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991.
Dr. Nan Chen Dr. Yuan Liu Yuanpei Li Prof. Dr. Chu Wang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(37):16203-16209
Protein 4′-phosphopantetheinylation is an essential post-translational modification (PTM) in prokaryotes and eukaryotes. So far, only five protein substrates of this specific PTM have been discovered in mammalian cells. These proteins are known to perform important functions, including fatty acid biosynthesis and folate metabolism, as well as β-alanine activation. To explore existing and new substrates of 4′-phosphopantetheinylation in mammalian proteomes, we designed and synthesized a series of new pantetheine analogue probes, enabling effective metabolic labelling of 4′-phosphopantetheinylated proteins in HepG2 cells. In combination with a quantitative chemical proteomic platform, we enriched and identified all the currently known 4′-phosphopantetheinylated proteins with high confidence, and unambiguously determined their exact sites of modification. More encouragingly, we discovered, using targeted chemical proteomics, a potential 4′-phosphopantetheinylation site in the protein of mitochondrial dehydrogenase/reductase SDR family member 2 (DHRS2). 相似文献
992.
Ning-Xin Xu Bi-Xiao Li Dr. Chao Wang Prof. Dr. Masanobu Uchiyama 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(26):10726-10731
Silicon-containing compounds are widely used as synthetic building blocks, functional materials, and bioactive reagents. In particular, silyl radicals are important intermediates for the synthesis and transformation of organosilicon compounds. Herein, we describe the first protocol for the generation of silyl radicals by photoinduced decarboxylation of silacarboxylic acids, which can be easily prepared in high yield on a gram scale and are very stable to air and moisture. Irradiation of silacarboxylic acids with blue LEDs (455 nm) in the presence of a commercially available photocatalyst releases silyl radicals, which can further react with various alkenes to give the corresponding silylated products in good-to-high yields with broad functional-group compatibility. This reaction proceeds in the presence of water, enabling efficient deuterosilylation of alkenes with D2O as the deuterium source. Germyl radicals were similarly obtained. 相似文献
993.
Dr. Hui Wang Dr. Changcheng Jing Dr. Adam Noble Prof. Dr. Varinder Kumar Aggarwal 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(39):17005-17018
The stereospecific 1,2-migration of boronate complexes is one of the most representative reactions in boron chemistry. This process has been used extensively to develop powerful methods for asymmetric synthesis, with applications spanning from pharmaceuticals to natural products. Typically, 1,2-migration of boronate complexes is driven by displacement of an α-leaving group, oxidation of an α-boryl radical, or electrophilic activation of an alkenyl boronate complex. The aim of this article is to summarize the recent advances in the rapidly expanding field of electrophile-induced stereospecific 1,2-migration of groups from boron to sp2 and sp3 carbon centers. It will be shown that three different conceptual approaches can be utilized to enable the 1,2-migration of boronate complexes: stereospecific Zweifel-type reactions, catalytic conjunctive coupling reactions, and transition metal-free sp2–sp3 couplings. A discussion of the reaction scope, mechanistic insights, and synthetic applications of the work described is also presented. 相似文献
994.
Dr. Shuang Pan Dr. Haiyang Zou Aurelia C. Wang Dr. Zewei Wang Jiwoo Yu Chuntao Lan Qiliang Liu Prof. Zhong Lin Wang Prof. Tianquan Lian Prof. Juan Peng Prof. Zhiqun Lin 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(35):15052-15059
Despite recent progress in producing perovskite nanowires (NWs) for optoelectronics, it remains challenging to solution-print an array of NWs with precisely controlled position and orientation. Herein, we report a robust capillary-assisted solution printing (CASP) strategy to rapidly access aligned and highly crystalline perovskite NW arrays. The key to the CASP approach lies in the integration of capillary-directed assembly through periodic nanochannels and solution printing through the programmably moving substrate to rapidly guide the deposition of perovskite NWs. The growth kinetics of perovskite NWs was closely examined by in situ optical microscopy. Intriguingly, the as-printed perovskite NWs array exhibit excellent optical and optoelectronic properties and can be conveniently implemented for the scalable fabrication of photodetectors. 相似文献
995.
Qunfeng Fu Dr. Hongyu Li Dongban Duan Changlun Wang Siyong Shen Prof. Dr. Huimin Ma Prof. Dr. Zhibo Liu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(48):21730-21736
Radiation-induced cleavage for controlled release in vivo is yet to be established. We demonstrate the use of 3,5-dihydroxybenzyl carbamate (DHBC) as a masking group that is selectively and efficiently removed by external radiation in vitro and in vivo. DHBC reacts mainly with hydroxyl radicals produced by radiation to afford hydroxylation at para/ortho positions, followed by 1,4- or 1,6-elimination to rescue the functionality of the client molecule. The reaction is rapid and can liberate functional molecules under physiological conditions. This controlled-release platform is compatible with living systems, as demonstrated by the release of a rhodol fluorophore derivative in cells and tumor xenografts. The combined benefits of the robust caging group, the good release yield, and the independence of penetration depth make DHBC derivatives attractive chemical caging moieties for use in chemical biology and prodrug activation. 相似文献
996.
