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本文对广义风险过程中的渐近方差作了非参数估计,得出并证明了两个定理,为广义风险过程中破产概率的区间估计作了理论准备. 相似文献
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8,8"-Biflavonoidsareantw0rtantclass0fbiflavonoids.Asasystematicresearchofthe8,8"-biflav0noids,wehavepreviouslyreportedthestudyonthereactionof2'-hydroxychaloneswithl2-H2SO4-DMSOsystem.'InthispaPer,thesynthesisof5,5",7,7',-tetTameth0xy-8,8"-biflavonela2,4,4",7,7"-tetramethoxy-8,8"-biflavone1b',4',4",,5,5,',7,7"-hexamethoxy-8,8"-biflav0ne1c4and4,4"-dibenZyl0xy-5,5",7,7"-tetramothoxy-8,8"-biflavoneldisreported.ThesyntheticmethodisshownintheSchemebelow.2-Hydroxyacet0phenonescondensedwithsubsti… 相似文献
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Heintzelman GR Fang WK Keen SP Wallace GA Weinreb SM 《Journal of the American Chemical Society》2002,124(15):3939-3945
A stereoselective total synthesis of the structure 1 proposed for the freshwater cyanobacterial heptatotoxin cylindrospermopsin has been accomplished in approximately 30 operations starting from commercially available 4-methoxypyridine. Utilizing methodology developed by Comins, the tetrasubstituted piperidine A-ring unit of the hepatotoxin was efficiently constructed. The two remaining stereocenters in the natural product were then set by a stereospecific intramolecular N-sulfinylurea Diels-Alder cyclization/Grignard ring opening/allylic sulfoxide [2,3]-sigmatropic rearrangement sequence previously developed in these laboratories, leading to key intermediate 29. The stereochemical assignment of alcohol 29, which contains all six of the stereogenic centers of the natural product, was confirmed by an X-ray crystal structure determination of a derivative. Installation of the D-ring uracil moiety was effected by using our new methodology developed for this purpose, and construction of the C-ring guanidine completed the total synthesis of racemic structure 1. However, the (1)H NMR data for this compound do not match that of cylindrospermopsin, but instead agree with the data reported for 7-epicylindrospermopsin, a minor toxic metabolite that co-occurs with cylindrospermopsin. Therefore, we propose a revision of the stereochemical assignments of these natural products such that cylindrospermopsin is now represented as structure 2 and 7-epicylindrospermopsin is 1. This reassignment was further confirmed by Mitsunobu inversion of the C-7 alcohol 51 to epimer 52, and conversion of this compound to tetracyclic diol 57, which has previously been transformed to cylindrospermopsin (2). 相似文献
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Two points involving molecular structure have been investigated using mass spectrometry. First, mass spectra have been obtained that indicate a rapid means for differentiating bimolecular compounds from other structural isomers. Second, the mass spectrometric method has been used to evaluate bonding within bimolecular compounds. Quinone compounds have been reacted with dhydroxybenzene compounds to produce quinhydrone products, and upon mass spectrometric analysis, the quinhydrones decompose to regenerate derivatives of the starting materials. Evaluation of the decomposition products suggests that the hydroxyl hydrogens are involved in a resonance structure, and while in symmetrical quinhydrones, the hydroxyl hydrogens are probably associated equally with each reactant, unsymmetrical quinhydrones generate an unbalanced electronic distribution that eliminates the complete equivalency of the hydrogens. 相似文献
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Consider the two-parameter family of real analytic maps $F_{a,b} :x \mapsto x + a + \tfrac{b}{{2\pi }}$ sin(2πx) which are lifts of degree one endomorphisms of the circle. The purpose of this paper is to provide a proof that for any closed intervalI, the set of mapsF a,b whose rotation interval isI, form a contractible set. 相似文献
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高效液相色谱氮杂冠醚键合固定相的合成及性能研究 总被引:2,自引:0,他引:2
我们曾用γ-氯丙基键合硅胶(CPS),在氢化钠(NaH)作用下合成了3-(氮杂-18-冠-6)丙基键合固定相(BCP)[1].该固定相对碱基、核苷酸、硝基苯酚等有较好的分离选择性,但由于NaH对硅胶基质腐蚀作用较大,导致BCP柱效及渗透性较低.本文采... 相似文献
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2,4,6-三硝基苯酚改性锆铝复合氧化物固定相分离富勒烯的色谱性能研究 总被引:1,自引:0,他引:1
制备了用于分离C60和C70的2,4,6-三硝基苯酚改性锆铝复合氧化物高效液相色谱固定相,考察了流动相中甲苯的含量、柱温及流速对C60和C70分离的影响,同时比较了酸腐蚀前后锆铝复合氧化物基质对分离的影响,结果表明,2,4,6-三硝基苯酚改性酸腐蚀后锆铝复合氧化物填料对富勒烯表现出较强的分离能力,具有作为富勒烯制备分离的潜力。 相似文献
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