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951.
Tunable Oxygen Activation for Catalytic Organic Oxidation: Schottky Junction versus Plasmonic Effects
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Ming Gong Shan Zhou Jiahua Hu Min Zhi Yang You Song Bai Prof. Jun Jiang Prof. Qun Zhang Prof. Xiaojun Wu Prof. Yujie Xiong 《Angewandte Chemie (International ed. in English)》2014,53(12):3205-3209
The charge state of the Pd surface is a critical parameter in terms of the ability of Pd nanocrystals to activate O2 to generate a species that behaves like singlet O2 both chemically and physically. Motivated by this finding, we designed a metal–semiconductor hybrid system in which Pd nanocrystals enclosed by {100} facets are deposited on TiO2 supports. Driven by the Schottky junction, the TiO2 supports can provide electrons for metal catalysts under illumination by appropriate light. Further examination by ultrafast spectroscopy revealed that the plasmonics of Pd may force a large number of electrons to undergo reverse migration from Pd to the conduction band of TiO2 under strong illumination, thus lowering the electron density of the Pd surface as a side effect. We were therefore able to rationally tailor the charge state of the metal surface and thus modulate the function of Pd nanocrystals in O2 activation and organic oxidation reactions by simply altering the intensity of light shed on Pd–TiO2 hybrid structures. 相似文献
952.
Nucleophilic Difluoromethylation of Epoxides with PhSO(NTBS)CF2H by a Preorganization Strategy
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Dr. Xiao Shen Qinghe Liu Tao Luo Prof. Dr. Jinbo Hu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(22):6795-6800
Unlike the facile synthesis of β‐monofluoromethyl alcohols by nucleophilic monofluoromethylation of epoxides, the synthesis of β‐difluoromethyl alcohols by nucleophilic difluoromethylation of epoxides still remains a challenge. Herein, studies on tackling this problem with PhSO(NTBS)CF2H ( 2 ; TBS=tert‐butyldimethylsilyl) are reported. The preorganization of 2 and epoxides with BF3 ? Et2O was found to be crucial for the reaction. The reaction shows excellent regioselectivity and has a broad substrate scope. The facile transformation of the ring‐opened products to β‐difluoromethyl, γ‐difluoromethyl, and β‐difluoromethylenyl alcohols demonstrates the synthetic utility of the reaction. 相似文献
953.
Hetero‐tri‐spin [2p‐3d‐4f] Chain Compounds Based on Nitronyl Nitroxide Lanthanide Metallo‐Ligands: Synthesis,Structure, and Magnetic Properties
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Mei Zhu Peng Hu Yungai Li Xiufeng Wang Prof. Licun Li Prof. Daizheng Liao V. M. L. Durga Prasad Goli Prof. S. Ramasesha Dr. Jean‐Pascal Sutter 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(41):13356-13365
Employing nitronyl nitroxide lanthanide(III) complexes as metallo‐ligands allowed the efficient and highly selective preparation of three series of unprecedented hetero‐tri‐spin (Cu?Ln‐radical) one‐dimensional compounds. These 2p–3d–4f spin systems, namely [Ln3Cu(hfac)11(NitPhOAll)4] (LnIII=Gd 1Gd , Tb 1Tb , Dy 1Dy ; NitPhOAll=2‐(4′‐allyloxyphenyl)‐4,4,5,5‐tetramethylimidazoline‐1‐oxyl‐3‐oxide), [Ln3Cu(hfac)11(NitPhOPr)4] (LnIII=Gd 2Gd , Tb 2Tb , Dy 2Dy , Ho 2Ho , Yb 2Yb ; NitPhOPr=2‐(4′‐propoxyphenyl)‐4,4,5,5‐tetramethyl‐imidazoline‐1‐oxyl‐3‐oxide) and [Ln3Cu(hfac)11(NitPhOBz)4] (LnIII=Gd 3Gd , Tb 3Tb , Dy 3Dy ; NitPhOBz=2‐(4′‐benzyloxyphenyl)‐4,4,5,5‐tetramethyl‐imidazoline‐1‐oxyl‐3‐oxide) involve O‐bound nitronyl nitroxide radicals as bridging ligands in chain structures with a [Cu‐Nit‐Ln‐Nit‐Ln‐Nit‐Ln‐Nit] repeating unit. The dc magnetic studies show that ferromagnetic metal–radical interactions take place in these hetero‐tri‐spin chain complexes, these and the next‐neighbor interactions have been quantified for the Gd derivatives. Complexes 1Tb and 2Tb exhibit frequency dependence of ac magnetic susceptibilities, indicating single‐chain magnet behavior. 相似文献
954.
建立了单滴微萃取结合气相色谱-质谱法测定纺织品中可分解芳香胺的方法。研究了萃取剂种类、萃取剂体积、萃取时间、pH和搅拌速度等条件对单滴微萃取效率的影响。确定最佳萃取条件:在室温条件下,取5 mL样液,调节被萃取液pH8,以2μL氯苯为萃取剂萃取20 min,搅拌速度为200 r/min。在优化的实验条件下,检出限为0.08~0.14 mg/kg,线性范围0.5~50 mg/kg,线性相关系数大于0.996,平均加标回收率为75.3%~96.7%,相对标准偏差为3.6%~8.7%。方法适合纺织品中可分解芳香胺的测定。 相似文献
955.
