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991.
Tiantian Chen Yashi Zou Yanhua Hu Prof. Dr. Zhenfeng Zhang Prof. Dr. Hao Wei Prof. Dr. Liangming Wei Prof. Dr. Wanbin Zhang 《Angewandte Chemie (International ed. in English)》2023,62(26):e202303488
Using the diphosphine-cobalt-zinc catalytic system, an efficient asymmetric hydrogenation of internal simple enamides has been realized. In particular, the Ph-BPE ligand can achieve convergent asymmetric hydrogenation of E/Z-substrates. High yields and excellent enantioselectivities were obtained for both acyclic and cyclic enamides bearing α-alkyl-β-aryl, α-aryl-β-aryl, and α-aryl-β-alkyl substituents. Hydrogenated products can be applied for the synthesis of useful chiral drugs such as Arfromoterol, Rotigotine, and Norsertraline. In addition, reasonable catalytic mechanism and stereocontrol mode are proposed based on DFT calculations. 相似文献
992.
Liangshen Duan Qin Nie Yongxin Hu Liming Wang Kaiyan Guo Zhuoyi Zhou Xu Song Yuanhong Tu Hui Liu Thomas Hansen Jian-song Sun Qingju Zhang 《Angewandte Chemie (International ed. in English)》2023,62(33):e202306971
Herein, we described the first synthesis of the pentasaccharide and decasaccharide of the A. baumannii ATCC 17961 O-antigen for developing a synthetic carbohydrate-based vaccine against A. baumannii infection. The efficient synthesis of the rare sugar 2,3-diacetamido-glucuronate was achieved using our recently introduced organocatalytic glycosylation method. We found, for the first time, that long-range levulinoyl group participation via a hydrogen bond can result in a significantly improved β-selectivity in glycosylations. This solves the stereoselectivity problem of highly branched galactose acceptors. The proposed mechanism was supported by control experiments and DFT computations. Benefiting from the long-range levulinoyl group participation strategy, the pentasaccharide donor and acceptor were obtained via an efficient [2+1+2] one-pot glycosylation method and were used for the target decasaccharide synthesis. 相似文献
993.
Nan Zhang Ying Li Dr. Sanyang Han Dr. Ying Wei Huan Hu Ran Huo Dr. Chunbo Duan Dr. Jing Zhang Dr. Chunmiao Han Prof. Guohua Xie Prof. Hui Xu 《Angewandte Chemie (International ed. in English)》2023,62(27):e202305018
Clusters combine the advantages of organic molecules and inorganic nanomaterials, which are promising alternatives for optoelectronic applications. Nonetheless, recently emerged cluster light-emitting diodes require further excited state optimization of cluster emitters, especially to reduce population of the cluster-centered triplet quenching state (3CC). Here we report that redox-active ligands enhance reverse intersystem crossing (RISC) of Cu4I4 cluster for triplet-to-singlet conversion, and thermally activated delayed fluorescence (TADF) host can provide an external RISC channel. It indicates that the complementarity between TADF host and cluster in RISC transitions gives rise to 100 % triplet conversion efficiency and complete singlet exciton convergence, rendering 100-fold increased singlet radiation rate constant and tenfold decreased triplet non-radiation rate constant. We achieve a photoluminescence quantum yield of 99 % and a record external quantum efficiency of 29.4 %. 相似文献
994.
Bingyu Huang Xiannong Tang Yaoshuai Hong Longbin Li Prof. Ting Hu Prof. Kai Yuan Prof. Yiwang Chen 《Angewandte Chemie (International ed. in English)》2023,62(33):e202306667
Catalysts with metal-Nx sites have long been considered as effective electrocatalysts for oxygen reduction reaction (ORR), yet the accurate structure-property correlations of these active sites remain debatable. Report here is a proof-of-concept method to construct 1,4,8,11-tetraaza[14]annulene (TAA)-based polymer nanocomposites with well-managed electronic microenvironment via electron-donors/acceptors interaction of altering electron-withdrawing β-site substituents. DFT calculation proves the optimal −Cl substituted catalyst (CoTAA−Cl@GR) tailored the key OH* intermediate interaction with Co−N4 sites under the d-orbital regulation, hence reaching the top of ORR performance with excellent turnover frequency (0.49 e s−1 site−1). The combination of in situ scanning electrochemical microscopy and variable-frequency square wave voltammetry techniques contribute the great ORR kinetics of CoTAA−Cl@GR to the relatively high accessible site density (7.71×1019 site g−1) and fast electron outbound propagation mechanism. This work provides theoretical guidance for rational design of high-performance catalysts for ORR and beyond. 相似文献
995.