Bastien Delayre Dr. Cyril Piemontesi Dr. Qian Wang Prof. Dr. Jieping Zhu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(33):14094-14101
2,3,3-Trisubstituted indolenine constitutes an integral part of many biologically important monoterpene indole alkaloids. We report herein an unprecedented access to this skeleton by a TiCl3-mediated reductive cyclization of tetrasubstituted alkenes bearing a 2-nitrophenyl substituent. The proof of concept is demonstrated firstly by accomplishing a concise total synthesis of (+)-1,2-dehydroaspidospermidine featuring a late-stage application of this key transformation. A sequence of reduction of nitroarene to nitrosoarene followed by 6π-electron-5-atom electrocyclization and a 1,2-alkyl shift of the resulting nitrone intermediate was proposed to account for the reaction outcome. A subsequent total synthesis of (+)-condyfoline not only illustrates the generality of the reaction, but also provides a mechanistic insight into the nature of the 1,2-alkyl shift. The exclusive formation of (+)-condyfoline indicates that the 1,2-alkyl migration follows a concerted Wagner–Meerwein pathway, rather than a stepwise retro-Mannich/Mannich reaction sequence. Conditions for almost quantitative conversion of (+)-condyfoline to (−)-tubifoline by way of a retro-Mannich/1,3-prototropy/transannular cyclization cascade are also documented. 相似文献
997.
Dr. Szymon Chorazy Tomasz Charytanowicz Dr. Dawid Pinkowicz Junhao Wang Dr. Koji Nakabayashi Stephen Klimke Prof. Dr. Franz Renz Prof. Dr. Shin-ichi Ohkoshi Prof. Dr. Barbara Sieklucka 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(36):15871-15879
A two-step hysteretic FeII spin crossover (SCO) effect was achieved in programmed layered Cs{[Fe(3-CNpy)2][Re(CN)8]}⋅H2O ( 1 ) (3-CNpy=3-cyanopyridine) assembly consisting of cyanido-bridged FeII-ReV square grid sheets bonded by Cs+ ions. The presence of two non-equivalent FeII sites and the conjunction of 2D bimetallic coordination network with non-covalent interlayer interactions involving Cs+, [ReV(CN)8]3− ions, and 3-CNpy ligands, leads to the occurrence of two steps of thermal SCO with strong cooperativity giving a double thermal hysteresis loop. The resulting spin-transition phenomenon could be tuned by an external pressure giving the room-temperature range of SCO, as well as by visible-light irradiation, inducing an efficient recovery of the high-spin FeII state at low temperatures. We prove that octacyanidorhenate(V) ion is an outstanding metalloligand for induction of a cooperative multistep, multiswitchable FeII SCO effect. 相似文献
998.
Dr. Ze-Jun Xu Yan Zong Ya-Nan Qiao Jiao-Zhen Zhang Xuyuan Liu Ming-Zhu Zhu Yuliang Xu Hongbo Zheng Liyuan Fang Dr. Xiao-ning Wang Prof. Hong-Xiang Lou 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(45):20091-20095
A divergent synthetic approach to biogenetically related diterpenoids such as ent-kauranes, ent-trachylobanes, ent-beyerane, and ent-atisane has been developed. The unified synthetic route involves the De Mayo reaction to rapidly generate the bicyclo[3.2.1]-octane moiety of ent-kaurane. The key reactions also include bioinspired nucleophilic cyclopropanation generating the [3.2.1.02,7]-tricyclic core of ent-trachylobane and regioselective cyclopropane fragmentation furnishing ent-beyerane and ent-atisane through the nucleophilic attack and protonation of the cyclopropane ring. This strategy enables the asymmetric total syntheses of six diterpenoids from the commercially available geraniol. 相似文献
999.
A quantification method for imatinib (IM), its major metabolite N-desmethyl imatinib (NDI), and a degradation by-product was developed using CE–MS combined with an online concentration technique. The use of multiple reaction monitoring (MRM)–MS/MS further improved the sensitivity of this technology. Liquid–liquid extraction (LLE) using tertiary butyl methyl ether yielded high recovery and reproducibility for the pretreatment of serum samples. The recovery rate exceeded 83% for all three analytes, and was 90% for IM. To improve quantification results, a conductivity-induced online analyte concentration technique, field-amplified sample stacking (FASS), was used. The S/N ratios were improved at least 10-fold when compared with conventional capillary zone electrophoresis. The detection limits were 0.2 ng/mL for IM, 0.4 ng/mL for NDI, and 4 ng/mL for the degradation by-product. These results are superior to those previously obtained by other reported methods. The new method was validated in terms of its selectivity, intra- and interday repeatability and accuracy, and sample storage stability, following the guidelines issued by the European Medicines Agency. Considering the convenient pretreatment procedure (LLE), superior sensitivity, and fast analysis speed (<15 min), this method can be useful in the determination of imatinib levels in blood. 相似文献
1000.
G-protein-coupled receptors (GPCRs) are the largest family of human membrane proteins and serve as primary targets of approximately one-third of currently marketed drugs. In particular, adenosine A1 receptor (A1AR) is an important therapeutic target for treating cardiac ischemia–reperfusion injuries, neuropathic pain, and renal diseases. As a prototypical GPCR, the A1AR is located within a phospholipid membrane bilayer and transmits cellular signals by changing between different conformational states. It is important to elucidate the lipid–protein interactions in order to understand the functional mechanism of GPCRs. Here, all-atom simulations using a robust Gaussian accelerated molecular dynamics (GaMD) method were performed on both the inactive (antagonist bound) and active (agonist and G-protein bound) A1AR, which was embedded in a 1-palmitoyl-2-oleoyl-glycero-3-phosphocholine (POPC) lipid bilayer. In the GaMD simulations, the membrane lipids played a key role in stabilizing different conformational states of the A1AR. Our simulations further identified important regions of the receptor that interacted distinctly with the lipids in highly correlated manner. Activation of the A1AR led to differential dynamics in the upper and lower leaflets of the lipid bilayer. In summary, GaMD enhanced simulations have revealed strongly coupled dynamics of the GPCR and lipids that depend on the receptor activation state. © 2019 Wiley Periodicals, Inc. 相似文献