A comparative study of protoheme and heme d catalases : role of the heme and the heme pocket in catalysis and ligand binding

Catalase dismutes H20 2 to O2 and H20. In successive twoelectron reactions H20 2 induces both oxidation and reduction at the heme group. In the first step the protoheme prosthetic group of beef liver catalase forms compound I, in which the heme has been oxidized from Fe3+ to Fe4+=0 and a porphyrin radical has been created. Compound II is formed by the oneelectron reduction of comp I. It retains Fe4+=0 but lacks the porphyrin radical and is catalytically inert. Molecular structures are available for Escherichia coli Hydroperoxidase II, Micrococcus Iysodeiktus, Penicillium vitale and beef liver enzymes, which contain different hemes and heme pockets. In the present work, the pockets and substrate access channels of protoheme (beef liver & Micrococcus) and heme d (HPII of E. coli and Penicillium) catalases have been analysed using Quanta™ and CharmMTM molecular modeling packages on the Silicon Graphics Iris Indigo 2 computer. Experimental studies have been carried out with two catalases, HPII (and its mutants) and beef liver. Fluoride and formate' are inhibitors of both enzymes, and their binding is modulated by the heme and by distal residues N201 & H128. Both HPII and beef liver enzymes form compound I with H202 or peracetate. The reduction of beef liver enzyme compound I to II and the decay of compound II are accelerated by fluoride. The decay of compound II is also accelerated by formate, and this reagent acts as a 2-electron donor towards compound I of both enzymes. It is concluded that heme d enzymes (Penicillium and HPII of E. coli) are formed by autocatalytic transformation of protoheme in a modified pocket which contains a characteristic serine residue as well as a partially occluded heme channel. They are less active than protoheme enzymes but also do not form the inactive compound II species. Binding of peroxide as well as fluoride and formate is prevented by mutation of H128 and modulated by mutation of N201.

Engineers and technicians : the effect of cognitive style and gender on visual information processing

The purpose of this project was to identify in a subject group of engineers and technicians (N = 62) a preferred mode of representation for facilitating correct recall of information from complex graphics. The modes of representation were black and white (b&w) block, b&w icon, color block, and color icon. The researcher's test instrument included twelve complex graphics (six b&w and six color - three per mode). Each graphics presentation was followed by two multiple-choice questions. Recall performance was better using b&w block mode graphics and color icon mode graphics. A standardized test, the Group Embedded Figures Test (GEFT) was used to identify a cognitive style preference (field dependence). Although engineers and technicians in the sample were strongly field-independent, they were not significantly more field-independent than the normative group in the Witkin, Oltman, Raskin, and Karp study (1971). Tests were also employed to look for any significant difference in cognitive style preference due to gender. None was found. Implications from the project results for the design of visuals and their use in technical training are discussed.

Molecular mechanics calculations on some phosphine oxide metal complexes in aqueous and organic solvents

Molecular mechanics calculations were done on tetrahedral phosphine oxide zinc complexes in simulated water, benzene and hexane phases using the DREIDING II force field in the BIOGRAF molecular modeling program. The SUN workstation computer (SUN_ 4c, with SPARK station 1 processor) was used for the calculations. Experimental structural information used in the parameterization was obtained from the September 1989 version of the Cambridge Structural Database. 2 Steric and solvation energies were calculated for complexes of the type ZnCl2 (RlO)2' The calculations were done with and without inclusion of electrostatic interactions. More reliable simulation results were obtained without inclusion of charges. In the simulated gas phase, the steric energies increase regularly with number of carbons in the alkyl group, whereas they go through a maximum when solvent shells are included in the calculation. Simulated distribution ratios vary with chain length and type of chain branching and the complexes are found to be more favourable for extraction by benzene than by hexane, in accord with experimental data. Also, in line with what would be expected for a favorable extraction, calculations without electrostatics predict that the complexes are better solvated by the organic solvents than by water.

Quadtree representation and compression of spatial data

Spatial data representation and compression has become a focus issue in computer graphics and image processing applications. Quadtrees, as one of hierarchical data structures, basing on the principle of recursive decomposition of space, always offer a compact and efficient representation of an image. For a given image, the choice of quadtree root node plays an important role in its quadtree representation and final data compression. The goal of this thesis is to present a heuristic algorithm for finding a root node of a region quadtree, which is able to reduce the number of leaf nodes when compared with the standard quadtree decomposition. The empirical results indicate that, this proposed algorithm has quadtree representation and data compression improvement when in comparison with the traditional method.