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61.
A comprehensive study on the efficient one‐pot synthesis of polyhedral octaphenylsilsesquioxane (OPS) is reported via the hydrolytic condensation of phenyltrimethoxysilane (PTMS) in the presence of basic catalyst to investigate the specific synthesis mechanism. The synthetic reactions are monitored with real time infrared (RTIR) spectroscopy. Then RTIR coupled with 29Si nuclear magnetic resonance spectroscopy (NMR) and matrix‐assisted laser desorption/ionization time of flight mass spectrometry (MALDI‐TOF‐MS) are used to monitor the reactions and identify the intermediary species during the reaction. The rapid hydrolysis of PTMS is detected by RTIR. Contrary to previous reports, the ladder‐like structured species are identified as intermediates during the reaction process. It is suggested that formation of caged T8 OPS is realized through the chain break and rearrangement of the ladder‐like phenyltrimethoxysilanes. Accordingly, a scheme from hydrolysis of the PTMS to formation of the OPS is provided. 相似文献
62.
Congcong Pei Dr. Chao Liu Dr. You Wang Dan Cheng Rongxin Li Weikang Shu Chaoqi Zhang Wenli Hu Dr. Aihua Jin Dr. Yannan Yang Prof. Jingjing Wan 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(27):10923-10927
High-throughput metabolic analysis is of significance in diagnostics, while tedious sample pretreatment has largely hindered its clinic application. Herein, we designed FeOOH@ZIF-8 composites with enhanced ionization efficiency and size-exclusion effect for laser desorption/ionization mass spectrometry (LDI-MS)-based metabolic diagnosis of gynecological cancers. The FeOOH@ZIF-8-assisted LDI-MS achieved rapid, sensitive, and selective metabolic fingerprints of the native serum without any enrichment or purification. Further analysis of extracted serum metabolic fingerprints successfully discriminated patients with gynecological cancers (GCs) from healthy controls and also differentiated three major subtypes of GCs. Given the low cost, high-throughput, and easy operation, our approach brings a new dimension to disease analysis and classification. 相似文献
63.
Lei Xu Chao Wang Yan-Xiang Li Xun-Hui Xu Dr. Li Zhou Dr. Na Liu Prof. Dr. Zong-Quan Wu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(38):16818-16825
Controlling the self-assembly morphology of π-conjugated block copolymer is of great interesting. Herein, amphiphilic poly(3-hexylthiophene)-block-poly(phenyl isocyanide)s (P3HT-b-PPI) copolymers composed of π-conjugated P3HT and optically active helical PPI segments were readily prepared. Taking advantage of the crystallizable nature of P3HT and the chirality of the helical PPI segment, crystallization-driven asymmetric self-assembly (CDASA) of the block copolymers lead to the formation of single-handed helical nanofibers with controlled length, narrow dispersity, and well-defined helicity. During the self-assembly process, the chirality of helical PPI was transferred to the supramolecular assemblies, giving the helical assemblies large optical activity. The single-handed helical assemblies of the block copolymers exhibited interesting white-light emission and circularly polarized luminescence (CPL). The handedness and dissymmetric factor of the induced CPL can be finely tuned through the variation on the helicity and length of the helical nanofibers. 相似文献
64.
Yuan-Yuan Che Yanni Yue Ling-Zhi Lin Bingbing Pei Xuezu Deng Prof. Dr. Chao Feng 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(38):16556-16561
Herein, we report a highly efficient and practical method for pyridine-derived heterobiaryl synthesis through palladium-catalyzed electrophilic functionalization of easily available pyridine-derived quaternary phosphonium salts. The nice generality of this reaction was goes beyond arylation, enabling facile incorporation of diverse carbon-based fragments, including alkenyl, alkynyl, and also allyl fragments, onto the pyridine core. Notably, the silver salt additive is revealed to be of vital importance for the success of this transformation and its pivotal role as transmetallation mediator, which guarantees a smooth transfer of pyridyl group to palladium intermediate, is also described. 相似文献
65.
Ruirui Xu Kun Wang Haoying Liu Prof. Dr. Weijun Tang Dr. Huaming Sun Prof. Dr. Dong Xue Prof. Dr. Jianliang Xiao Prof. Dr. Chao Wang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(49):22143-22148
A ruthenium-catalyzed formal anti-Markovnikov hydroamination of allylic alcohols for the synthesis of chiral γ-amino alcohols is presented. Proceeding via an asymmetric hydrogen-borrowing process, the catalysis allows racemic secondary allylic alcohols to react with various amines, affording enantiomerically enriched chiral γ-amino alcohols with broad substrate scope and excellent enantioselectivities (68 examples, up to >99 % ee). 相似文献
66.