以熔融纺丝聚氯乙烯(PVC)中空纤维多孔膜为增强体,聚偏氟乙烯(PVDF)为成膜聚合物,聚乙烯吡咯烷酮(PVP)为添加剂,N,N-二甲基乙酰胺(DMAc)为溶剂,配置铸膜液,采用同心圆牵引-涂覆法制备了异质增强型PVDF中空纤维膜.制备过程中,采用预湿溶液对增强体基膜表面进行预处理,研究了预湿溶液组成及含量对异质增强型PVDF中空纤维膜结构与性能的影响.结果表明,未经预湿处理的异质增强型PVDF中空纤维膜具有较厚的致密界面层;预湿溶液可对基膜表面孔起到保护作用,使异质增强型PVDF中空纤维膜的界面层变薄或形成多孔界面层,有益于改善增强型PVDF中空纤维膜的通透性能;与二甲基乙酰胺(DMAc)水溶液相比,以乙醇水溶液为预湿溶液所得异质增强型PVDF中空纤维膜的性能较优;当预湿液中乙醇含量为60 wt%时,所得增强型PVDF中空纤维膜的渗透性能较优,拉伸强度可达8.61 MPa. 相似文献
956.
Wei‐Li Li Dr. Ya‐Fan Zhao Dr. Han‐Shi Hu Prof. Dr. Jun Li Prof. Dr. Lai‐Sheng Wang 《Angewandte Chemie (International ed. in English)》2014,53(22):5540-5545
Chirality is vital in chemistry. Its importance in atomic clusters has been recognized since the discovery of the first chiral fullerene, the D2 symmetric C76. 1 A number of gold clusters have been found to be chiral, 2 raising the possibility to use them as asymmetric catalysts. The discovery of clusters with enantiomeric structures is essential to design new chiral materials with tailored chemical and physical properties. 3 Herein we report the first inherently chiral boron cluster of [B30]? in a joint photoelectron spectroscopy and theoretical study. The most stable structure of [B30]? is found to be quasiplanar with a hexagonal hole. Interestingly, a pair of enantiomers arising from different positions of the hexagonal hole are found to be degenerate in our global minimum searches and both should co‐exist experimentally because they have identical electronic structures and give rise to identical simulated photoelectron spectra. 相似文献
957.
Dr. Tao Xu Dr. Chi Wai Cheung Prof. Dr. Xile Hu 《Angewandte Chemie (International ed. in English)》2014,53(19):4910-4914
Iron catalysis has been developed for the intermolecular 1,2‐addition of perfluoroalkyl iodides to alkynes and alkenes. The catalysis has a wide substrate scope and high functional‐group tolerance. A variety of perfluoroalkyl iodides including CF3I can be employed. The resulting perfluoroalkylated alkyl and alkenyl iodides can be further functionalized by cross‐coupling reactions. This methodology provides a straightforward and streamlined access to perfluoroalkylated organic molecules. 相似文献
958.
A Supercharged Fluorescent Protein as a Versatile Probe for Homogeneous DNA Detection and Methylation Analysis
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Chunyang Lei Dr. Yan Huang Prof. Dr. Zhou Nie Jun Hu Lijun Li Guoyan Lu Yitao Han Prof. Dr. Shouzhuo Yao 《Angewandte Chemie (International ed. in English)》2014,53(32):8358-8362
Supercharged proteins are a new class of functional proteins with exceptional stability and potent ability to deliver bio‐macromolecules into cells. As a proof‐of‐principle, a novel application of supercharged proteins as a versatile biosensing platform for nucleic acid detection and epigenetics analysis is presented. Taking supercharged green fluorescent protein (ScGFP) as the signal reporter, a simple turn‐on homogenous method for DNA detection has been developed based on the polyionic nanoscale complex of ScGFP/DNA and toehold strand displacement. This assay shows high sensitivity and potent ability to detect single‐base mismatch. Furthermore, combined with bisulfite conversion, this ScGFP‐based assay was further applied to analyze site‐specific DNA methylation status of genomic DNA extracted from real human colon carcinoma tissue sample with ultrahigh sensitivity (4 amol methylated DNA). 相似文献
959.
Rong Hu Prof. Xiaobing Zhang Dr. Zilong Zhao Dr. Guizhi Zhu Dr. Tao Chen Ting Fu Prof. Weihong Tan 《Angewandte Chemie (International ed. in English)》2014,53(23):5821-5826
We present a facile approach to make aptamer‐conjugated FRET (fluorescent resonance energy transfer) nanoflowers (NFs) through rolling circle replication for multiplexed cellular imaging and traceable targeted drug delivery. The NFs can exhibit multi‐fluorescence emissions by a single‐wavelength excitation as a result of the DNA matrix covalently incorporated with three dye molecules able to perform FRET. Compared with the conventional DNA nanostructure assembly, NF assembly is independent of template sequences, avoiding the otherwise complicated design of DNA building blocks assembled into nanostructures by base‐pairing. The NFs were uniform and exhibited high fluorescence intensity and excellent photostability. Combined with the ability of traceable targeted drug delivery, these colorful DNA NFs provide a novel system for applications in multiplex fluorescent cellular imaging, effective screening of drugs, and therapeutic protocol development. 相似文献
960.
Silver‐Catalyzed Decarboxylative Trifluoromethylthiolation of Aliphatic Carboxylic Acids in Aqueous Emulsion
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Dr. Feng Hu Xinxin Shao Dianhu Zhu Prof. Dr. Long Lu Prof. Dr. Qilong Shen 《Angewandte Chemie (International ed. in English)》2014,53(24):6105-6109
A silver‐catalyzed decarboxylative trifluoromethylthiolation of secondary and tertiary carboxylic acids under mild conditions tolerates a wide range of functional groups. The reaction was dramatically accelerated by its performance in an aqueous emulsion, which was formed by the addition of sodium dodecyl sulfate to water. It was proposed that the radical, which was generated from the silver‐catalyzed decarboxylation in the “oil‐in‐water” droplets, could easily react with the trifluoromethylthiolating reagent to form the product. 相似文献