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1.
2.
Alexander Premet has stated the following problem: what is a relation between subregular nilpotent representations of a classical semisimple restricted Lie algebra and non-commutative deformations of the corresponding singularities? We solve this problem for type A. 相似文献
3.
Ghandi K Addison-Jones B Brodovitch JC McCollum BM McKenzie I Percival PW 《Journal of the American Chemical Society》2003,125(32):9594-9595
Muoniated free radicals have been detected in muon-irradiated aqueous solutions of acetone at high temperatures and pressures. At temperatures below 250 degrees C, the radical product is consistent with muonium addition to the keto form of acetone. However, at higher temperatures, a different radical was detected, which is attributed to muonium addition to the enol form. Muon hyperfine coupling constants have been determined for both radicals over a wide range of temperatures, significantly extending the range of conditions under which these radicals and the keto-enol equilibrium have been studied. 相似文献
4.
Ramnial T McKenzie I Gorodetsky B Tsang EM Clyburne JA 《Chemical communications (Cambridge, England)》2004,(9):1054-1055
One-electron oxidation of N-heterocyclic carbenes (NHCs) has been carried out using oxidising agents such as tetracyanoethylene (TCNE) and ferrocenium [Cp(2)Fe](+); the formation of carbene radical cations is postulated. 相似文献
5.
Coldham I Crapnell KM Fernàndez JC Moseley JD Rabot R 《The Journal of organic chemistry》2002,67(17):6181-6187
A synthesis of the core ABC ring system of the manzamine alkaloids is described, starting from arecoline. The key steps involve a Claisen rearrangement to set up a 4-substituted-3-methylenepiperidine and a stereoselective azomethine ylide dipolar cycloaddition reaction. Condensation of the aldehyde 6 and sarcosine ethyl ester hydrochloride salt gives an intermediate azomethine ylide, which undergoes an intramolecular cycloaddition reaction to set up two new rings and three new chiral centers stereoselectively. The aldehyde 6 was not a suitable substrate for related azomethine ylide cycloaddition reactions with other amines. However, the related dimethyl acetal 26 could be condensed with a variety of amines to give the desired tricyclic products. The cycloaddition reaction with N-methyl or N-allyl glycine ethyl ester gave almost exclusively the exo adduct, whereas cycloaddition with glycine ethyl ester gave the endo adduct. 相似文献
6.
A computational study has been performed to examine the reactions of a model beta-diketiminatoaluminium (I) complex with the hydrogen atom and with the electron. It was found that the hydrogen atom adds to the metal centre exothermically (DeltaH(rxn)=-202 kJ mol(-1)), and the spin density in the resulting radical resides entirely on the beta-diketiminato ligand. The spin density of the corresponding radical anion is very similar to the H-adduct. 相似文献
7.
RNA targeting is an exciting frontier for drug design. Intriguing targets include functional RNA structures in structurally-conserved untranslated regions (UTRs) of many lethal viruses. However, computational docking screens, valuable in protein structure targeting, fail for inherently flexible RNA. Herein we harness MD simulations with Markov state modeling to enable nanosize metallo-supramolecular cylinders to explore the dynamic RNA conformational landscape of HIV-1 TAR untranslated region RNA (representative for many viruses) replicating experimental observations. These cylinders are exciting as they have unprecedented nucleic acid binding and are the first supramolecular helicates shown to have anti-viral activity in cellulo: the approach developed in this study provides additional new insight about how such viral UTR structures might be targeted with the cylinder binding into the heart of an RNA-bulge cavity, how that reduces the conformational flexibility of the RNA and molecular details of the insertion mechanism. The approach and understanding developed represents a new roadmap for design of supramolecular drugs to target RNA structural motifs across biology and nucleic acid nanoscience.MD simulations and Markov state modeling explore induced fit binding of metallo-helicates to bulges in dynamic TAR RNA, reproduce experimental data, show how RNA conformational flexibility is reduced, and give mechanistic insight into insertion. 相似文献
8.
Summary Consider estimating the mean vector from dataN
n
(,
2
I) withl
q
norm loss,q1, when is known to lie in ann-dimensionall
p
ball,p(0, ). For largen, the ratio of minimaxlinear risk to minimax risk can bearbitrarily large ifp
. Obvious exceptions aside, the limiting ratio equals 1 only ifp=q=2. Our arguments are mostly indirect, involving a reduction to a univariate Bayes minimax problem. Whenp, simple non-linear co-ordinatewise threshold rules are asymptotically minimax at small signal-to-noise ratios, and within a bounded factor of asymptotic minimaxity in general. We also give asymptotic evaluations of the minimax linear risk. Our results are basic to a theory of estimation in Besov spaces using wavelet bases (to appear elsewhere). 相似文献
9.
Thanks to Hall's documentation of a situation he described asa Comedy of errors in the earlier literature onstable distributions, there is now general agreement as to theparametrization of these distributions when standardized asto location and scale. However, two subtly different parametrizationsof location and scale remain current in the afocal stable cases,defined as those with characteristic exponent = 1 and skewnessparameter ß 0. The more widely used parametrization,adopted by Hall and two recent monographs, lacks the linearityproperty that is ordinarily expected of location and scale parameters.This note shows that the alternative parametrization has thislinearity property, and compares the implications of the twoparametrizations for properties of stable distributions. A thirdrecent monograph seeks to avoid these issues by denying thatthe afocal stable distributions are stable at all, but it isshown that they are, in fact, integral members of the stablefamily. 相似文献
10.
Functionalized branched aziridines can be prepared in high yields and with high levels of regioselectivity using unprotected aziridines as nitrogen sources in palladium-catalyzed allylic amination. High levels of enantioselectivity can be achieved with BINAP on palladium. This methodology allows for strategic placement of an aziridine-containing fragment within a complex molecule environment for further elaboration. 相似文献