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1.
Experimental and Theoretical Studies on the Rearrangement of 2‐Oxoazepane α,α‐Amino Acids into 2′‐Oxopiperidine β2,3,3‐Amino Acids: An Example of Intramolecular Catalysis 下载免费PDF全文
Dr. Diego Núñez‐Villanueva Dr. M. Ángeles Bonache Laura Lozano Dr. Lourdes Infantes Prof. José Elguero Prof. Ibon Alkorta Prof. M. Teresa García‐López Dr. Rosario González‐Muñiz Dr. Mercedes Martín‐Martínez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(6):2489-2500
Enantiopure β‐amino acids represent interesting scaffolds for peptidomimetics, foldamers and bioactive compounds. However, the synthesis of highly substituted analogues is still a major challenge. Herein, we describe the spontaneous rearrangement of 4‐carboxy‐2‐oxoazepane α,α‐amino acids to lead to 2′‐oxopiperidine‐containing β2,3,3‐amino acids, upon basic or acid hydrolysis of the 2‐oxoazepane α,α‐amino acid ester. Under acidic conditions, a totally stereoselective synthetic route has been developed. The reordering process involved the spontaneous breakdown of an amide bond, which typically requires strong conditions, and the formation of a new bond leading to the six‐membered heterocycle. A quantum mechanical study was carried out to obtain insight into the remarkable ease of this rearrangement, which occurs at room temperature, either in solution or upon storage of the 4‐carboxylic acid substituted 2‐oxoazepane derivatives. This theoretical study suggests that the rearrangement process occurs through a concerted mechanism, in which the energy of the transition states can be lowered by the participation of a catalytic water molecule. Interestingly, it also suggested a role for the carboxylic acid at position 4 of the 2‐oxoazepane ring, which facilitates this rearrangement, participating directly in the intramolecular catalysis. 相似文献
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Let f be a smooth map between unit spheres of possibly different dimensions. We prove the global existence and convergence of the mean curvature flow of the graph of f under various conditions. A corollary is that any area‐decreasing map between unit spheres (of possibly different dimensions) is isotopic to a constant map. © 2004 Wiley Periodicals, Inc. 相似文献
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Jing Zhang Dan Shan Shaolin Mu 《Journal of polymer science. Part A, Polymer chemistry》2007,45(23):5573-5582
A copolymer, poly(aniline‐co‐o‐aminophenol), was prepared chemically by using ammonium peroxydisulfate as an oxidant. The monomer concentration ratio of o‐aminophenol to aniline strongly influences the copolymerization rate and properties of the copolymer. The optimum composition of a mixture for the chemical copolymerization consisted of 0.3 M aniline, 0.021 M o‐aminophenol, 0.42 M ammonium peroxydisulfate, and 2 M H2SO4. The result of cyclic voltammograms in a potential region of ?0.20 to 0.80 V (vs.SCE) indicates that the electrochemical activity of the copolymer prepared under the optimum condition is similar to that of polyaniline in more acid solutions. However, the copolymer still holds the good electrochemical activity until pH 11.0. Therefore, the pH dependence of the electrochemical property of the copolymer is improved, compared with poly(aniline‐co‐o‐aminophenol) prepared electrochemically, and is much better than that of polyaniline. The spectra of IR and 1H NMR confirm that o‐aminophenol units are included in the copolymer chain, which play a key role in extending the usable pH region of the copolymer. The visible spectra of the copolymers show that a high concentration ratio of o‐aminophenol to aniline in a mixture inhibits the chain growth. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5573–5582, 2007 相似文献
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针对认知无线电(CR)系统中频谱感知技术能量效率低的问题,提出了一种基于二分法迭代寻优的联合优化算法。该算法通过联合传输功率与感知时隙进行优化,最大化地提高了CR系统的能量效率,并且在针对优化参数ξ的寻优过程中,使用了二分法与迭代算法结合的寻优方法。通过理论分析,与其他类似算法相比,该算法的寻优速度更快,算法复杂度更低,函数收敛速度更快,实际应用的可扩展性更强。数值仿真分析结果表明,在保证检测性能的前提下,提出的算法能够很好地解决能效的最优化问题,在恒定检测概率Pd=0.9和Pd=0.7条件下,所提出算法的能耗开销均低于其他算法,在系统吞吐量中所提出算法均优于其他算法,为CR系统的发展提供了理论支撑,更加符合未来CR系统的节能发展方向。 相似文献
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Refractive-diffractive visual system for micro-display of LCOS 总被引:1,自引:0,他引:1
One head-mounted display visual system for computer entertainment and three-dimensional display of virtual-reality was achieved,
which consists of a hybrid refractive-diffractive eyepiece and a relay reflector. It can be used in micro-display of liquid
crystal on silicon (LCOS) diagonal of 18 mm. The whole system has better performance, with 60° field of view, 10 mm exit pupil,
23 mm eye relief, and reduces weight and size. 相似文献