A series of new heteromultinuclear FeI/RuII clusters are described. The complexes (η6-arene)RuFe2S2(CO)6 (arene = p-cymene 1 , C6Me6 2 ) and Fe2[μ-S (Cp*Ru)(CO)2]2(CO)6 (Cp* = η5-C5Me5) ( 3 ) were prepared by the reduction reactions of (μ-S)2Fe2(CO)6 with 2 equiv of LiHBEt3, followed by treatment (μ-SLi)2Fe2(CO)6 with ruthenium-arene complexes Ru2(μ-Cl)2Cl2(η6-arene)2 or Cp*Ru (CO)2Cl in 22–33% yields. Further reactions of 1 and 2 with 1 equiv of triphenylphosphine in the presence of the decarbonylating agent Me3NO·2H2O, afforded the corresponding monophosphine-substituted FeI/RuII complexes (η6-arene)RuFe2S2(CO)5(Ph3P) (arene = p-cymene 4 , C6Me6 5 ) in 75% and 78% yields. While treatment of parent complex 1 or 2 with 1 equiv of diphosphine Ph2PCH2PPh2 (dppm) in xylene at reflux temperature resulted in the formation of the diphosphine-bridged RuFe2S2(CO)9 derivate RuFe2S2(CO)7(dppm) ( 6 ). The possible pathway for the formation was proposed. Two isomers of novel macrocyclic complexes involve the (η6-arene) Ru-bridged quadruple-butterfly Fe/S clusters [{μ-S (CH2)3S-μ}{(μ-CS2)Fe2(CO)6}2]2[(η6-arene)Ru]2 (arene = p-cymene 7a and 7b , C6Me6 8a and 8b ) were isolated by reactions of two μ-CS2-containing dianion [{μ-S (CH2)3S-μ}{(μ-S=CS)Fe2(CO)6}2]2− with [Ru2(μ-Cl)2Cl2(η6-arene)2], in which the propylene groups are attached to two S atoms by ee and ea types of bonds respectively. All the new complexes 1 – 8 have been characterized by elemental analysis, spectroscopy, and particularly for 1 – 6 , 7b and 8a by X-ray crystallography. In addition, the electrochemical properties of representative complexes 1 – 4 and 6 have been investigated. 相似文献
67.
Alpha-phenylethanol (PE) is an essential chemical in the field of medicine and synthetic perfumery. Therefore, in this work, we used a supported Ni–B–P amorphous alloy catalyst (Ni–B–P/SiO2) in the hydrogenation of acetophenone (AP) to α-PE, which demonstrated excellent catalytic activity and selectivity, compared with Ni–B/SiO2 (KBH4 reduction of nickel salt). Ni–B–P/SiO2 exhibited a high AP hydrogenation conversion of approximately 99%, whereas the PE selectivity reached up to 94%, which is approximately 1.4-fold higher than that of Ni–B/SiO2 (about 69%), thereby directly proving the unique inhibition of AP hydrogenation over hydrogenation of P in the Ni–B catalytic system. The doped P in Ni–B–P/SiO2 enhances the oxidation resistance and maintains the valence stability of Ni and B. Furthermore, sufficient experimental data were collected to determine the kinetic parameters. Based on the Langmuir–Hinshelwood model, we assumed that (i) AP and H2 compete for adsorption on Ni–B–P/SiO2; (ii) AP has strong adsorptive capacity on Ni–B–P/SiO2; and (iii) PE coverage on the catalyst was negligible. Then, the dynamic equation was derived, which indicated that experimental data agree well with the dynamic model. Finally, the activation energy was confirmed to be 50.73 KJ/mol. This report will open up an avenue for the industrialization of amorphous alloy catalysts. 相似文献
68.
Dr. Yaru Gong Chao Qin Yuteng Zhang Prof. Chunyi Sun Prof. Qinhe Pan Xinlong Wang Zhongmin Su 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(49):22218-22222
Systematic design and self-assembly of metal–organic polyhedra with predictable configurations has been a long-standing challenge in crystal engineering. Herein a concave polyoxovanadate cluster, [V6O6(OCH3)9(SO4)4]5−, which can be generated in situ under specific reaction conditions, is reported. Based on this cluster, a potential trivalent molecular building block, [V6O6(OCH3)9(SO4)(CO2)3]2−, can be obtained by the bridging-ligand-substitution strategy and it possesses appropriate angle information for the design of molecular cubes. Utilizing the face-directed assembly of the trivalent molecular building block and a diverse set of tetratopic carboxylate linkers, a series of metal–organic cubes ( VMOC-1 – VMOC-5 ) with the same topology but different functionalities and dimensions were designed and constructed. An inclusion study using VMOC-3 shows that they are potential molecular receptors for selective capture of size-matching polycyclic aromatic hydrocarbon guest molecules. 相似文献
69.
Qianqian Gao Dr. Yumeng Zhao Kangli Xu Dr. Chao Zhang Dr. Qian Ma Liqing Qi Dandan Chao Tingting Zheng Linlin Yang Dr. Yanyan Miao Prof. Da Han 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(52):23770-23774
A single-step method for isolation of specific cells based on multiple surface markers will have unique advantages because of its scalability, efficacy, and mildness. Herein, we developed multi-aptamer-mediated proximity ligation method on live cell membranes that leverages a multi-receptor co-recognition design for enhanced specificity, as well as a robust in situ signal amplification design for improved sensitivity of cell isolation. We demonstrated the promising efficacy of our method on differentiating tumor cell subtypes in both cell mixtures and clinical samples. Owing to its simple and fast operation with excellent cell isolation sensitivity and accuracy, this approach will have broad applications in biological science, biomedical engineering, and personalized medicine. 相似文献
70.
高等教育要适应世界潮流和时代变化,本科教育须进一步提高实践教学的比重,加强理论教学与实践教学相结合,完善协同育人机制。结合学科发展和企业发展需求,中山大学化学学院与金发科技股份有限公司(简称金发科技)共同建设大学生实践教学基地。本文以中山大学-金发科技本科实践教学基地为例,探讨大学生校外实践基地建设过程中遇到的问题以及实践基地的建设内容与成果体会。 相似文献