Ni-Yuan Zhang Da-Yong Hou Xing-Jie Hu Jian-Xiao Liang Man-Di Wang Zhang-Zhi Song Li Yi Zhi-Jia Wang Prof. Hong-Wei An Prof. Wanhai Xu Prof. Hao Wang 《Angewandte Chemie (International ed. in English)》2023,62(37):e202308049
Proteolysis targeting chimera (PROTAC) is an emerging pharmacological modality with innovated post-translational protein degradation capabilities. However, off-target induced unintended tissue effects and intrinsic “hook effect” hinder PROTAC biotechnology to be maturely developed. Herein, an intracellular fabricated nano proteolysis targeting chimeras (Nano-PROTACs) modality with a center-spoke degradation network for achieving efficient dose-dependent protein degradation in tumor is reported. The PROTAC precursors are triggered by higher GSH concentrations inside tumor cells, which subsequently in situ self-assemble into Nano-PROTACs through intermolecular hydrogen bond interactions. The fibrous Nano-PROTACs can form effective polynary complexes and E3 ligases degradation network with multi-binding sites, achieving dose-dependent protein degradation with “anti-hook effect”. The generality and efficacy of Nano-PROTACs are validated by degrading variable protein of interest (POI) such as epidermal growth factor receptor (EGFR) and androgen receptor (AR) in a wide-range dose-dependent manner with a 95 % degradation rate and long-lasting potency up to 72 h in vitro. Significantly, Nano-PROTACs achieve in vivo dose-dependent protein degradation up to 79 % and tumor growth inhibition in A549 and LNCap xenograft mice models, respectively. Taking advantages of in situ self-assembly strategy, the Nano-PROTACs provide a generalizable platform to promote precise clinical translational application of PROTAC. 相似文献
996.
Xiuxiu Zhang Chenyu Yang Chen Gong Meihuan Liu Wanlin Zhou Hui Su Feifan Yu Fengchun Hu Qinghua Liu Shiqiang Wei 《Angewandte Chemie (International ed. in English)》2023,62(33):e202308082
Synthesis of highly active and durable oxygen evolution reaction (OER) catalysts applied in acidic water electrolysis remains a grand challenge. Here, we construct a type of high-loading iridium single atom catalysts with tunable d-band holes character (h-HL−Ir SACs, ∼17.2 wt % Ir) realized in the early OER operation stages. The in situ X-ray absorption spectroscopy reveals that the quantity of the d-band holes of Ir active sites can be fast increased by 0.56 unit from the open circuit to a low working potential of 1.35 V. More remarkably, in situ synchrotron infrared and Raman spectroscopies demonstrate the quick accumulation of *OOH and *OH intermediates over holes-modulated Ir sites in the early reaction voltages, achieving a rapid OER kinetics. As a result, this well-designed h-HL−Ir SACs exhibits superior performance for acidic OER with overpotentials of 216 mV @10 mA cm−2 and 259 mV @100 mA cm−2, corresponding to a small Tafel slope of 43 mV dec−1. The activity of catalyst shows no evident attenuation after 60 h operation in acidic environment. This work provides some useful hints for the design of superior acidic OER catalysts. 相似文献
997.
Yanmin Hu Tingting Chao Yapeng Li Peigen Liu Tonghui Zhao Ge Yu Cai Chen Xiao Liang Huile Jin Shuwen Niu Wei Chen Dingsheng Wang Yadong Li 《Angewandte Chemie (International ed. in English)》2023,62(35):e202308800
Water electrolysis for H2 production is restricted by the sluggish oxygen evolution reaction (OER). Using the thermodynamically more favorable hydrazine oxidation reaction (HzOR) to replace OER has attracted ever-growing attention. Herein, we report a twisted NiCoP nanowire array immobilized with Ru single atoms (Ru1−NiCoP) as superior bifunctional electrocatalyst toward both HzOR and hydrogen evolution reaction (HER), realizing an ultralow working potential of −60 mV and overpotential of 32 mV for a current density of 10 mA cm−2, respectively. Inspiringly, two-electrode electrolyzer based on overall hydrazine splitting (OHzS) demonstrates outstanding activity with a record-high current density of 522 mA cm−2 at cell voltage of 0.3 V. DFT calculations elucidate the cooperative Ni(Co)−Ru−P sites in Ru1−NiCoP optimize H* adsorption, and enhance adsorption of *N2H2 to significantly lower the energy barrier for hydrazine dehydrogenation. Moreover, a self-powered H2 production system utilizing OHzS device driven by direct hydrazine fuel cell (DHzFC) achieve a satisfactory rate of 24.0 mol h−1 m−2. 相似文献
998.
