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51.
Kamila B. Muchowska Dominic J. Pascoe Stefan Borsley Ivan V. Smolyar Ioulia K. Mati Catherine Adam Gary S. Nichol Kenneth B. Ling Scott L. Cockroft 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(34):14710-14716
Interactions between carbonyl groups are prevalent in protein structures. Earlier investigations identified dominant electrostatic dipolar interactions, while others implicated lone pair n→π* orbital delocalisation. Here these observations are reconciled. A combined experimental and computational approach confirmed the dominance of electrostatic interactions in a new series of synthetic molecular balances, while also highlighting the distance-dependent observation of inductive polarisation manifested by n→π* orbital delocalisation. Computational fiSAPT energy decomposition and natural bonding orbital analyses correlated with experimental data to reveal the contexts in which short-range inductive polarisation augment electrostatic dipolar interactions. Thus, we provide a framework for reconciling the context dependency of the dominance of electrostatic interactions and the occurrence of n→π* orbital delocalisation in C=O⋅⋅⋅C=O interactions. 相似文献
52.
Yulu Jiang Dr. Taro Ozaki Mei Harada Tadachika Miyasaka Dr. Hajime Sato Dr. Kazunori Miyamoto Dr. Junichiro Kanazawa Dr. Chengwei Liu Prof. Dr. Jun-ichi Maruyama Dr. Masaatsu Adachi Dr. Atsuo Nakazaki Prof. Dr. Toshio Nishikawa Prof. Dr. Masanobu Uchiyama Dr. Atsushi Minami Prof. Dr. Hideaki Oikawa 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(41):18152-18158
Lolitrems are tremorgenic indole diterpenes that exhibit a unique 5/6 bicyclic system of the indole moiety. Although genetic analysis has indicated that the prenyltransferase LtmE and the cytochrome P450 LtmJ are involved in the construction of this unique structure, the detailed mechanism remains to be elucidated. Herein, we report the reconstitution of the biosynthetic pathway for lolitrems employing a recently established genome-editing technique for the expression host Aspergillus oryzae. Heterologous expression and bioconversion of the various intermediates revealed that LtmJ catalyzes multistep oxidation to furnish the lolitrem core. We also isolated the key reaction intermediate with an epoxyalcohol moiety. This observation allowed us to establish the mechanism of radical-induced cyclization, which was firmly supported by density functional theory calculations and a model experiment with a synthetic analogue. 相似文献
53.
Haruka Takeuchi Prof. Dr. Shinsuke Inuki Kohei Nakagawa Takaaki Kawabe Dr. Atsuhiko Ichimura Prof. Dr. Shinya Oishi Prof. Dr. Hiroaki Ohno 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(47):21396-21401
We report herein a nonbiomimetic strategy for the total synthesis of the plicamine-type alkaloids zephycarinatines C and D. The key feature of the synthesis is a stereoselective reductive radical ipso-cyclization using visible-light-mediated photoredox catalysis. This cyclization enabled the construction of a 6,6-spirocyclic core structure through the addition of a carbon-centered radical onto the aromatic ring. Biological evaluation of zephycarinatines and their derivatives revealed that the synthetic derivative with a keto group displays moderate inhibitory activity against LPS-induced NO production. This approach could offer future opportunities to expand the chemical diversity of plicamine-type alkaloids as well as providing useful intermediates for their syntheses. 相似文献
54.
In this work, a vanillin complex is immobilized onto MCM-41 and characterized by FT-IR, X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy, thermogravimetric analysis, and BET techniques. This supported Schiff base complex was found to be an efficient and recoverable catalyst for the chemoselective oxidation of sulfides into sulfoxides and thiols into their corresponding disulfides (using hydrogen peroxide as a green oxidant) and also a suitable catalyst for the preparation of 2,3-dihydroquinazolin-4(1H)-one derivatives in water at 90°C. Using this protocol, we show that a variety of disulfides, sulfoxides, and 2,3-dihydroquinazolin-4(1H)-one derivatives can be synthesized in green conditions. The catalyst can be recovered and recycled for further reactions without appreciable loss of catalytic performance. 相似文献
55.
56.
Qian Jin Luo 《数学学报(英文版)》2020,36(6):711-722
Let B be the unit disc in R~2, H be the completion of C_0∞(B) under the norm■ .By the method of blow-up analysis and an argument of rearrangement with respect to the standard hyperbolic metric ■, we prove that, for any fixed■ ,the supremum■ .This is an analog of early results of Lu–Yang(Discrete Contin. Dyn. Syst., 2009) and Yang(Trans.Amer. Math. Soc., 2007), and extends those of Wang–Ye(Adv. Math., 2012) and Yang–Zhu(Ann.Global Anal. Geom., 2016). 相似文献
57.
58.
ShiJun Liao 《中国科学:物理学 力学 天文学(英文版)》2020,(3):70-81
A new non-perturbative approach is proposed to solve time-independent Schr?dinger equations in quantum mechanics.It is based on the homotopy analysis method(HAM)that was developed by the author in 1992 for highly nonlinear equations and has been widely applied in many fields.Unlike perturbative methods,this HAM-based approach has nothing to do with small/large physical parameters.Besides,convergent series solution can be obtained even if the disturbance is far from the known status.A nonlinear harmonic oscillator is used as an example to illustrate the validity of this approach for disturbances that might be one thousand times larger than the possible superior limit of the perturbative approach.This HAM-based approach could provide us rigorous theoretical results in quantum mechanics,which can be directly compared with experimental data.Obviously,this is of great benefit not only for improving the accuracy of experimental measurements but also for validating physical theories. 相似文献
59.
60.
为玻色Hofstadter梯子模型引入交错跃迁,来扩展模型支持的量子流相.基于精确对角化和密度矩阵重整化群计算发现,无相互作用时,系统中包含横流相、涡旋相和纵流相;横流相来自均匀跃迁时Hofstadter梯子模型的Meissner相,纵流相是交错跃迁时才可见的流相.强相互作用极限下系统的超流区也包含横流相、纵流相和涡旋相,但存在更多的相变级数;超流区的横流相、纵流相之间存在相变但Mott区的不存在,把Mott区的"横、纵流相"称为Mott-均匀相,在Mott区只存在均匀相和涡旋相.跃迁的交错会压缩涡旋相存在的区域,使Mott区最终只剩下均匀相;跃迁的交错不仅能驱动Mott-超流相变,还使磁通的改变也能够驱动系统的Mott-超流相变.对这一系统的研究丰富了磁通系统中的量子流相,同时为研究拓扑流特性提供了模型支持. 相似文献