Direct electrochemistry of enzymes from the cytochrome P4502C family

The human cytochromes P450 are responsible for the clearance of similar to 90% of xenobiotics yet comparatively little is known about their electrochemistry. Here we report the first direct electrochemistry of P450s from the 2C subfamily; one of the major groups of enzymes from this family. Specifically, the proteins that we have examined are recombinant human P450s 2C9, 2C 18 and 2C 19 and reversible Fe-III/II couples are seen in the absence of dioxygen. Even in the presence of trace amounts of dioxygen, a pronounced cathodic response is seen which is assigned to catalytic reduction of the bound dioxygen ligand by the ferrous P450. (c) 2005 Elsevier B.V. All rights reserved.

Preparation and characterization of copper catalysts supported on mesoporous Al2O3 nanofibers for N2O reduction to N2

A series of mesoporous Al2O3 samples with different porous structures and phases were prepared and used as supports for Cu/Al2O3 catalysts. These catalysts were characterized by N-2 adsorption, NMR, TGA, XRD, and UV - vis spectroscopic techniques and tested for the catalytic reaction of N2O decomposition. The activity increased with the increasing calcination temperatures of supports from 450 to 900 degreesC; however, a further increase in calcination temperature up to 1200 degreesC resulted in a significant reduction in activity. Characterization revealed that the calcination temperatures of supports influenced the porous structures and phases of the supports, which in turn affected the dispersions, phases, and activities of the impregnated copper catalyst. The different roles of surface spinel, bulk CuAl2O4, and bulk CuO is clarified for N2O catalytic decomposition. Two mechanism schemes were thus proposed to account for the varying activities of different catalysts.

The tyrosine phosphatase DEP-1 induces cytoskeletal rearrangements, aberrant cell-substratum interactions and a reduction in cell proliferation

The receptor protein tyrosine phosphatase density-enhanced phosphatase-1 (DEP-1) has been implicated in aberrant cancer cell growth and immune cell function, however, its function within cells has yet to be properly elucidated. To investigate the cellular function of DEP-1, stable cell lines inducibly expressing DEP-1 were generated. Induction of DEP-1 expression was found to decrease PDGF-stimulated tyrosine phosphorylation of a number of cellular proteins including the PDGF receptor, and to inhibit growth factor-stimulated phosphorylation of components of the MAPK pathway, indicating that DEP-1 antagonised PDGF receptor signalling. This was supported by data showing that DEP-1 expression resulted in a reduction in cell proliferation. DEP-1-expressing cells had fewer actin-containing microfilament bundles, reduced vinculin and paxillin-containing adhesion plaques, and were defective in interactions with fibronectin. Defective cell-substratum adhesion correlated with lack of activation of FAK in DEP-1-expressing cells. Time-lapse interference reflection microscopy of live cells revealed that although small focal contacts at the leading edge were generated in DEP-1-expressing cells, they failed to mature into stable focal adhesions, as found in control cells. Further motility analysis revealed that DEP-1-expressing cells retained limited random motility, but showed no chemotaxis towards a gradient of PDGF. In addition, cell-cell contacts were disrupted, with a change in the localisation of cadherin from discrete areas of cell-cell contact to large areas of membrane interaction, and there was a parallel redistribution of beta-catenin. These results demonstrate that DEP-1 is a negative regulator of cell proliferation, cell-substratum contacts, motility and chemotaxis in fibroblasts.

Effect of the preparation technique on the catalytic properties of mesoporous V-HMS for the oxidation of toluene

Various mesoporous catalysts with vanadium loadings between 0.5 and 6 V wt.% and surface areas around 1300 m(2)/g were synthesized using the isomorphous substitution (IS) and molecular designed dispersion (MDD) techniques. Their catalytic properties were tested using toluene as a model VOC in a fixed bed reactor at temperatures between 300 and 550 degrees C. It was found that during the oxidation of toluene, over V-HMS synthesized via IS, conversion of toluene mainly results in carbon oxides, benzene, benzaldehyde and water. Total conversion is greatly improved when the vanadium content is increased from around 1.5 to 3.0 wt.%, but an increase in the textural porosity (V-TEX/V-MESO) from 0.3 to 0.6 had no discernable effect on the conversion. This can be explained by the fact that a V-TEX/V-MESO as low as 0.3 is sufficient to facilitate the access of toluene into the framework confined mesopores without any molecular transport limitations. However, when using V-HMS synthesized by MDD, conversion of toluene is greatly improved when the V-TEX/ V-MESO ratio is increased from 0.1 to 0.6. This is because the diffusion limitations are minimized by this increase. V-HMS synthesized via MDD does not exhibit selectivity to benzaldehyde, favoring total oxidation to CO and CO2. This different oxidation mechanism can be explained in terms of location, accessibility and number of active species on the surface of the HMS support. (c) 2005 Elsevier Inc. All rights reserved.