Improved Kinetic Resolution by Enzyme-Catalyzed Parallel Reactions

Competitive parallel reactions with opposite enantioselectivity are presented as a strategy to enhance the enantiomeric product purity in enzymatic kinetic resolution. Lipase-catalyzed simultaneous hydrolysis and amidation of racemic methy 12-chloropropionate led to significantly improved amide yield and enantiomeric excess. Process results can be controlled by changing the hydrolysis/amidation reaction rates through variation of the solvent and the initial amine concentration. This is described by a kinetic model.     

Autochthonous outer ramp sedimentation: The Alamogordo Member of the Lake Valley Formation,New Mexico

Summary Paleozoic carbonate ramp sedimentation has generally been described in terms of downlapping clinoforms composed of allochthonous sediment derived from shallower environments. However, during transgressive episodes when carbonate sediment production is low and down slope sediment transport by gravity becomes inactive, autochthonous carbonate sediment accumulates in vertical stacks of essentially in situ sediment. Autochthonous outer ramp deposition is probably a part of many Paleozoic ramp strata, but has heretofore not been recognized because of the general absence of adequate exposures. Evidence of autochthonous, in situ deposition and preservation of sediments in a starved setting is well displayed in the Alamogordo Member of the Lake Valley Formation in south central New Mexico. This evidence includes: 1) beds and bed sets that are individually continuous and traceable along ramp slope for 32 km, 2) down-ramp sequential distributions of depth-sensitive organisms and assemblages but patchy distribution of rock types, 3) lack of sedimentary structures indicative of transport, 4) well preserved, unabraded fossils, 5) the common occurrence of fossils in life position, 6) beds traceable into and through mounds 7) bed thickness trends ascribed to biotic productivity, and 8) geopetal structures in original position. Integrated paleontologic, sedimentologic, and stratigraphic data provide information about depositional processes and setting. The depositional slope was approximately 0.5^o based on the distribution of fossil algae; this is comparable to dips reported for other Mississippian homoclinal ramps. An oxygen minimum zone may have impinged on the ramp during a major flooding event. Shifts in biotic gradients from bed to bed reveal transgressive-regressive patterns that would not be resolvable without detailed paleontological evidence. The Alamogordo Member formed as a result of transgressive and early highstand starved carbonate sedimentation along a narrow, homoclinal outer ramp. The surface of maximum flooding and the boundary between the TST and HST are within the Alamogordo Member.     

Electron Paramagnetic Resonance investigation of the interaction of nitroxyl spin labels with photosynthetic membranes

The interactions of four nytroxyl spin labels with photosynthetic membranes (thylakoids and liposomes) have been investigated by the Electron Paramagnetic Resonance technique (EPR). The obtained data (shapes of EPR spectra and kinetics of light induced reactions) allow us to localize the interactions between the markers and photosynthetic membranes. The pH influence on the reaction kinetics has also been investigated. On the basis of these experimental data, a theoretical model of the interaction between spin labels and the photosynthetic electron transport chain is proposed.     

Interaction between atmospheric and pedospheric nitrogen nutrition in spruce (Picea abies L. Karst) seedlings

The effect of NO₂ fumigation on root N uptake and metabolism was investigated in 3-month-old spruce (Picea abics L. Karst) seedlings. In a first experiment, the contribution of NO₂ to the plant N budget was measured during a 48 h fumigation with 100mm³m^?3 NO₂. Plants were pre-treated with various nutrient solutions containing NO₂ and NH₄⁺, NO₃^? only or no nitrogen source for 1 week prior to the beginning of fumigation. Absence of NH₄⁺ in the solution for 6d led to an increased capacity for NO₃^? uptake, whereas the absence of both ions caused a decrease in the plant N concentration, with no change in NO₃^? uptake. In fumigated plants, NO₂ uptake accounted for 20–40% of NO₃^? uptake. Root NO₃^? uptake in plants supplied with NH₄⁺plus NO₃^? solutions was decreased by NO₂ fumigation, whereas it was not significantly altered in the other treatments. In a second experiment, spruce seedlings were grown on a solution containing both NO₂ and NH₄⁺ and were fumigated or not with 100mm³m^?3 NO₂ for 7 weeks. Fumigated plants accumulated less dry matter, especially in the roots. Fluxes of the two N species were estimated from their accumulations in shoots and roots, xylem exudate analysis and ¹⁵N labelling. Root NH₄⁺ uptake was approximately three times higher than NO₃^? uptake. Nitrogen dioxide uptake represented 10–15% of the total N budget of the plants. In control plants, N assimilation occurred mainly in the roots and organic nitrogen was the main form of N transported to the shoot. Phloem transport of organic nitrogen accounted for 17% of its xylem transport. In fumigated plants, neither NO₃^? nor NH₄⁺ accumulated in the shoot, showing that all the absorbed NO₂ was assimilated. Root NO₃^? reduction was reduced whereas organic nitrogen transport in the phloem increased by a factor of 3 in NO₂-fimugated as compared with control plants. The significance of the results for the regulation of whole-plant N utilization is discussed.