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991.
Photocatalytically Renewable Micro‐electrochemical Sensor for Real‐Time Monitoring of Cells 下载免费PDF全文
Jia‐Quan Xu Yan‐Ling Liu Qian Wang Huan‐Huan Duo Xin‐Wei Zhang Dr. Yu‐Tao Li Prof. Wei‐Hua Huang 《Angewandte Chemie (International ed. in English)》2015,54(48):14402-14406
Electrode fouling and passivation is a substantial and inevitable limitation in electrochemical biosensing, and it is a great challenge to efficiently remove the contaminant without changing the surface structure and electrochemical performance. Herein, we propose a versatile and efficient strategy based on photocatalytic cleaning to construct renewable electrochemical sensors for cell analysis. This kind of sensor was fabricated by controllable assembly of reduced graphene oxide (RGO) and TiO2 to form a sandwiching RGO@TiO2 structure, followed by deposition of Au nanoparticles (NPs) onto the RGO shell. The Au NPs‐RGO composite shell provides high electrochemical performance. Meanwhile, the encapsulated TiO2 ensures an excellent photocatalytic cleaning property. Application of this renewable microsensor for detection of nitric oxide (NO) release from cells demonstrates the great potential of this strategy in electrode regeneration and biosensing. 相似文献
992.
Feng‐Yang Bai Xiao‐Le Zhu Zi‐Man Jia Xu Wang Yan‐Qiu Sun Prof. Rong‐Shun Wang Prof. Xiu‐Mei Pan 《Chemphyschem》2015,16(8):1768-1776
The mechanism and kinetics of the reactions of CF3COOCH2CH3, CF2HCOOCH3, and CF3COOCH3 with Cl and OH radicals are studied using the B3LYP, MP2, BHandHLYP, and M06‐2X methods with the 6‐311G(d,p) basis set. The study is further refined by using the CCSD(T) and QCISD(T)/6‐311++G(d,p) methods. Seven hydrogen‐abstraction channels are found. All the rate constants, computed by a dual‐level direct method with a small‐curvature tunneling correction, are in good agreement with the experimental data. The tunneling effect is found to be important for the calculated rate constants in the low‐temperature range. For the reaction of CF3COOCH2CH3+Cl, H‐abstraction from the CH2 group is found to be the dominant reaction channel. The standard enthalpies of formation for the species are also calculated. The Arrhenius expressions are fitted within 200–1000 K as kT(1)=8.4×10?20T 2.63exp(381.28/T), kT(2)=2.95×10?21T 3.13exp(?103.21/T), kT(3)=1.25×10?23T 3.37exp(791.98/T), and kT(4)=4.53×10?22T 3.07exp(465.00/T). 相似文献
993.
Direct Determination of Trace Dopamine in an Ascorbic Acid Solution at a Bare Glassy Carbon Electrode Using Differential Pulse Voltammetry 下载免费PDF全文
Lijian Sun Jing Chen Fangmin Zhao Na Liu Yingqiu Zhang Jianbo Jia Jianguo Wang 《Electroanalysis》2015,27(6):1411-1415
It is difficult to monitor dopamine (DA) accurately with a bare glassy carbon electrode because of the interference of ascorbic acid (AA). In this paper, a method for the determination of DA in an AA solution using differential pulse voltammetry was established. Because AA loses its electrochemical activity after being oxidized, hydrogen peroxide was used to oxidize AA, and the interference of AA was completely eliminated. As a result, trace DA could be directly determined in the AA solution with a bare glassy carbon electrode. When trace DA was determined in a 1.0 mmol L?1 AA solution, there was a wide linear range from 3.0×10?8 mol L?1 to 1.0×10?5 mol L?1. The application of this method was demonstrated by the selective measurement of DA in an injection without pretreatment. 相似文献
994.
Reversing the Stereoselectivity of a Palladium‐Catalyzed O‐Glycosylation through an Inner‐Sphere or Outer‐Sphere Pathway 下载免费PDF全文
Shaohua Xiang Kim Le Mai Hoang Jingxi He Yu Jia Tan Prof. Dr. Xue‐Wei Liu 《Angewandte Chemie (International ed. in English)》2015,54(2):604-607
An efficient and concise method for the construction of various O‐glycosidic bonds by a palladium‐catalyzed reaction with a 3‐O‐picoloyl glucal has been developed. The stereochemistry of the anomeric center derives from either an inner‐sphere or outer‐sphere pathway. Harder nucleophiles, such as aliphatic alcohols and sodium phenoxides give β‐products, and α products result from using softer nucleophiles, such as phenol. 相似文献
995.
Formation of DNA:RNA Hybrid G‐Quadruplex in Bacterial Cells and Its Dominance over the Intramolecular DNA G‐Quadruplex in Mediating Transcription Termination 下载免费PDF全文
996.
