Novel proresolving aspirin-triggered DHA pathway

Endogenous mechanisms in the resolution of acute inflammation are of interest because excessive inflammation underlies many pathologic abnormalities. We report an aspirin-triggered DHA metabolome that biosynthesizes a potent product in inflammatory exudates and human leukocytes, namely aspirin-triggered Neuroprotectin D1/Protectin D1 [AT-(NPD1/PD1)]. The complete stereochemistry of AT-(NPD1/PD1) proved to be 10R,17R-dihydroxydocosa-4Z,7Z,11E,13E,15Z,19Z-hexaenoic acid. The chirality of hydroxyl groups and geometry of the conjugated triene system essential for bioactivity were established by matching biological materials with stereochemically pure isomers prepared by organic synthesis. AT-(NPD1/PD1) reduced neutrophil (PMN) recruitment in murine peritonitis in a dose-dependent fashion whereby neither a Δ(15)-trans-isomer nor DHA was effective. With human cells, AT-(NPD1/PD1) decreased transendothelial PMN migration as well as enhanced efferocytosis of apoptotic human PMN by macrophages. These results indicate that AT-(NPD1/PD1) is a potent anti-inflammatory proresolving molecule.     

Electron tunneling through sensitizer wires bound to proteins

We report a quantitative theoretical analysis of long-range electron transfer through sensitizer wires bound in the active-site channel of cytochrome P450cam. Each sensitizer wire consists of a substrate group with high binding affinity for the enzyme active site connected to a ruthenium-diimine through a bridging aliphatic or aromatic chain. Experiments have revealed a dramatic dependence of electron transfer rates on the chemical composition of both the bridging group and the substrate. Using combined molecular dynamics simulations and electronic coupling calculations, we show that electron tunneling through perfluorinated aromatic bridges is promoted by enhanced superexchange coupling through virtual reduced states. In contrast, electron flow through aliphatic bridges occurs by hole-mediated superexchange. We have found that a small number of wire conformations with strong donor–acceptor couplings can account for the observed electron tunneling rates for sensitizer wires terminated with either ethylbenzene or adamantane. In these instances, the rate is dependent not only on electronic coupling of the donor and acceptor but also on the nuclear motion of the sensitizer wire, necessitating the calculation of average rates over the course of a molecular dynamics simulation. These calculations along with related recent findings have made it possible to analyze the results of many other sensitizer-wire experiments that in turn point to new directions in our attempts to observe reactive intermediates in the catalytic cycles of P450 and other heme enzymes.     

Zur Tryptophanreaktion

Ohne Zusammenfassung     

Die Anwendung des Magnesiums als Reagens

Ohne Zusammenfassung     

Liquid-Phase Epitaxy of (Hg,Cd)Te on CdTe Substrates by a Vertical Dipping Technique

Hg_1−xCd_xTe layers on CdTe substrates were grown from Te-rich melt solutions by a vertical dipping technique using a special quasi-closed system with ground-glass sealing. Results are good reproducibilities of the electrical properties after annealing in Hg-rich atmosphere (p77 ≈ 2 · 10¹⁶ cm⁻³ μ77 ≈ 500 cm² V⁻¹ s⁻¹) and of the x-value, respectively. A horizontal position of the substrate downwards to the melt solution yields, in difference to a vertical one, to homogeneous layer thicknesses. Short meltback steps before growth leads to sharper profiles of composition.     

Zur Bestimmung der Mikrohärte von Baryt-Einkristallen bei hohem hydrostatischen Druck

An apparatus to generate high pressure up to 12000 kp · cm⁻² and a microhardness device to be put in it are described. The pyramid identations originate from the moving force of the falling indenter. To compare microhardnesses at normal and high pressure the viscosities of the pressure fluids are assimilated. For that purpose the microhardness device served as viscosimeter. With extrapolated falling height zero of the idennter and a load of 36 g the (001)-surface of Baryt single crystals have a microhardness of about 210 kp · mm⁻² at a hydrostatic pressure of 10000 kp · cm⁻². The corresponding microhardness at normal pressure is 90 kp · mm⁻²     

Radial segregation due to weak convection in a floating zone

The influence of weak convection, caused by surface tension forces, on radial dopant segregation occurring in crystals grown under microgravity conditions is studied numerically. The geometry considered corresponds to a floating-zone configuration with partially coated melt surfaces consisting of small evenly distributed spots of free surfaces. In order to distinguish dopant distribution due to weak convection clearly from distribution due to diffusion the spots only cover one quarter of the periphery. Thus, surface tension-driven convection is allowed only over one quarter of the floating-zone configuration resulting in an asymmetric dopant distribution. The percentage of free surfaces present is varied in order to alter the Marangoni flow rates. The maximum dopant concentration due to radial segregation is plotted as a function of a certain convection level. The results of the present numerical study are supposed to be used to design corresponding space experiments launched at the end of the year 2000.