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11.
LetV() be a smooth, non-constant function on the torus and letT be a hyperbolic toral automorphism. Consider a discrete one dimensional Schrödinger operatorH, whose potential at sitej is given bygV
j
=gV(T
j
). We prove that wheng0 is small andg
1/2
|E|2–g
1/2
, the Lyapunov exponent for the cocycle generated byH-E is proportional tog
2. The proof relies on a formula of Pastur and Figotin and on symbolic dynamics. 相似文献
12.
13.
J. N. Spencer Jarusha DeGarmo I. M. Paul Qing He Xiaoming Ke Zhenqing Wu C. H. Yoder Shuyun Chen J. E. Mihalick 《Journal of solution chemistry》1995,24(6):601-609
Calorimetric studies of the inclusion complexes of straight and branched alcohols and of diols with alpha-cyclodextrin (-CD) have been carried out in water solvent. The data suggest that straight and branched chain alcohols enter the cavity of -CD alkyl end first. The hydroxyl group hydrogen bonds to the outer oxygen ring of the cyclodextrin. For branched chain alcohols the longer alkyl part of the molecule penetrates the -CD cavity up to the hydroxyl group. Diols form two hydrogen bonds to the outer oxygen ring of the cyclodextrin with some penetration into its interior. 相似文献
14.
15.
Gu P Haas P Hogan WP Kim SK Matthews JN Myung SS Schnetzer S Thomson GB Zou Y Arisaka K Roberts D Slater W Spencer MB Weaver M Briere RA Cheu E Harris DA Krolak P McFarland KS Roodman A Schwingenheuer B Somalwar SV Wah YW Winstein B Winston R Barker AR Swallow EC Bock GJ Coleman R Crisler M Enagonio J Ford R Hsiung YB Jensen DA O'Dell VR Ramberg E Tschirhart R Collins EM Gollin GD Nakaya T Yamanaka T 《Physical review letters》1996,76(23):4312-4315
16.
In an unsuccessful attempt to effect remote functionalization at C9, 4,4-dimethyloxazolidine-N-oxyl (doxyl) derivatives at C3 of 5β-androstan-3,17-dione and 5β-androstan-17β-ol-3-one were prepared and photolyzed. The former doxyl yielded its C13 stereoisomer; the latter was converted very slowly to intractable material. 相似文献
17.
Ashton PR Ballardini R Balzani V Credi A Dress KR Ishow E Kleverlaan CJ Kocian O Preece JA Spencer N Stoddart JF Venturi M Wenger S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2000,6(19):3558-3574
A molecular-level abacus-like system driven by light inputs has been designed in the form of a [2]rotaxane, comprising the pi-electron-donating macrocyclic polyether bis-p-phenylene-34-crown-10 (BPP34C10) and a dumbbell-shaped component that contains 1) a Ru(II) polypyridine complex as one of its stoppers in the form of a photoactive unit, 2) a p-terphenyl-type ring system as a rigid spacer, 3) a 4,4'-bipyridinium unit and a 3,3'-dimethyl-4,4'-bipyridinium unit as pi-electron-accepting stations, and 4) a tetraarylmethane group as the second stopper. The synthesis of the [2]rotaxane was accomplished in four successive stages. First of all, the dumbbell-shaped component of the [2]rotaxane was constructed by using conventional synthetic methodology to make 1) the so-called "west-side" comprised of the Ru(II) polypyridine complex linked by a bismethylene spacer to the p-terphenyl-type ring system terminated by a benzylic bromomethyl function and 2) the so-called "east-side" comprised of the tetraarylmethane group, attached by a polyether linkage to the bipyridinium unit, itself joined in turn by a trismethylene spacer to an incipient 3,3'-dimethyl-4,4'-bipyridinium unit. Next, 3) the "west-side" and "east-side" were fused together by means of an alkylation to give the dumbbell-shaped compound, which was 4) finally subjected to a thermodynamically driven slippage reaction, with BPP34C10 as the ring, to afford the [2]rotaxane. The structure of this interlocked molecular compound was characterized by mass spectrometry and NMR spectroscopy, which also established, along with cyclic voltammetry, the co-conformational behavior of the molecular shuttle. The stable translational isomer is the one in which the BPP34C10 component encircles the 4,4'-bipyridinium unit, in keeping with the fact that this station is a better pi-electron acceptor than the other station. This observation raises the question- can the BPP34C10 macrocycle be made to shuttle between the two stations by a sequence of photoinduced electron transfer processes? In order to find an answer to this question, the electrochemical, photophysical, and photochemical (under continuous and pulsed excitation) properties of the [2]rotaxane, its dumbbell-shaped component, and some model compounds containing electro- and photoactive units have been investigated. In an attempt to obtain the photoinduced abacus-like movement of the BPP34C10 macrocycle between the two stations, two strategies have been employed-one was based fully on processes that involved only the rotaxane components (intramolecular mechanism), while the other one required the help of external reactants (sacrificial mechanism). Both mechanisms imply a sequence of four steps (destabilization of the stable translational isomer, macrocyclic ring displacement, electronic reset, and nuclear reset) that have to compete with energy-wasteful steps. The results have demonstrated that photochemically driven switching can be performed successfully by the sacrificial mechanism, whereas, in the case of the intramolecular mechanism, it would appear that the electronic reset of the system is faster than the ring displacement. 相似文献
18.
J. N. Spencer S. K. Berger C. R. Powell B. D. Henning G. S. Furman W. M. Loffredo E. M. Rydberg R. A. Neubert C. E. Shoop D. N. Blauch 《Journal of solution chemistry》1981,10(7):501-509
Enthalpies of solution and of transfer of amides for the solvents chloroform (CHCl3), methylenechloride (CH2Cl2), carbontetrachloride (CCl4), cyclohexane (C6H12), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMA), and ethylacetate (EtOAc) have been used to isolate and quantify the solvation interactions of amides in chlorinated solvents. Specific interactions at the aminde carbonyl and N–H groups have been identified. An analysis of the transfer enthalpies of pyrrole and methylpyrrole from cyclohexane to the chlorinated solvents shows that specific interactions between the pyrroles and these solvents are similar in nature. A means of calculating differences in the transfers of different solutes between the same solvent pair is given.Work done at Lebanon Valley College. 相似文献
19.
20.
Huang F Haydock SF Mironenko T Spiteller D Li Y Spencer JB 《Organic & biomolecular chemistry》2005,3(8):1410-1418
The biosynthetic gene cluster of the 2-deoxystreptamine (DOS)-containing aminoglycoside antibiotic neomycin has been cloned for the first time by screening of a cosmid library of Streptomyces fradiae NCIMB 8233. Sequence analysis has identified 21 putative open reading frames (ORFs) in the neomycin gene cluster (neo) with significant protein sequence similarity to gene products involved in the biosynthesis of other DOS-containing aminoglycosides, namely butirosin (btr), gentamycin (gnt), tobramycin (tbm) and kanamycin (kan). Located at the 5'-end of the neo gene cluster is the previously-characterised neomycin phosphotransferase gene (apH). Three genes unique to the neo and btr clusters have been revealed by comparison of the neo cluster to btr, gnt, tbm and kan clusters. This suggests that these three genes may be involved in the transfer of a ribose moiety to the DOS ring during the antibiotic biosynthesis. The product of the neo-6 gene is characterised here as the L-glutamine : 2-deoxy-scyllo-inosose aminotransferase responsible for the first transamination in DOS biosynthesis, which supports the assignment of the gene cluster. 相似文献