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921.
Poon DK Schubert M Au J Okon M Withers SG McIntosh LP 《Journal of the American Chemical Society》2006,128(48):15388-15389
We have investigated the lysine side chain amines in the 34 kDa catalytic domain from Cellulomonas fimi beta-(1,4)-glycosidase Cex (or CfXyn10A) using 1H-detected 15N heteronuclear correlation NMR spectroscopy. Signals from the 1Hzeta ( approximately 8 ppm) and 15Nzeta ( approximately 35 ppm) of Lys302 in the unmodified enzyme and Lys47 in a trapped cellobiosyl-enzyme intermediate were detected in a 1H-15N HMQC spectrum (pH 6.5 and 30 degrees C). The amine of Lys302 forms a buried ion pair, and that of Lys47 is hydrogen bonded to the cellobioside. Both lysines are positively charged, as unambiguously demonstrated by the splitting of their 15Nzeta signals into quartets (|1JNH| approximately 75 Hz) in a 1H-15N HSQC spectrum recorded without 1H decoupling during 15N evolution. Qualitative insights into the dynamic properties of these lysines are also provided by the deviations of their quartet intensity ratios from that of approximately 3:1:1:3 expected for a highly mobile amine. On the basis of the observed ratios of approximately 1:1:1:1 for the quartet of Lys302 and approximately 0.5:1:1:0.5 for Lys47, the amine of the latter active site residue is most rigidly positioned. Signals from at least 8 and 10 additional positively charged, mobile amines in Cex were observed at 10 degrees C and pH 6.5 and 5.6, respectively. By using conditions of reduced temperature, slightly acidic pH, and low general base concentrations, as well as water flipback pulses to minimize the effects of hydrogen exchange, 1H-15N correlation experiments provide a sensitive route to directly investigate the charge states and dynamic properties of the N-terminal and side chain amines in proteins and protein complexes. 相似文献
922.
Roman Schubert 《Annales Henri Poincare》2006,7(6):1085-1098
We study the semiclassical behaviour of eigenfunctions of quantum systems with ergodic classical limit. By the quantum ergodicity
theorem almost all of these eigenfunctions become equidistributed in a weak sense. We give a simple derivation of an upper
bound of order
on the rate of quantum ergodicity if the classical system is ergodic with a certain rate. In addition we obtain a similar
bound on transition amplitudes if the classical system is weak mixing. Both results generalise previous ones by Zelditch.
Communicated by Jens Marklof
Submitted: March 16, 2005 Accepted: February 2, 2006 相似文献
923.
We employ numerical computations of the full Navier-Stokes equations to investigate non-Boussinesq convection in a rotating system using water as the working fluid. We identify two regimes. For weak non-Boussinesq effects the Hopf bifurcation from steady to oscillating (whirling) hexagons is supercritical and typical states exhibit defect chaos that is systematically described by the cubic complex Ginzburg-Landau equation. For stronger non-Boussinesq effects the Hopf bifurcation becomes subcritical and the oscillations exhibit localized chaotic bursting, which is modeled by a quintic complex Ginzburg-Landau equation. 相似文献
924.
The refractive-index contrast in dielectric multilayer structures, optical resonators, and photonic crystals is an important figure of merit that creates a strong demand for high-quality thin films with a low refractive index. A SiO2 nanorod layer with low refractive index of n = 1.08, to our knowledge the lowest ever reported in thin-film materials, is grown by oblique-angle electron-beam deposition of SiO2. A single-pair distributed Bragg reflector employing a SiO2 nanorod layer is demonstrated to have enhanced reflectivity, showing the great potential of low-refractive-index films for applications in photonic structures and devices. 相似文献
925.
Shiri Artstein-Avidan Hermann König Vitali Milman 《Journal of Functional Analysis》2010,259(11):2999-1344
We consider operators T from C1(R) to C(R) satisfying the “chain rule”
926.
Let A be a group. What can be said about the group B to ensure that A and the normal product AB belong to the same prescribed class of groups? Results in this direction are given for the classes of supersolvable groups, absolutely solvable groups and Lagrange groups. 相似文献
927.
As a demonstration of the flexibility of constructive mathematics, we propose an interpretation of propositional answer set programming (ASP) in terms of intuitionistic proof theory, in particular in terms of simply typed lambda calculus. While connections between ASP and intuitionistic logic are well-known, they usually take the form of characterizations of stable models with the help of some intuitionistic theories represented by specific classes of Kripke models. As such the known results are model-theoretic rather than proof-theoretic. In contrast, we offer an explanation of ASP using constructive proofs. 相似文献
928.
Robert Lichtenberger Stefan O. Baumann Maria Bendova Michael Puchberger Ulrich Schubert 《Monatshefte für Chemie / Chemical Monthly》2010,50(2):717-727
Abstract
Depending on the reaction conditions, different aluminium dialkylmalonate derivatives were obtained by reaction of aluminium alkoxides Al(OR)3 (R = Et, iPr, tBu) with dialkylmalonates, viz. Al(malonate)3 (malonate = dimethyl, diethyl, di-iso-propyl and di-tert-butyl malonate), Al2(OiPr)4(malonate)2 (malonate = di-iso-propyl and di-tert-butyl malonate), Al2(OiPr)2(di-iso-propylmalonate)4 and Al3(OH)(OEt)3(diethylmalonate)5. All compounds were characterized by NMR spectroscopy, and single crystal structure analyses are reported for each type of compound. An Al2(OiPr)2(dialkylmalonate)4 derivative was only obtained by disproportionation of Al2(OiPr)4(di-iso-propylmalonate)2, but not by reaction of Al(OiPr)3 with dialkylmalonates in the corresponding molar ratio. Reactions of Al(OtBu)3 only resulted in Al(malonate)3 derivatives, but no transesterification was observed, contrary to the reaction of Al(OiPr)3 with dimethyl or diethyl malonate. 相似文献929.
All papers published in the Journal of Radioanalytical and Nuclear Chemistry (JRNC) in the period 2005–2009 (source dataset)
and all papers citing these papers and published in other journals (target dataset) have been compiled. A scientometric analysis
of the datasets has been performed using Hirsch-type statistics. A comprehensive bibliography of the citing papers is presented. 相似文献
930.
Kaloudi-Chantzea A Karakostas N Raptopoulou CP Psycharis V Saridakis E Griebel J Hermann R Pistolis G 《Journal of the American Chemical Society》2010,132(46):16327-16329
The two sp(3) hybridized fluorine atoms of a Bodipy dye have been synthetically replaced with the linear donor ligand 4-ethynylpyridine (-C≡C-Py) to form a rigid and highly symmetrical 109.5° building block in which the fluorophore subunit is vertically aligned to the plane formed by the -C≡C-Py donors. Upon reaction of the above tecton with a 90° organoplatinum acceptor unit, an intensely fluorescent rhomboid cavitand was manifested in solution. In contrast to the vast majority of coordination-driven self-assembled chromophoric systems, the present one fully conserves the excellent photophysical properties of the parent Bodipy dye. These unique features of the present metallosupramolecular entity constitute a fascinating metal-to-ligand self-assembled prototype for building compact and intensely luminescent materials with host-guest capabilities. 相似文献