sections for ionization of heavy atoms can exhibit much structure, which presents a challenge to both theory and experiment. Particular cases of 5s and 4d ionization of Xe are given as examples of situations worthy of experimental investigation. Comparison is made with very recent measurements of ionization of He in asymmetric perpendicular plane geometry. In agreement with experiment, DWBA shows at all incident energies a single main peak at φ=180°, where φ is the angle between the outgoing electrons. It is demonstrated that at high energies this peak arises from a double collison mechanism. This contrasts with energy-sharing ionization into the perpendicular plane where the double collision mechanism, dominant at high energies, gives a peak at φ=90°, and where with reducing energy this peak is replaced by one at φ=180° coming from the single collision mechanism. Suggestions are made for further experiments.     

The efficiency of immobilised glutamate oxidase decreases with surface enzyme loading: an electrostatic effect, and reversal by a polycation significantly enhances biosensor sensitivity

The apparent Michaelis constant, K(M), for glutamate oxidase (GluOx) immobilised on Pt electrodes increased systematically with enzyme loading. The effect was due, at least in part, to electrostatic repulsion between neighbouring oxidase molecules and the anionic substrate, glutamate (Glu). This understanding has allowed us to increase the Glu sensitivity of GluOx-based amperometric biosensors in the linear response region (100+/-11 nA cm(-2)microM(-1) at pH 7.4; SD, n=23) by incorporating a polycation (polyethyleneimine, PEI) to counterbalance the polyanionic protein. Differences in the behaviour of glucose biosensors of a similar configuration highlight a limitation of using glucose oxidase as a model enzyme in biosensor design.     

Absolute net charge and the biological activity of oligopeptides

Sequences of human proteins are frequently prepared as synthetic oligopeptides to assess their functional ability to act as compounds modulating pathways involving the parent protein. Our objective was to analyze a set of oligopeptides, to determine if their solubility or activity correlated with features of their primary sequence, or with features of properties inferred from three-dimensional structural models derived by conformational searches. We generated a conformational database for a set of 78 oligopeptides, derived from human proteins, and correlated their 3D structures with solubility and biological assay activity (as measured by platelet activation and inhibition). Parameters of these conformers (frequency of coil, frequency of turns, the degree of packing, and the energy) did not correlate with solubility, which was instead partly predicted by two measures obtained from primary sequence analysis, that is, the hydrophobic moment and the number of charges. The platelet activity of peptides was correlated with a parameter derived from the structural modeling; this was the second virial coefficient (a measure of the tendency for a structure to autoaggregate). This could be explained by an excess among the active peptides of those which had either a large number of positive charges or in some cases a large number of negative charges, with a corresponding deficit of peptides with a mixture of negative and positive charges. We subsequently determined that a panel of 523 commercially available (and biologically active) peptides shared this elevation of absolute net charge: there were significantly lower frequencies of peptides of mixed charges compared to expectations. We conclude that the design of biologically active peptides should consider favoring those with a higher absolute net charge.     

Alpha-oximono-esters as precursors to heterocycles--generation of oxazinone N-oxides and cycloaddition to alkene dipolarophiles

Preparation of a series of terminally and internally substituted delta-alkenyl and delta-alkynyl esters 6, 7 and 9, potential precursors to oxazin-2-one nitrones, has been attempted. Condensation between pyruvic or benzoylformic acid and the appropriate alcohol proceeded smoothly in some cases whilst allylic transposition was a major feature in other cases--most especially during reactions with alpha-vinylbenzyl alcohol. Oximation of pyruvic acid derivatives furnished E-oxime isomers whilst benzoylformic acid derivatives afforded mixed geometrical isomers. The E-oxime of 4a1 carrying an internal Me group undergoes facile thermal cyclisation affording nitrones 1c and 1d in good yield. Oximes E-5a,b with a terminal methyl substituent on the alkene moiety furnish nitrone only under the influence of an external electrophile [PhSeBr/AgBF4]. A terminal Ph substituent on 5c,d prohibits formation of the cyclic dipole irrespective of reaction conditions, and whilst 5d reacts to afford a bicyclic isoxazolofuranone 13 by an IOOC reaction (intramolecular oxime olefin cyclisation) 5c remains thermally inert. Finally delta-alkynyl oximes 9c,d also failed to cyclise. The regio- and stereochemical characteristics of the cycloadditions between the new dipoles and electron poor olefinic dipolarophiles have been investigated. The conditions needed for reaction were rather forcing since the dipoles are somewhat stabilised by the adjacent alkoxycarbonyl group. All reactions proceeded regiospecifically to give adducts with 5-substituted isoxazolidine rings whilst diastereoselectivity varied with the choice of dipolarophile and the steric demands of the nitrone substituents. The phenylselenyl dipole 10a could not be trapped by any dipolarophiles bar dimethyl acetylenedicarboxylate.     

Warm cascades and anomalous scaling in a diffusion model of turbulence

A phenomenological turbulence model in which the energy spectrum obeys a nonlinear diffusion equation is analyzed. The general steady state contains a nonlinear mixture of the constant-flux Kolmogorov and fluxless thermodynamic components. Such "warm cascade" solutions describe a bottleneck phenomenon of spectrum stagnation near the dissipative scale. Transient self-similar solutions describing a finite-time formation of steady cascades are analyzed and found to exhibit nontrivial scaling behavior.