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701.
During investigations of cyclization reactions between chiral allylsilanes and N-acyliminium ions, it was discovered that a suitably positioned benzyloxy group on the allylsilane component caused a reversal in the diastereoselectivity of these reactions relative to that normally observed with alkyl-substituted allylsilanes. This effect was subsequently observed in two other reaction types. Investigations into this effect led to the proposal of product formation through thermodynamic control facilitated by neighboring group interactions with a transient cationic species. This hypothesis was experimentally supported by the isolation of an intermediate in the proposed mechanistic pathway. 相似文献
702.
J. Zhu S. L. Ban S. H. Ha 《The European Physical Journal B - Condensed Matter and Complex Systems》2012,85(2):67
The binding energy of an exciton screened by the electron-hole plasma in a wurtzite
GaN/In
x
Ga1−x
N quantum well (in
the case of 0.1 < x < 1 within which the interface phonon
modes play a dominant role) is calculated including the exciton-phonon interaction by a
variational method combined with a self-consistent procedure. The coupling between the
exciton and various longitudinal-like optical phonon modes is considered to demonstrate
the polaronic effect which strongly depends on the exciton wave function. All of the
built-in electric field, the exciton-phonon interaction and the electron-hole plasma
weaken the Coulomb coupling between an electron and a hole to reduce the binding energy
since the former separates the wave functions of the electron and hole in the
z direction and the later two enlarge the exciton Bohr radius. The
electron-hole plasma not only restrains the built-in electric field, but also reduces the
polaronic effect to the binding energy. 相似文献
703.
Shuqin Liu Xican Li Ban Chen Xiaojian Ouyang Yulu Xie Dongfeng Chen 《Molecules (Basel, Switzerland)》2022,27(15)
Phytophenol dimerization, which is a radical-mediated coupling reaction, plays a critical role in many fields, including lignin biosynthesis. To understand the reaction, 2,2-diphenyl-1-picrylhydrazyl radical was used to initiate a series of phytophenol dimerization reactions in methanol. The products were identified using ultra-performance liquid chromatography coupled with electrospray ionization quadrupole time-of-flight tandem mass spectrometry (UHPLC-ESI-Q-TOF-MS/MS) analysis in situ. The identified products mainly included biphenols, magnolol, honokiol, gingerol 6,6′-dimers, 3,6-dimethoxylcatechol β,β′ dimer, euphorbetin, bis-eugenol, dehydrodiisoeugenol, trans-ε-viniferin, (+) pinoresinol, and (−) pinoresinol. Structure–function relationship analysis allowed four basic rules to be defined: meta-excluded, C–C bonding domination, ortho-diOH co-activation, and exocyclic C=C involvement. The exocyclic C=C involvement, however, required conjugation with the phenolic core and the para-site of the -OH group, to yield a furan-fused dimer with two chiral centers. Computational chemistry indicated that the entire process was completed via a radical coupling reaction and an intramolecular conjugate addition reaction. Similar results were also found for the horseradish peroxidase (HRP)-catalyzed coniferyl alcohol dimerization, which produced (+) and (−) pinoresinols (but no (−) epipinoresinol), suggesting that the HRP-catalyzed process was essentially an exocyclic C=C-involved phytophenol dimerization reaction. The reaction was highly diastereoselective. This was attributed to the intramolecular reaction, which prohibited Re-attack. The four basic rules and diastereoselectivity can explain and even predict the main products in various chemical and biological events, especially oxidase-catalyzed lignin cyclization. 相似文献
704.
Shuqin Liu Xican Li Rongxin Cai Ban Chen Jingyuan Zeng Chunhou Li Xianxi Zhou Yueying Li 《Journal of separation science》2023,46(13):2300041
Eucommiae Folium (Duzhongye) is a traditional Chinese medicine with a long history of use in China. However, its quality-marker in Chinese Pharmacopoeia is poorly defined nowadays. The study, therefore, conducted an ultra-high-performance liquid chromatography coupled with hybrid quadrupole-orbitrap tandem mass spectrometry analysis to obtain accurate data. The obtained data were then compared with the authentic standards library using Xcalibur 4.1 software package and TraceFinder General Quan. Through the comparison, the study has putatively identified 26 bioactive compounds, which include 17 flavonoid derivatives (catechin, quercetin 3-gentiobioside, quercetin 3-O-β-D-glucose-7-O-β-D-gentiobioside, taxifolin, myricetin 3-O-galactoside, myricitrin, hyperoside, rutin, isoquercitrin, quercetin 3-O-β-xylopyranoside, quercitrin, isorhamnetin 3-O-β-D-glucoside, quercetin, kaempferol, S-eriodictyol, S-naringenin, and phloridzin), four caffeoylquinic acids (neochlorogenic acid, chlorogenic acid, isochlorogenic acid A, and isochlorogenic acid C), two alkaloids (vincamine and jervine), one lignan (pinoresinol), one xanthone (cowaxanthone B), and one steroid (cholesteryl acetate). Of these, flavonoid isoquercitrin is recommended as the new and additional pharmacopeia quality-marker candidate, which can not only overcome the unreliability of old quality-marker but also recognize the possible counterfeit. 相似文献
705.
Dr. Zongkun Chen Xingkun Wang Dr. Zhongkang Han Dr. Siyuan Zhang Dr. Simone Pollastri Qiqi Fan Dr. Zhengyao Qu Debalaya Sarker Prof. Christina Scheu Prof. Minghua Huang Prof. Helmut Cölfen 《Angewandte Chemie (International ed. in English)》2023,62(10):e202215728
Layered double hydroxides (LDHs), whose formation is strongly related to OH− concentration, have attracted significant interest in various fields. However, the effect of the real-time change of OH− concentration on LDHs’ formation has not been fully explored due to the unsuitability of the existing synthesis methods for in situ characterization. Here, the deliberately designed combination of NH3 gas diffusion and in situ pH measurement provides a solution to the above problem. The obtained results revealed the formation mechanism and also guided us to synthesize a library of LDHs with the desired attributes in water at room temperature without using any additives. After evaluating their oxygen evolution reaction performance, we found that FeNi-LDH with a Fe/Ni ratio of 25/75 exhibits one of the best performances so far reported. 相似文献