Hypervalent Iodine Reagents Enable Chemoselective Deboronative/Decarboxylative Alkenylation by Photoredox Catalysis 下载免费PDF全文
Hanchu Huang Kunfang Jia Prof. Dr. Yiyun Chen 《Angewandte Chemie (International ed. in English)》2015,54(6):1881-1884
Chemoselective C(sp3)? C(sp2) coupling reactions under mild reaction conditions are useful for synthesizing alkyl‐substituted alkenes having sensitive functional groups. Reported here is a visible‐light‐induced chemoselective alkenylation through a deboronation/decarboxylation sequence under neutral aqueous reaction conditions at room temperature. This reaction represents the first hypervalent‐iodine‐enabled radical decarboxylative alkenylation reaction, and a novel benziodoxole‐vinyl carboxylic acid reaction intermediate was isolated. This C(sp3)? C(sp2) coupling reaction leads to aryl‐and acyl‐substituted alkenes containing various sensitive functional groups. The excellent chemoselectivity, stable reactants, and neutral aqueous reaction conditions of the reaction suggest future biomolecule applications. 相似文献
997.
Redox‐Neutral α‐Allylation of Amines by Combining Palladium Catalysis and Visible‐Light Photoredox Catalysis 下载免费PDF全文
Jun Xuan Ting‐Ting Zeng Zhu‐Jia Feng Qiao‐Hui Deng Prof. Dr. Jia‐Rong Chen Dr. Liang‐Qiu Lu Prof. Dr. Wen‐Jing Xiao Prof. Dr. Howard Alper 《Angewandte Chemie (International ed. in English)》2015,54(5):1625-1628
An unprecedented α‐allylation of amines was achieved by combining palladium catalysis and visible‐light photoredox catalysis. In this dual catalysis process, the catalytic generation of allyl radical from the corresponding π‐allylpalladium intermediate was achieved without additional metal reducing reagents (redox‐neutral). Various allylation products of amines were obtained in high yields through radical cross‐coupling under mild reaction conditions. Moreover, the transformation was applied to the formal synthesis of 8‐oxoprotoberberine derivatives which show potential anticancer properties. 相似文献
998.
Le Guo Xiaochen Ma Huaquan Fang Xiangqing Jia Prof. Dr. Zheng Huang 《Angewandte Chemie (International ed. in English)》2015,54(13):4023-4027
Catalytic α‐alkylation of esters with primary alcohols is a desirable process because it uses low‐toxicity agents and generates water as the by‐product. Reported herein is a NCP pincer/Ir catalyst which is highly efficient for α‐alkylation of a broad scope of unactivated esters under mild reaction conditions. For the first time, alcohols alkylate unactivated α‐substituted acyclic esters, lactones, and even methyl and ethyl acetates. This method can be applied to the synthesis of carboxylic acid derivatives with diverse structures and functional groups, some of which would be impossible to access by conventional enolate alkylations with alkyl halides. 相似文献
999.
Teng‐Shuo Zhang Rui Du Yan‐Yin Zhao Jia‐Dan Xue Hui‐Gang Wang Xuming Zheng 《Journal of Raman spectroscopy : JRS》2016,47(3):299-309
The B‐band resonance Raman spectra of 2(1H)‐pyridinone (NHP) in water and acetonitrile were obtained, and their intensity patterns were found to be significantly different. To explore the underlying excited state tautomeric reaction mechanisms of NHP in water and acetonitrile, the vibrational analysis was carried out for NHP, 2(1D)‐pyridinone (NDP), NHP–(H2O)n (n = 1, 2) clusters, and NDP–(D2O)n (n = 1, 2) clusters on the basis of the FT‐Raman experiments, the B3LYP/6‐311++G(d,p) computations using PCM solvent model, and the normal mode analysis. Good agreements between experimental and theoretically predicted frequencies and intensities in different surrounding environments enabled reliable assignments of Raman bands in both the FT‐Raman and the resonance Raman spectra. The results indicated that most of the B‐band resonance Raman spectra in H2O was assignable to the fundamental, overtones, and combination bands of about ten vibration modes of ring‐type NHP–(H2O)2 cluster, while most of the B‐band resonance Raman spectra in CH3CN was assigned to the fundamental, overtones, and combination bands of about eight vibration modes of linear‐type NHP–CH3CN. The solvent effect of the excited state enol‐keto tautomeric reaction mechanisms was explored on the basis of the significant difference in the short‐time structural dynamics of NHP in H2O and CH3CN. The inter‐molecular and intra‐molecular ESPT reaction mechanisms were proposed respectively to explain the Franck–Condon region structural dynamics of NHP in H2O and CH3CN.Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
1000.
Wei-Wei Jiang Jia Su Xing-De Wu Juan He Li-Yan Peng Xiao Cheng 《Natural product research》2015,29(9):842-847
Geissoschizine methyl ether N-oxide, a new oxindole alkaloid, along with 14 known alkaloids, was isolated from the aerial part of Uncaria rhynchophylla. Their structures were identified by comprehensive spectral methods, including 2D NMR experiments, and confirmed by comparing with the literature data. In vitro acetylcholinesterase (AChE) inhibitory activity assay showed that the new compound exhibited anti-AChE activity with IC50 value of 23.4 μM. 相似文献