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91.
Trost BM Shen HC Horne DB Toste FD Steinmetz BG Koradin C 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(8):2577-2590
The Ru-catalyzed intramolecular [5+2] cycloaddition of cyclopropylenynes is investigated with respect to the regio- and diastereoselectivity as well as the functional group compatibility of the reaction. Evidence for the mechanism as occurring through a ruthenacyclopentene intermediate is elucidated from 1) the study of the diastereoselectivity of the cycloaddition; 2) the effect of variation of substituents on the regioselectivity of cyclopropyl bond cleavage in 1,2-trans- and 1,2-cis-disubstituted cyclopropanes and 3) examples that clearly do not involve ruthenacyclohexene as intermediates as products still incorporate the cyclopropyl moiety. The scope and limitations of the Ru-catalyzed cycloaddition are discussed and compared with the Rh-catalyzed reaction. The potential power of this methodology towards natural product total synthesis is demonstrated by the formation of several polycyclic systems with the chosen reaction conditions and readily available cyclopropylenyne substrates. 相似文献
92.
The amount of chemiluminescence (CL) or light that is emitted from human polymorphonuclear leukocytes (PMN) during phagocytosis or activation by soluble stimuli is dependent on the emission of photons from the oxidation of particulate or bystander molecules. Because the compounds luminol and lucigenin yield photons with high quantum efficiency these agents have been introduced to sensitively assess PMN-CL. Since there is limited information about the pathways involved in the chemiluminescence of these compounds, we investigated the role of both myeloperoxidase (MPO) and superoxide anion (· O2?) in luminol-and lucigenin-PMN-CL. We compared the CL between normal and MPO- deficient PMN using zymosan for phagocytosis and N-formylmethionyleucylphenylalanine (FMLP) as a soluble stimulus. Our data demonstrated that luminol-CL was dependent on the presence of MPO and independent of · O2? generation during phagocytosis but independent of MPO during FMLP activation. In contrast lucigenin-CL was independent of MPO during both phagocytosis and FMLP activation and appeared to reflect · O2? production. Consequently, dependent on the type of activation, it appears that luminol- and lucigenin-CL are generated via different oxidative pathways and may serve as potentially useful tools to differentiate the redox activity of phagocytic cells. 相似文献
93.
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95.
We study compact connected surfaces inm-dimensional Euclidean spaceE
m (3 m 5) with a point through which every geodesic is aW-curve regarded as a curve in Em. 相似文献
96.
97.
Ahlen S Ambrosio M Antolini R Auriemma G Baker R Baldini A Bam BB Barbarino GC Barish BC Battistoni G Bellotti R Bemporad C Bernandini P Bilokon H Bisi V Bloise C Bower C Bussino S Cafagna F Calicchio M Campana D Campana P Carboni M Cecchini S Cei F Chiarella V Cormack R Corona A Coutu S De Cataldo G Dekhissi H De Marzo C De Vincenzi M Di Credico A Diehl E Erriquez O Favuzzi C Ficenec D Forti C Fusco P Giacomelli G Giannini G Giglietto N Giubellino P Grassi M Green P Grillo A Guarino F 《Physical review letters》1994,72(5):608-612
98.
99.
Mössbauer measurements in a-(Fe0.765Mn0.235)78Sn2Si6B14 have been performed with57Fe and119Sn. Both hyperfine fields show a kink near 70 K, indicating a freezing of the transverse spins. The ratio of the two hyperfine fields contains information about the correlation of the transverse spins. The ratioB
hf(Sn)/B
hf(Fe) stays constant aboveT
xy
and rises belowT
xy
. This indicates an alignment of the transverse spins on a local scale, as was also found inAuFe and a-FeZr. 相似文献
100.