The electron impact ionization of magnesium (2p)

A systematic study of the triple differential cross section for the electron impact ionization of magnesium is presented. Complete sets of theoretical results using both the first Born and the distorted wave Bom approximation are given for a range of asymmetric kinematical regimes. How the physical significance of the different approximations enter the character of the cross sections will be explicitly demonstrated. Comparison is made with experiments of the Maryland group and suggestions are made for new experiments.

Multiphoton absorption by helium, magnesium and H-2 at high frequencies and intensities

We review principally some recent work carried out in Belfast and Heraklion which handles the few-electron dynamics of atomic and molecular systems exposed to high frequency. high intensity laser fields. The design and application of the quantitatively accurate computational methods is discussed. The Belfast work is illustrated by results for double ionization of helium and the hydrogen molecule where in each case the two electrons have been handled in full-dimensionality. The first results for multiphoton, double ionization of a complex atom, namely magnesium demonstrate an important application of the Heraklion approach.

A novel approach to dynamic modelling of polymer extrusion for improved process control

Polymer extrusion is a complex process and the availability of good dynamic models is key for improved system operation. Previous modelling attempts have failed adequately to capture the non-linearities of the process or prove too complex for control applications. This work presents a novel approach to the problem by the modelling of extrusion viscosity and pressure, adopting a grey box modelling technique that combines mechanistic knowledge with empirical data using a genetic algorithm approach. The models are shown to outperform those of a much higher order generated by a conventional black box technique while providing insight into the underlying processes at work within the extruder.

Enhancing process insight in polymer extrusion by grey box modelling

Due to the complexity and inherent instability in polymer extrusion there is a need for process models which can be run on-line to optimise settings and control disturbances. First-principle models demand computationally intensive solution, while ‘black box’ models lack generalisation ability and physical process insight. This work examines a novel ‘grey box’ modelling technique which incorporates both prior physical knowledge and empirical data in generating intuitive models of the process. The models can be related to the underlying physical mechanisms in the extruder and have been shown to capture unpredictable effects of the operating conditions on process instability. Furthermore, model parameters can be related to material properties available from laboratory analysis and as such, lend themselves to re-tuning for different materials without extensive remodelling work.

Spectral simulation of laser ablated magnesium plasmas

We describe a collisional-radiative equilibrium model for predicting the optical emission spectrum of low-temperature magnesium plasmas, specifically those created by laser ablation. In the model, levels are populated by a balance of collisional and radiative rates. We include Stark widths of lines and trapping of radiation in the calculations. By use of this model we discuss various issues of importance in spectral analysis of laser ablated plasma plumes, such as the partial local thermodynamic equilibrium approximation, line trapping and time dependence.

Dioxygenase-catalysed mono-, di- and tri-oxygenation of dialkyl sulfides and thioacetals: chemoenzymatic synthesis of enantiopure cis-diol sulfoxides

Toluene dioxygenase (TDO)-catalysed monooxygenation of methylsulfanylmethyl phenyl sulfide 1 and methylsulfanylmethyl 2-pyridyl sulfide 4, using whole cells of Pseudomonas putida UV4, occurred exclusively at the alkyl aryl sulfur centre to yield the alkyl aryl sulfoxides 2 and 5 respectively. These sulfoxides, accompanied by the dialkyl sulfoxides 3 and 6, were also obtained from naphthalene dioxygenase (NDO)-catalysed sulfoxidation of thioacetals 1 and 4 using intact cells of P. putida NCIMB 8859. Enzymatic oxidation of methyl benzyl sulfide 7, 2-phenyl-1,3-dithiane 19, and 2-phenyl-1,3-dithiolane 23, using TDO, gave the corresponding dialkyl sulfoxides 8, 20 and 24 as minor bioproducts. TDO-catalysed dioxygenation of the alkyl benzyl sulfides 7, 15 and 17 and the thioacetals 19 and 23, with P. putida UV4, yielded the corresponding enantiopure cis-dihydrodiols 9, 16, 18, 21 and 25 as major metabolites and cis-dihydrodiol sulfoxides 14, 22 and 26 as minor metabolites, resulting from a tandem trioxygenation of substrates 7, 19 and 23 respectively. Chemical oxidation, of the enantiopure cis-dihydrodiol sulfides 9, 16, 18 and 21 with dimethyldioxirane (DMD), gave separable mixtures of the corresponding pairs of cis-dihydrodiol sulfoxide diastereoisomers 14 and 27, 28 and 29, 30 and 31, 22 and 32. While dialkyl sulfoxide bioproducts 3, 6, 20 and 24 were of variable enantiopurity (27-greater than or equal to 98% ee), alkyl aryl monosulfoxides 2 and 5, cis-dihydrodiols 9, 16, 18, 21 and 25 and cis-dihydrodiol sulfoxide bioproducts 14, 22 and 26 were all single enantiomers (greater than or equal to 98% ee). The absolute configurations of the products, obtained from enzyme-catalysed (TDO and NDO) and chemical (DMD) oxidation methods, were determined by stereochemical correlation, circular dichroism, and X-ray crystallographic methods.

DPP IV resistance and insulin releasing activity of a novel di-substituted analogue of glucose-dependent insulinotropic polypeptide, (Ser(2)-Asp(13))GIP

Structure-function studies suggest that preservation of the N-terminus and secondary structure of glucose-dependent insulinotropic polypeptide (GIP) is important for biological activity. Therefore, a novel di-substituted analogue of GIP, (Ser(2)-Asp(13))GIP, containing a negatively charged Asp residue in place of an Ala in position 13, seas synthesised and evaluated for in vitro biological activity. Incubation with dipeptidyl peptidase IV (DPP IV) showed the half-lives of GIP and (Ser(2)-Asp(13))GIP to be 2.3 and >4 h, respectively. Insulin releasing studies in clonal pancreatic BRIN-BD11 cells demonstrated that (Ser(2)-Asp(13))GIP (10(-12) to 10(-7) mol/l) was significantly less potent (60-90%; P

Effect of pH and temperature on the formation of volatile compounds in cysteine/reducing sugar/starch mixtures during extrusion cooking

Mixtures of cysteine, reducing sugar (xylose or glucose), and starch were extrusion cooked using feed pH values of 5.5, 6.5, and 7.5 and target die temperatures of 120, 150, and 180 degreesC. Volatile compounds were isolated by headspace trapping onto Tenax and analyzed by gas chromatography-mass spectrometry. Eighty and 38 compounds, respectively, were identified from extrudates prepared using glucose and xylose. Amounts of most compounds increased with temperature and pH. Aliphatic sulfur compounds, thiophenes, pyrazines, and thiazoles were the most abundant chemical classes for the glucose samples, whereas for xylose extrudates highest levels were obtained for non-sulfur-containing furans, thiophenes, sulfur-containing furans, and pyrazines. 2-Furanmethanethiol and 2-methyl-3-furanthiol were present in extrudates prepared using both sugars, but levels were higher in xylose samples. The profiles of reaction products were different from those obtained from aqueous or reduced-moisture systems based on cysteine and either glucose or ribose.