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Reaction Centre (reaction + centre)
Selected AbstractsThe Origin of the High Enantioselectivity in Asymmetric Cyclopropanation of Unfunctionalized OlefinsADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 11-12 2010Yiying Zheng Abstract The mechanism of the asymmetric Simmons,Smith cyclopropanation for unfunctionalized olefins was investigated using density functional theory (DFT) methods. The calculated results of model reactions showed that the coordinated Lewis acidic zinc halide ZnX2 (X=Cl, I) and/or halomethylzinc halide XZnCH2X in the catalyst play an important role in the enantioselectivity. The catalyst not only forms the ring with the substance in the reaction centre, but also establishes two steric repulsions that can lead to an explanation for the high enantioselectivity. Hence, these results highlight some important insights for the prerequisites of an effective catalyst and a proper substrate towards high enantioselectivity for this kind of reaction. [source] Effects of long-term chilling on growth and photosynthesis of the C4 gramineae Paspalum dilatatumPHYSIOLOGIA PLANTARUM, Issue 1 2003Ana M. Cavaco Dallis grass (Paspalum dilatatum Poir.) is a C4/NADP-ME gramineae, previously classified as semi-tolerant to cold, although a complete study on this species acclimation process under a long-term chilling and controlled environmental conditions has never been conducted. In the present work, plants of the variety Raki maintained at 25/18°C (day/night) (control) were compared with plants under a long-term chilling at 10/8°C (day/night) (cold-acclimated) in order to investigate how growth and carbon assimilation mechanisms are engaged in P. dilatatum chilling tolerance. Although whole plant mean relative growth rate (mean RGR) and leaf growth were significantly decreased by cold exposure, chilling did not impair plant development nor favour the investment in biomass below ground. Cold-acclimated P. dilatatum cv. Raki had a lower leaf chlorophyll content, but a higher photosynthetic capacity at optimal temperatures, its range being shifted to lower values. Associated with this higher capacity to use the reducing power in CO2 assimilation, cold-acclimated plants further showed a higher capacity to oxidize the primary stable quinone electron acceptor of PSII, QA. The activity and activation of phosphoenolpyruvate carboxylase (PEPC; EC 4.1.1.31) and ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco; EC 4.1.1.39) were not significantly affected by the long-term chilling. Cold-acclimated P. dilatatum cv. Raki apparently showed a lower transfer of excitation energy from the light-harvesting complex of photosystem II to the respective reaction centre and enhancement of radiationless energy-dissipating mechanisms at suboptimal temperatures. Overall, long-term chilling resulted in several effects that comprise responses with an intermediate character of both chilling-tolerant and ,sensitive plants, which seem to play a significant role in the survival and acclimation of P. dilatatum cv. Raki at low temperature. [source] Monitoring structural transformations in crystals.ACTA CRYSTALLOGRAPHICA SECTION B, Issue 6 2007Structural changes proceeding in a crystal during the Yang photocyclization of the salt 6,6-diethyl-5-oxo-5,6,7,8-tetrahydronaphthalene-2-carboxylate with (1S)-1-(4-methylphenyl)ethylamine were monitored by means of X-ray structure analysis. The course of the photoreaction was evaluated on the basis of the geometrical parameters for the pure reactant crystal. Variations in the cell constants, the product content, the geometry of the reaction centre, the orientation of molecular fragments and the geometry of hydrogen bonds were described and analyzed. It was found that the cell volume increased until 56% product content and decreased thereafter. The distance between the directly reacting C atoms was constant, ,,3.0,Å, until ,,75% reaction progress. Analysis of the distance between atoms that would participate in the formation of the second (unobserved) enantiomorph excluded the formation of such an isomer. Molecular fragments varied their orientation during the photoreaction, and the largest change was observed for the carboxylate group despite its participation in strong hydrogen bonds. The geometry of the hydrogen bonds changed during the photoreaction. The largest change was 0.17,Å for the D...A distance and 13° for the D,H...A angle. A comparison of the intra- and intermolecular parameters for the studied salt with data for other compounds undergoing the Yang photocyclization in crystals revealed a diversity of structural changes brought about by this type of photochemical reaction. [source] Oxygen evolution and respiration of the cyanobacterium Synechocystis sp.PHYSIOLOGIA PLANTARUM, Issue 3 2005PCC 6803 under two different light regimes applying light/dark intervals in the time scale of minutes The photosynthetic performance of the cyanobacterium Synechocystis sp. PCC 6803 exposed to intermittent light was studied by measuring oxygen evolution, respiration and the fluorescence parameters for maximum efficiency of excitation energy capture by photosystem II (PSII) reaction centres (Fv/Fm), PSII quantum yield (,F/Fm1) and non-photochemical quenching (NPQ). Cultures were pre-acclimated to constant light conditions. Block and sinusoidal light regimes were tested using four photon-flux densities (PFDs) applied in light/dark intervals of 1:1, 5:5 and 10:10 min. Light use was higher under the sinusoidal light regime compared with the block regime. The accumulated gross photosynthesis of the cyanobacterium was lower under intermittent light conditions compared with predictions from the photosynthesis-irradiance curve (PI curve). The respiration rates were similar for all light/dark intervals tested. However, the respiration slightly increased with increasing oxygen production for both block and sinusoidal light regime. NPQ, ,F/Fm, and Fv/Fm depended on the PFD rather than on the duration of the light/dark intervals tested, and there was no detected influence of the two applied light regimes. [source] Use of chlorophyll fluorescence to evaluate the cold acclimation and freezing tolerance of winter and spring oatsPLANT BREEDING, Issue 5 2001F. Rizza Abstract The efficiency of the excitation capture by open Photosystem II (PSII) reaction centres was measured by the Fv/Fm ratios in a collection of winter and spring oats in order to assess the effects of hardening and freezing on the functionality of PSII and also the suitability of a chlorophyll fluorescence-based method to screen oat cultivars for frost tolerance. A significant reversible decrease in Fv/Fm was found in all genotypes during acclimation to low, non-freezing temperatures. Fv/Fm analysis appears to be an attractive test for the evaluation of frost tolerance in oats, being rapid, non-invasive and capable of monitoring a trait related to a crucial stage in the acquisition of frost tolerance. It is more sensitive and precise than other standard methods and highly correlated with field-evaluated frost damage. The measurements made during recovery 1 or 2 days after stress when the visual symptoms are not yet expressed, were especially advantageous because of the large variability in genotype response. The r-values (close to 0.8) were reduced due to the non-standard behaviour of the winter cultivar ,Aintree'. The cold acclimation response of this genotype has been analysed in detail and the limits of artificial freezing tests are discussed. [source] The structure of allophycocyanin from Thermosynechococcus elongatus at 3.5,Å resolutionACTA CRYSTALLOGRAPHICA SECTION F (ELECTRONIC), Issue 12 2007James William Murray Cyanobacteria and red algae use light-harvesting pigments bound by proteins to capture solar radiation and to channel excitation energy into their reaction centres. In most cyanobacteria, a multi-megadalton soluble structure known as the phycobilisome is a major light-harvesting system. Allophycocyanin is the main component of the phycobilisome core, forming a link between the rest of the phycobilisome and the reaction-centre core. The crystal structure of allophycocyanin from Thermosynechococcus elongatus (TeAPC) has been determined and refined at 3.5,Å resolution to a crystallographic R value of 26.0% (Rfree = 28.5%). The structure was solved by molecular replacement using the allophycocyanin structure from Spirulina platensis as the search model. The asymmetric unit contains an (,,) monomer which is expanded by symmetry to a crystallographic trimer. [source] | |||||||||||||