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91.
Dr. David Scheerer Prof. Dr. Heng Chi Dr. Dan McElheny Prof. Dr. Timothy A. Keiderling Prof. Dr. Karin Hauser 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(16):3524-3534
Site-specific isotopic labeling of molecules is a widely used approach in IR spectroscopy to resolve local contributions to vibrational modes. The induced frequency shift of the corresponding IR band depends on the substituted masses, as well as on hydrogen bonding and vibrational coupling. The impact of these different factors was analyzed with a designed three-stranded β-sheet peptide and by use of selected 13C isotope substitutions at multiple positions in the peptide backbone. Single-strand labels give rise to isotopically shifted bands at different frequencies, depending on the specific sites; this demonstrates sensitivity to the local environment. Cross-strand double- and triple-labeled peptides exhibited two resolved bands that could be uniquely assigned to specific residues, the equilibrium IR spectra of which indicated only weak local-mode coupling. Temperature-jump IR laser spectroscopy was applied to monitor structural dynamics and revealed an impressive enhancement of the isotope sensitivity to both local positions and coupling between them, relative to that of equilibrium FTIR spectroscopy. Site-specific relaxation rates were altered upon the introduction of additional cross-strand isotopes. Likewise, the rates for the global β-sheet dynamics were affected in a manner dependent on the distinct relaxation behavior of the labeled oscillator. This study reveals that isotope labels provide not only local structural probes, but rather sense the dynamic complexity of the molecular environment. 相似文献
92.
Xiaojuan Liu Qingqing Wen Prof. Dr. Li Xiang Dr. Xuebing Leng Prof. Dr. Yaofeng Chen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(24):5494-5499
The synthesis and catalytic applications of trivalent rare-earth metal alkyl complexes have been well developed, but the chemistry of divalent rare-earth metal alkyl complexes lagged much behind. Herein, we report the synthesis, structure, and catalytic applications of a samarium(II) monoalkyl complex supported by a β-diketiminato-based tetradentate ligand, [LSmCH(SiMe3)2] (L=[MeC(NDipp)CHC(Me)NCH2CH2N(Me)CH2CH2NMe2]−, Dipp=2,6-(iPr)2C6H3). This complex is synthesized by the salt metathesis reaction of samarium iodide [LSm(μ-I)]2 and KCH(SiMe3)2 in 63 % yield. Its structure is characterized by single-crystal X-ray diffraction, showing a distorted square-pyramid coordination geometry. This samarium(II) monoalkyl complex exhibits high catalytic activity in the hydrosilylation of aryl and methyl-substituted unsymmetrical internal alkynes with secondary hydrosilanes, selectively providing the α-(E) products in high yields. 相似文献
93.
Dr. Stefano Elli Dr. Eduardo Stancanelli Dr. Zhangjie Wang Dr. Maurice Petitou Prof. Jian Liu Dr. Marco Guerrini 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(51):11814-11818
Heparin binds to and activates antithrombin (AT) through a specific pentasaccharide sequence, in which a trisaccharide subsite, containing glucuronic acid (GlcA), has been considered as the initiator in the recognition of the polysaccharide by the protein. Recently it was suggested that sulfated iduronic acid (IdoA2S) could replace this “canonical” GlcA. Indeed, a heparin octasaccharidic sequence obtained by chemoenzymatic synthesis, in which GlcA is replaced with IdoA2S, has been found to similarly bind to and activate antithrombin. By using saturation-transfer-difference (STD) NMR, NOEs, transferred NOEs (tr-NOEs) NMR and molecular dynamics, we show that, upon binding to AT, this IdoA2S unit develops comparable interactions with AT as GlcA. Interestingly, two IdoA2S units, both present in a 1C4-2S0 equilibrium in the unbound saccharide, shift to full 2S0 and full 1C4 upon binding to antithrombin, providing the best illustration of the critical role of iduronic acid conformational flexibility in biological systems. 相似文献
94.