Qingbin Li Yihan Zhang Junfeng Lin Ye Zou Pu Wang Dr. Zhengsheng Qin Yongshuai Wang Dr. Yang Li Prof. Dr. Yu Zhang Dr. Can Gao Prof. Dr. Yaping Zang Prof. Dr. Wenping Hu Prof. Dr. Huanli Dong 《Angewandte Chemie (International ed. in English)》2023,62(42):e202308146
The development of blue-emissive ambipolar organic semiconductor is an arduous target due to the large energy gap, but is an indispensable part for electroluminescent device, especially for the transformative display technology of simple-structured organic light-emitting transistor (SS-OLET). Herein, we designed and synthesized two new dibenzothiophene sulfone-based high mobility blue-emissive organic semiconductors (DNaDBSOs), which demonstrate superior optical property with solid-state photoluminescent quantum yield of 46–67 % and typical ambipolar-transporting properties in SS-OLETs with symmetric gold electrodes. Comprehensive experimental and theoretical characterizations reveal the natural of ambipolar property for such blue-emissive DNaDBSOs-based materials is ascribed to a synergistic effect on lowering LUMO level and reduced electron injection barrier induced by the interfacial dipoles effect on gold electrodes due to the incorporation of appropriate DBSO unit. Finally, efficient electroluminescence properties with high-quality blue emission (CIE (0.179, 0.119)) and a narrow full-width at half-maximum of 48 nm are achieved for DNaDBSO-based SS-OLET, showing good spatial control of the recombination zone in conducting channel. This work provides a new avenue for designing ambipolar emissive organic semiconductors by incorporating the synergistic effect of energy level regulation and molecular-metal interaction, which would advance the development of superior optoelectronic materials and their high-density integrated optoelectronic devices and circuits. 相似文献
999.
ChangYan Hu Dr. Ying Li Dr. Dong Wang Dr. Chunjin Wu Feng Chen Linghong Zhang Prof. Fang Wan Prof. Weibo Hua Prof. Yan Sun Prof. Benhe Zhong Dr. Zhenguo Wu Prof. Xiaodong Guo 《Angewandte Chemie (International ed. in English)》2023,62(46):e202312310
Na2Ti6O13 (NTO) with high safety has been regarded as a promising anode candidate for sodium-ion batteries. In the present study, integrated modification of migration channels broadening, charge density re-distribution, and oxygen vacancies regulation are realized in case of Nb-doping and have obtained significantly enhanced cycling performance with 92 % reversible capacity retained after 3000 cycles at 3000 mA g−1. Moreover, unexpected low-temperature performance with a high discharge capacity of 143 mAh g−1 at 100 mA g−1 under −15 °C is also achieved in the full cell. Theoretical investigation suggests that Nb preferentially replaces Ti3 sites, which effectively improves structural stability and lowers the diffusion energy barrier. What's more important, both the in situ X-ray diffraction (XRD) and in situ Raman furtherly confirm the robust spring effect of the Ti−O bond, making special charge compensation mechanism and respective regulation strategy to conquer the sluggish transport kinetics and low conductivity, which plays a key role in promoting electrochemical performance. 相似文献
1000.
Prof. Tong-Xin Liu Xin Wang Shilu Xia Prof. Muqing Chen Mingjie Li Panting Yang Prof. Nana Ma Ziqi Hu Prof. Shangfeng Yang Prof. Guisheng Zhang Prof. Guan-Wu Wang 《Angewandte Chemie (International ed. in English)》2023,62(46):e202313074
Herein, we report divergent additions of 2,2′-diazidobiphenyls to C60 and Sc3N@Ih-C80. In stark contrast to that of the previously reported bis-azide additions, the unexpected cascade reaction leads to the dearomative formation of azafulleroids 2 fused with a 7-6-5-membered ring system in the case of C60. In contrast, the corresponding reaction with Sc3N@Ih-C80 switches to the C−H insertion pathway, thereby resulting in multiple isomers, including a carbazole-derived [6,6]-azametallofulleroid 3 and a [5,6]-azametallofulleroid 4 and an unusual 1,2,3,6-tetrahydropyrrolo[3,2-c]carbazole-derived metallofullerene 5 , whose molecular structures have been unambiguously determined by single-crystal X-ray diffraction analyses. Among them, the addition type of 5 is observed for the first time in all reported additions of azides to fullerenes. Furthermore, unexpected isomerizations from 3 to 5 and from 4 to 5 have been discovered, providing the first examples of the isomerization of an azafulleroid to a carbazole-derived fullerene rather than an aziridinofullerene. In particular, the isomerism of the [5,6]-isomer 4 to the [5,6]-isomer 5 is unprecedented in fullerene chemistry, contradicting the present understanding that isomerization generally occurs between [5,6]- and [6,6]-isomers. Control experiments have been carried out to rationalize the reaction mechanism. Furthermore, representative azafulleroids have been applied in organic solar cells, thereby resulting in improved power conversion efficiencies. 相似文献