排序方式: 共有74条查询结果,搜索用时 15 毫秒
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Ömer Taspinar Tobias Wilczek Julian Erver Dr. Martin Breugst Dr. Jörg-Martin Neudörfl Prof. Dr. Hans-Günther Schmalz 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(19):4256-4260
We report the first chemical synthesis of eurysterol A, a cytotoxic and antifungal marine steroidal sulfate with a unique C8−C19 oxy-bridged cholestane skeleton. After C19 hydroxylation of cholesteryl acetate, used as an inexpensive commercial starting material, the challenging oxidative functionalization of ring B was achieved by two different routes to set up a 5α-hydroxy-7-en-6-one moiety. As a key step, an intramolecular oxa-Michael addition was exploited to close the oxy-bridge (8β,19-epoxy unit). DFT calculations show this reversible transformation being exergonic by about −30 kJ mol−1. Along the optimized (scalable) synthetic sequence, the target natural product was obtained in only 11 steps in 5 % overall yield. In addition, an access to (isomeric) 7β,19-epoxy steroids with a previously unknown pentacyclic ring system was discovered. 相似文献
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Single crystals of MCd(NO2)3, with M=NH4, K, Rb, Cs, and Tl, respectively, were grown and investigated by means of optical and dielectric methods. The crystals show rhombohedral symmetry (possible space group R 3) and multi-domain patterns at ambient temperature. The compounds exhibit phase transitions above room-temperature of first (M=K) and second order (M=Rb, Cs, Tl), respectively, into cubic high-temperature phases. Observed dielectric anomalies and hysteresis loops point to ferroelectric properties and suggest a relaxational order-disorder mechanism of the nitrite ions to be responsible for the transitions. The MCd-(NO2)3-compounds are seen to represent a new family of ferroelectrics with a cubic prototypic phase closely related to the structural type of the perovskites. The transions are classified by symmetry considerations, and a possible structure of the cubic high-temperature phase with space group Pm3 is proposed. 相似文献
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The CO oxidation using mixtures of oxygen and nitrogen monoxide has been studied under stationary conditions. The measured selectivities could not always be foreseen from the results obtained in the binary systems CO/O2 and CO/NO. At high temperatures the amount of NO reduced is directly proportional to its fraction in the oxidizing gas. At low temperatures, NO may be reduced with high selectivity even in the presence of high oxygen concentration. 相似文献
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Velcicky J Lanver A Lex J Prokop A Wieder T Schmalz HG 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(20):5087-5110
A diversity-oriented, enantioselective synthesis of new (monoprotected) carbocyclic nucleoside analogues (CNAs) with the nucleobase attached to a 3-hydroxymethyl-4-trialkylsilyloxymethylcyclopent-2-en-1-yl scaffold was developed. As a key intermediate, racemic (5SR,8RS)-8-allyloxy-2-trimethylsilyl-7-oxa-bicyclo[3.3.0]-oct-1-en-3-one was prepared from 1,1-diallyloxy-3-trimethylsilyl-2-propyne in a cobalt-mediated Pauson-Khand reaction. The enantiomerically pure material was obtained through efficient kinetic resolution (selectivity factor s >/= 40 at -78 degrees C) by means of an oxazaborolidine-catalyzed borane reduction (CBS reduction) with catecholborane. The absolute configuration of the resolved products was determined by CD spectroscopy, Mosher ester analysis, and chemical correlation. Subsequent steps involve diastereoselective ketone reduction and fully regio- and diastereoselective introduction of the nucleobase through Pd(0)-catalyzed allylic substitution. The generality of the method was demonstrated by preparation of CNAs in both enantiomeric series with all five natural nucleobases, as well as 5-bromouracil, 5-fluorouracil, and 6-chloropurine. Screening of the various compounds in a cytotoxicity assay with BJAB and ALL tumor cell lines revealed that some of the compounds possess pronounced antitumoral properties (LD50 values down to 9 microM, as determined by lactate dehydrogenase release after 48 h). By measuring DNA fragmentation, it could be shown that the activity results from induction of apoptosis. 相似文献
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Döbereiner HG Gompper G Haluska CK Kroll DM Petrov PG Riske KA 《Physical review letters》2003,91(4):048301
The bending elasticity of a fluid membrane is characterized by its modulus and spontaneous curvature. We present a new method, advanced flicker spectroscopy of giant nonspherical vesicles, which makes it possible to simultaneously measure both parameters for the first time. Our analysis is based on the generation of a large set of reference data from Monte Carlo simulations of randomly triangulated surfaces. As an example of the potential of the procedure, we monitor thermal trajectories of vesicle shapes and discuss the elastic response of zwitterionic membranes to transmembrane pH gradients. Our technique makes it possible to easily characterize membrane curvature as a function of environmental conditions. 相似文献
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[reaction: see text] As a contribution to bioorganometallic chemistry, an enantioselective synthesis of novel carbocyclic nucleoside analogues with a ferroceno-cyclopentene backbone was developed. Diastereoselective cuprate 1,4-addition or Mukaiyama-Michael addition to a planar-chiral enoate (ethyl (E)-2-[2-methoxycarbonyl-ferrocenyl]-acrylate) allowed for the introduction of different side chains (RCH(2)). Other important steps include a Dieckmann cyclization and the attachment of the nucleobase (NB) in an iron-assisted S(N)1 reaction. Some of the target compounds were shown to exhibit significant apoptosis-inducing activity (LD(50) = 10-20 microM) against tumor cells. 相似文献
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Döbereiner HG Dubin-Thaler BJ Hofman JM Xenias HS Sims TN Giannone G Dustin ML Wiggins CH Sheetz MP 《Physical review letters》2006,97(3):038102
We have monitored active movements of the cell circumference on specifically coated substrates for a variety of cells including mouse embryonic fibroblasts and T cells, as well as wing disk cells from fruit flies. Despite having different functions and being from multiple phyla, these cell types share a common spatiotemporal pattern in their normal membrane velocity; we show that protrusion and retraction events are organized in lateral waves along the cell membrane. These wave patterns indicate both spatial and temporal long-range periodic correlations of the actomyosin gel. 相似文献