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1.
Laurens Kooijman Dr. Matthias Schuster Christian Baumann Simon Jurt Dr. Frank Löhr Dr. Boris Fürtig Prof. Dr. Peter Güntert Prof. Dr. Oliver Zerbe 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(47):21151-21158
To achieve efficient proton pumping in the light-driven proton pump bacteriorhodopsin (bR), the protein must be tightly coupled to the retinal to rapidly convert retinal isomerization into protein structural rearrangements. Methyl group dynamics of bR embedded in lipid nanodiscs were determined in the dark-adapted state, and were found to be mostly well ordered at the cytosolic side. Methyl groups in the M145A mutant of bR, which displays only 10 % residual proton pumping activity, are less well ordered, suggesting a link between side-chain dynamics on the cytosolic side of the bR cavity and proton pumping activity. In addition, slow conformational exchange, attributed to low frequency motions of aromatic rings, was indirectly observed for residues on the extracellular side of the bR cavity. This may be related to reorganization of the water network. These observations provide a detailed picture of previously undescribed equilibrium dynamics on different time scales for ground-state bR. 相似文献
2.
Synthesis of Highly Substituted γ‐Butyrolactones by a Gold‐Catalyzed Cascade Reaction of Benzyl Esters
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Maria Camila Blanco Jaimes Alexander Ahrens Daniel Pflästerer Dr. Matthias Rudolph Prof. Dr. A. Stephen K. Hashmi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(1):427-433
Easily accessible benzylic esters of 3‐butynoic acids in a gold‐catalyzed cyclization/rearrangement cascade reaction provided 3‐propargyl γ‐butyrolactones with the alkene and the carbonyl group not being conjugated. Crossover experiments showed that the formation of the new C?C bond is an intermolecular process. Initially propargylic–benzylic esters were used, but alkyl‐substituted benzylic esters worked equally well. In the case of the propargylic–benzylic products, a simple treatment of the products with aluminum oxide initiated a twofold tautomerization to the allenyl‐substituted γ‐butyrolactones with conjugation of the carbonyl group, the olefin, and the allene. The synthetic sequence can be conducted stepwise or as a one‐pot cascade reaction with similar yields. Even in the presence of the gold catalyst the new allene remains intact. 相似文献
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The modification of the number field sieve which Joux and Lercier recently used to compute logarithms in a prime field of a record 120 decimal digits makes use of the notion of a virtual logarithm of a prime ideal in a number ring. We provide necessary and sufficient conditions for their method to succeed and give an explicit formula for the virtual logarithm of an ideal. 相似文献
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In this article, we present results of an empirical study with 500 German students of grades 7 and 8. The study focussed on students' mathematics achievement and their interest in mathematics as well as on the relation between these two constructs. In particular, the results show that the development of an individual student's achievement between grade 7 and grade 8 depends on the achievement level of the specific classroom and therefore on the specific mathematics instruction Interest in mathematics could be regarded a predictor for mathematics achievement Moreover, our findings suggest that the students show hardly any fear of mathematics independent of their achievement level. 相似文献
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Marcel Oliver 《Theoretical and Computational Fluid Dynamics》1997,9(3-4):311-324
The so-called lake equations arise as the shallow-water limit of the rigid-lid equations—three-dimensional Euler equations
with a rigid-lid upper boundary condition—in a horizontally periodic basin with bottom topography. We prove an a priori estimate in the Sobolev space H
m
for m≥ 3 which shows that a solution to the rigid-lid equations can be approximated by a solution of the lake equations for an
interval of time which can be estimated in terms of the initial deviation from a columnar configuration and the magnitude
of the initial data in H
m
, the gradient of the bottom topography in H
m+1
, and the aspect ratio of the basin. In particular, any solution to the lake equations remains close to some solution of the
rigid-lid equations for an interval of time that can be made arbitrarily large by choosing the aspect ratio of the basin small.
Received 10 October 1996 and accepted 15 May 1997 相似文献
9.
The consecutive reactions of (CH3)2Si(OC2H5)2 and CH3Si(OC2H5)3 with methoxide ions were investigated in methanol solutions. The reverse transesterification reactions with ethoxide ions could be neglected in both cases since the concentration of ethoxide in methanol solution was assumed to be low due to the fast equilibrium reaction C2H5O? + CH3OH ? C2H5OH + CH3O?. The progress of the reactions was followed by monitoring the formation of ethanol with a Fourier-transform infrared spectrometer. All rate constants were determined at 295 K. The reactions between the dialkoxydimethylsilanes and methoxide ions were assumed to consist of two consecutive steps that can be represented by the net reaction; (CH3)2Si(OC2H5)2 + 2CH3O? → (CH3)2Si(OCH3)2 + 2C2H5O?. The two consecutive rate constants were established as 1.93 ± 0.12M?1s?1 and 1.00 ± 0.12M?1s?1, respectively. The consecutive rate constants for the reactions between the trialkoxymethylsilanes and methoxide ions can be written according to the total reaction; CH3Si(OC2H5)3 + 3CH3O? → CH3Si(OCH3)3 + 3C2H5O?. The three rate constants corresponding to each consecutive step were established as 1.12 ± 0.09 M?1s?1, 0.82 ± 0.10 M?1s?1, and 0.51 ± 0.06 M?1s?1, respectively. © 1995 John Wiley & Sons, Inc. 相似文献
10.