Dr. Zhenghai Yang Dr. Srinivas Doddipatla Dr. Chao He Vladislav S. Krasnoukhov Prof. Dr. Valeriy N. Azyazov Prof. Dr. Alexander M. Mebel Prof. Dr. Ralf I. Kaiser 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(60):13584-13589
The silene molecule (H2SiCH2; X1A1) has been synthesized under single collision conditions via the bimolecular gas phase reaction of ground state methylidyne radicals (CH) with silane (SiH4). Exploiting crossed molecular beams experiments augmented by high-level electronic structure calculations, the elementary reaction commenced on the doublet surface through a barrierless insertion of the methylidyne radical into a silicon-hydrogen bond forming the silylmethyl (CH2SiH3; X2A′) complex followed by hydrogen migration to the methylsilyl radical (SiH2CH3; X2A′). Both silylmethyl and methylsilyl intermediates undergo unimolecular hydrogen loss to silene (H2SiCH2; X1A1). The exploration of the elementary reaction of methylidyne with silane delivers a unique view at the widely uncharted reaction dynamics and isomerization processes of the carbon–silicon system in the gas phase, which are noticeably different from those of the isovalent carbon system thus contributing to our knowledge on carbon silicon bond couplings at the molecular level. 相似文献
95.
96.
97.
Based on the quasi-classical trajectory (QCT) method and Matlab GUI technology, we developed a program code for visualizing the collision process of the elementary chemical reactions of the a + bc type. The general methodology of QCT, abstraction of dynamical properties of molecular collisions and the making of Graphical User Interface are introduced. The running results of an application to the reaction F + HCl→HF + Cl is also presented. The results showed that this program could vividly demonstrate the behavior and final state of the atom-diatom collision process in animated form. Students can interact with internal MATLAB code through graphical user interface, observe the reactive behavior and final results in real-time from multiple angles, which helps students to understand the complex reaction mechanism and deepen their perceptual impression of the chemical process at a microscopic atomic/molecular level. 相似文献
98.
The development of catalysts capable of catalyzing amidation of esters with amines to construct amides under mild conditions is of great importance. Compared to aliphatic amines, the direct catalytic amidation of esters with less nucleophilic aromatic amines is rather difficult. Employing simple lanthanide tris (amide) complexes Ln[N (SiMe3)2]3(μ-Cl)Li (THF)3 as the catalysts, it was found a broad range of aromatic amines and esters were efficiently converted into various amides in good yields under mild conditions. A plausible mechanism for this transformation was experimentally supported as starting from an amide exchange reaction between the lanthanide tris (amide) complex and the substrate amine. 相似文献
99.
Yujia Xu Weijing Zhang Tonglai Zhang Wei Guo Yongjun Lü 《Journal of computational chemistry》2020,41(10):1026-1033
Metal azides have attracted increasing attention as precursors for synthesizing polymeric nitrogen. In this article, we report the amorphous polymerization of nitrogen by compressing cupric azide. The ab initio molecular dynamics simulations show that crystalline cupric azide transforms into a disordered network composed of singly bonded nitrogen at a hydrostatic pressure of 40 GPa and room temperature. The transformation manifests the formation of a π delocalization along the disordered Cu-N network, thus resulting in a semiconductor–metal transition. The estimated heat of formation of the amorphous polymeric nitrogen system is comparable to conventional high-energy-density materials. The amorphization provides an alternative route to the polymerization of nitrogen under moderate conditions. 相似文献
100.
Liam J. R. McGeachie Cameron L. Carpenter-Warren David B. Cordes Michael Bühl Steven J. Gray Guoxiong Hua Alexandra M. Z. Slawin J. Derek Woollins 《无机化学与普通化学杂志》2020,646(22):1795-1798
An improved route to d-block and main group NSO complexes is presented including the synthesis of the first antimony(V) complexes, (Ar3Sb(NSO)2), and copper examples [CuBipy(PPh3)NSO]. The structures of eight complexes are reported. The observed variation in M–N–S bond angles is due to the combination of orbital overlap (ligand-to-metal bonding) and the degree of ionicity of the bonding. 相似文献