排序方式: 共有83条查询结果,搜索用时 28 毫秒
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Garner P Anderson JT Cox PB Klippenstein SJ Leslie R Scardovi N 《The Journal of organic chemistry》2002,67(17):6195-6209
The development of an effective chiral auxiliary for hydroxyalkyl radicals is delineated. Both the 2-tetrahydropyranyl (THP) and tri-O-benzyl-2-deoxy-alpha-D-glucopyranosyl (GLU) auxiliaries resulted in diastereoselective radical additions to methyl acrylate at -78 degrees C (ds = 6/1 and 11/1, respectively). The developing stereochemistry at the radical center was completely under auxiliary control. Correlation experiments showed that the D-GLU auxiliary led to attack on the radical Si-face. The selectivity of these radical additions dropped-off considerably when the more reactive 2-nitropropene trap was employed. Computational studies suggested that the observed facial selectivity was due primarily to entropic factors in the transition state but that a smaller temperature-dependent enthalpic contribution was also involved. It was hypothesized that incorporation of a quaternary center at C-6 (THP numbering) would restore the facial selectivity with more reactive radical traps by restricting the orientations available to the incoming alkene. In the event, the trans-6-tert-butyltetrahydropyranyl (tBu-THP) auxiliary resulted in very good diastereoselection with 2-nitropropene (ds = 35/1 at -78 degrees C, 15/1 at 0 degrees C, and 8/1 at RT) as did the tri-O-benzyl-6,6-dimethyl-2-alpha-D-deoxyglucopyranosyl (diMe-GLU) auxiliary during additions to ethyl alpha-trifluoroacetoxyacrylate (ds = 10/1 at 0 degrees C). A protocol for recovery of the sugar-derived chiral auxiliaries was also established. This work sets the stage for the development of a novel approach to 1, 3, 5.(2n + 1) polyols based on iterative radical homologation as well as the application of these pyranosidic auxiliaries to other synthetically important reactions. 相似文献
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RITVA LINDBERG GORAN SUNDHOLM JOHAN SJö BLOM PETRI AHONEN ESKO I. KAUPPINEN 《Journal of Dispersion Science and Technology》2013,34(1-2):715-722
The zeta-potentials of silica, copper, platinum and gold particles have been measured as a function of pH. The isoelectric points were found to be at pH 3.0, 5.8, 3.0 and 3.5, respectively. In the pH range 3.0 to 5.8 copper and silica particles are oppositely charged and accordingly the coating of silica with copper particles could be demonstrated. In the case of gold and platinum the sign of the charge is such that direct adhesion to silica particles cannot be expected and this was also demonstrated in the case of platinum. 相似文献
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van Enk SJ 《Physical review letters》2000,84(4):789; author reply 790
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Yujie Tao Ahren W. Jasper Yuri Georgievskii Stephen J. Klippenstein Raghu Sivaramakrishnan 《Proceedings of the Combustion Institute》2021,38(1):515-522
Recent theoretical studies have shown that termolecular chemistry can be facilitated through reactions of flame radicals (H, O, and OH) or O2 with highly-energized collision complexes (either radical or stable species) formed in exothermic reactions. In this work, radical-radical recombination reaction induced termolecular chemistry and its impact on combustion modeling was studied. Two recombination reactions, H + CH3 + M → CH4 + M and H + OH + M → H2O + M, were analyzed using ab-initio master equation analyses guided by quasiclassical trajectory results. The dynamics results and the master equation calculations indicate that CH4? and H2O? (formed in the two radical-radical reactions outlined above) react rapidly with flame radicals and O2 at rates that are competitive with collisional cooling. The addition of these processes into conventional combustion modeling requires two modifications: the inclusion of the new nonthermal termolecular reaction rates and the simultaneous reduction of the competing recombination reaction rates. The former is described with newly derived Arrhenius expressions based on quasiclassical trajectories, and the latter is achieved by perturbing the recombination reaction rate during the simulation. Kinetic modeling was used to gauge the impact of including this nonthermal chemistry for H2/CH4-air laminar flames speeds. Inclusion of this nonthermal chemistry has a noticeable impact on simulated flame speeds. The procedure developed here can be utilized to properly quantify the effects of such nonthermal reactions in macroscopic kinetic models. 相似文献
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Douglas McHugh Sherry SJ Hu Neta Rimmerman Ana Juknat Zvi Vogel J Michael Walker Heather B Bradshaw 《BMC neuroscience》2010,11(1):44
Background
Microglia provide continuous immune surveillance of the CNS and upon activation rapidly change phenotype to express receptors that respond to chemoattractants during CNS damage or infection. These activated microglia undergo directed migration towards affected tissue. Importantly, the molecular species of chemoattractant encountered determines if microglia respond with pro- or anti-inflammatory behaviour, yet the signaling molecules that trigger migration remain poorly understood. The endogenous cannabinoid system regulates microglial migration via CB2 receptors and an as yet unidentified GPCR termed the 'abnormal cannabidiol' (Abn-CBD) receptor. Abn-CBD is a synthetic isomer of the phytocannabinoid cannabidiol (CBD) and is inactive at CB1 or CB2 receptors, but functions as a selective agonist at this Gi/o-coupled GPCR. N-arachidonoyl glycine (NAGly) is an endogenous metabolite of the endocannabinoid anandamide and acts as an efficacious agonist at GPR18. Here, we investigate the relationship between NAGly, Abn-CBD, the unidentified 'Abn-CBD' receptor, GPR18, and BV-2 microglial migration. 相似文献9.
Klippenstein SJ Georgievskii Y Harding LB 《Physical chemistry chemical physics : PCCP》2006,8(10):1133-1147
An ab initio transition state theory based procedure for accurately predicting the combination kinetics of two alkyl radicals is described. This procedure employs direct evaluations of the orientation dependent interaction energies at the CASPT2/cc-pvdz level within variable reaction coordinate transition state theory (VRC-TST). One-dimensional corrections to these energies are obtained from CAS+1+2/aug-cc-pvtz calculations for CH3 + CH3 along its combination reaction path. Direct CAS+1+2/aug-cc-pvtz calculations demonstrate that, at least for the purpose of predicting the kinetics, the corrected CASPT2/cc-pvdz potential energy surface is an accurate approximation to the CAS+1+2/aug-cc-pvtz surface. Furthermore, direct trajectory simulations, performed at the B3LYP/6-31G* level, indicate that there is little local recrossing of the optimal VRC transition state dividing surface. The corrected CASPT2/cc-pvdz potential is employed in obtaining direct VRC-TST kinetic predictions for the self and cross combinations of methyl, ethyl, iso-propyl, and tert-butyl radicals. Comparisons with experiment suggest that the present dynamically corrected VRC-TST approach provides quantitatively accurate predictions for the capture rate. Each additional methyl substituent adjacent to a radical site is found to reduce the rate coefficient by about a factor of two. In each instance, the rate coefficients are predicted to decrease quite substantially with increasing temperature, with the more sterically hindered reactants having a more rapid decrease. The simple geometric mean rule, relating the capture rate for the cross reaction to those for the self-reactions, is in remarkably good agreement with the more detailed predictions. With suitable generalizations the present approach should be applicable to a wide array of radical-radical combination reactions. 相似文献
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