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941.
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Structure of Amido Pyridinium Betaines: Persistent Intermolecular C−H⋅⋅⋅N Hydrogen Bonding in Solution
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Dr. Robert J. Thatcher Dr. David G. Johnson Dr. John M. Slattery Dr. Richard E. Douthwaite 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(10):3414-3421
A hydrogen bond of the type C?H???X (X=O or N) is known to influence the structure and function of chemical and biological systems in solution. C?H???O hydrogen bonding in solution has been extensively studied, both experimentally and computationally, whereas the equivalent thermodynamic parameters have not been enumerated experimentally for C?H???N hydrogen bonds. This is, in part, due to the lack of systems that exhibit persistent C?H???N hydrogen bonds in solution. Herein, a class of molecule based on a biologically active norharman motif that exhibits unsupported intermolecular C?H???N hydrogen bonds in solution has been described. A pairwise interaction leads to dimerisation to give bond strengths of about 7 kJ mol?1 per hydrogen bond, which is similar to chemically and biologically relevant C?H???O hydrogen bonding. The experimental data is supported by computational work, which provides additional insight into the hydrogen bonding by consideration of electrostatic and orbital interactions and allowed a comparison between calculated and extrapolated NMR chemical shifts. 相似文献
945.
Paul M. Bogie Lauren R. Holloway Courtney Ngai Tabitha F. Miller Divine K. Grewal Prof. Richard J. Hooley 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(43):10232-10238
A self-assembled Fe4L6 cage complex internally decorated with acid functions is capable of accelerating the thioetherification of activated alcohols, ethers and amines by up to 1000-fold. No product inhibition is seen, and effective supramolecular catalysis can occur with as little as 5 % cage. The substrates are bound in the host with up to micromolar affinities, whereas the products show binding that is an order of magnitude weaker. Most importantly, the cage host alters the molecularity of the reaction: whereas the reaction catalyzed by simple acids is a unimolecular, SN1-type substitution process, the rate of the host-mediated process is dependent on the concentration of nucleophile. The molecularity of the cage-catalyzed reaction is substrate-dependent, and can be up to bimolecular. In addition, the catalysis can be prevented by a large excess of nucleophile, where substrate inhibition dominates, and the use of tritylated anilines as substrates causes a negative feedback loop, whereby the liberated product destroys the catalyst and stops the reaction. 相似文献
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Nana Amponsah Kyeremateng Frederic Dumur Philippe Knauth Brigitte Pecquenard Thierry Djenizian 《Comptes Rendus Chimie》2013,16(1):80-88
The electrochemical synthesis of a copolymer electrolyte (PEO-PMMA) into titania nanotubes is described and studied. Compared with the electrochemical systems based on solid electrolytes deposited by top-down techniques, the copolymer/titania nanotube material reveals high electrochemical performance, opening new perspectives for the fabrication of 3D all-solid-state microbatteries. 相似文献
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Richard Marcuson 《Linear and Multilinear Algebra》2013,61(1):49-55
Recently, Marcuson extended the classical construction of Tits systems in Steinberg groups to include the Kac-Moody Steinberg groups associated with the infinite dimensional versions of the great Lie algebras. If these Lie algebras and their Kac-Moody groups are viewed as limits of their finite dimensional counterparts, more direct methods may be employed. In fact, the Kac-Moody Chevalley groups of these Lie algebras are seen to be simple. 相似文献
950.
Abstract. The method of vanishing artificial viscosity is used to obtain smooth, largedata travelling-wave solutions to a class of conservation laws with semidefinite viscosity. The one-dimensional Navier-Stokes equations serve as an illustrating example. 相似文献