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1.
Solvent Influence on Cellulose 1,4‐β‐Glycosidic Bond Cleavage: A Molecular Dynamics and Metadynamics Study 下载免费PDF全文
Claudia Loerbroks Eliot Boulanger Prof. Dr. Walter Thiel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(14):5477-5487
We explore the influence of two solvents, namely water and the ionic liquid 1‐ethyl‐3‐methylimidazolium acetate (EmimAc), on the conformations of two cellulose models (cellobiose and a chain of 40 glucose units) and the solvent impact on glycosidic bond cleavage by acid hydrolysis by using molecular dynamics and metadynamics simulations. We investigate the rotation around the glycosidic bond and ring puckering, as well as the anomeric effect and hydrogen bonds, in order to gauge the effect on the hydrolysis mechanism. We find that EmimAc eases hydrolysis through stronger solvent–cellulose interactions, which break structural and electronic barriers to hydrolysis. Our results indicate that hydrolysis in cellulose chains should start from the ends and not in the centre of the chain, which is less accessible to solvent. 相似文献
2.
Walter Benz 《Monatshefte für Mathematik》2004,141(1):1-10
The lines of euclidean and hyperbolic geometries are characterized as metric lines in the sense of Blumenthal–Menger, and the lines of spherical and elliptic geometry as periodic ones. In euclidean geometries there do not exist periodic lines. 相似文献
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Hans-Rudolf Buser Michael Oehme Walter Vetter Bernd Luckas 《Fresenius' Journal of Analytical Chemistry》1993,347(12):502-512
Summary Conventional electron ionization (EI) mass spectrometry (MS) and MS/MS techniques were applied to the analysis of two abundant octa and nonachlorobornanes isolated from seals of the Baltic sea and originating from technical toxaphene. The exact sterical structures of the two compounds were previously determined using nuclear magnetic resonance (NMR) spectroscopy by two independent research groups. The MS and MS/MS data generated in this study allowed partial structure elucidation of these polychlorobornanes, in particular revealing the distribution of the Cl substituents between the six-membered carbon ring, the bridge and the bridgehead in the parent bornane structure. Fragmentation of the six-membered carbon ring and the bridge by retro-Diels-Alder (RDA) and related mechanisms was discovered by studying specific parent/daughter ion transitions. The detailed fragmentation pathways formulated may be applicable to the structure elucidation of other toxaphene congeners and the monitoring of strategic transitions is highly selective for the detection of these compounds in technical toxaphene and in environmental samples. 相似文献
4.
Walter Benz Hamburg 《Results in Mathematics》2003,44(1-2):41-43
It will be proved that the functional equation of periodic lines has no solution for hyperbolic distances. 相似文献
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We investigate function spaces of generalised smoothness of Besov and Triebel–Lizorkin type. Equivalent quasi-norms in terms
of maximal functions and local means are given. An atomic decomposition theorem for this type of spaces is proved.
Mathematics Subject Classification (2000) 46E35 相似文献
8.
6-Thia-l-aza-5λ5-phosphabicyclo[3.2.0]hept-3-enes and Isothiocyanatophosphine-sulfides from (Methylidenamino)phosphines, Carbon Disulfide, and Acetylene- or Ethylene Derivatives (Methylidenamino)phosphines react with carbon disulfide to 1,3,2-thiazaphosphete derivatives 2 . Acetylenedicarboxylates give with 2 6-thia-l-aza-5λ5-phosphabicyclo[3.2.0]hept-3-enes 4a , b , and acrylates yield isothio-cyanatophosphin-sulfides 5a – c . The structures of 4a and 5a are proven by an X-ray diffraction analysis. 相似文献
9.
We study the transversal spin–spin correlations in the non-equilibrium steady state of the XY chain constructed by coupling a finite cutout of the chain to the two infinite parts to its left and right acting as thermal reservoirs at different temperatures. We prove that the spatial decay of these correlations is at least exponentially fast. 相似文献
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