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Pingli Lv Rongxiu Zhu Tongxiang Lu Steven E. Wheeler Dongju Zhang Ruoxi Wang Chengbu Liu 《Tetrahedron: Asymmetry》2013,24(24):1598-1604
Computational studies to determine the origin of enantioselectivity in the (1R,2R)-1,2-diphenylethane-1,2-diamine (DEPN)–Brønsted acid catalyzed epoxidation of 2-cyclohexen-1-one have been performed using density functional theory. Transition states for conjugate addition and ring closure steps of the epoxidations catalyzed by three different catalyst systems were characterized. Our calculations show that the Csp2H?O H-bond interaction between the benzene ring of the catalyst and H2O is mainly responsible for the chiral discrimination observed. The Brønsted acid counterion plays a very important role in ensuring high enantioselectivity by improving the rigidity of the transition state structures to allow the efficient formation of the Csp2H?O H-bond. Moreover, we explain why these two diamine catalysts (1S,2S)-DACH and (1R,2R)-DPEN display consistent enantioselectivities in the catalytic epoxidation of 2-cyclohexen-1-one when combining with three different cocatalysts; achiral TFA, and chiral (R)- and (S)-TRIP. 相似文献
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Determination of glutathione in single HepG2 cells by capillary electrophoresis with reduced graphene oxide modified microelectrode 下载免费PDF全文
Determination of intracellular bioactive species will afford beneficial information related to cell metabolism, signal transduction, cell function, and disease treatment. In this study, the electrochemically reduced graphene oxide modified carbon fiber microdisk electrode (ER‐GOME) was used as a detector of CZE‐electrochemical detection and developed to detect glutathione (GSH). The electrocatalytic activity of the modified microelectrode was characterized by cyclic voltammetry. Under optimized experimental conditions, the concentration linear range of GSH was from 1 to 60 μM. When the S/N ratio was 3, the concentration detection limit was 1 μM. Compared with the unmodified carbon fiber microdisk electrode, the sensitivity was enhanced more than five times. With the use of this method, the average contents of GSH in single HepG2 cells were found to be 7.13 ± 1.11 fmol (n = 10). Compared with gold/mercury amalgam microelectrode, which was usually used in determining GSH, the electrochemically reduced graphene oxide modified carbon fiber microdisk electrode was friendly to environment for free mercury. Furthermore, there were several merits of the novel electrochemical detector coupled with CE, such as comparative repeatability, easy fabrication, and high sensitivity, hold great potential for the single‐cell assay. 相似文献
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Young-Woon Cho Kyung-Seok Kang Chanhyuk Jee Ji-Hyun Kim Dongju Jang 《Molecular Crystals and Liquid Crystals》2016,634(1):73-81
Polyamic acid (PAA) made from 3,3, 4,4-biphenyltetracarboxylic dianhydride and 4,4-diaminodiphenyl ether was synthesized and used as the backbone of nanoporous polyimide. Thermally labile polyethylene glycol (PEG) at 10, 20 or 30 wt% was introduced to the end group of PAA. Self-assembled PAA-b-PEG micelle-like nanoparticles could be formed as a result of amphiphilic characteristics of hydrophobic PAA and hydrophilic PEG. Thermal imidization and degradation of spin-coated amphiphilic PAA-b-PEG film were performed sequentially through one-step heat treatment to obtain polyimide film with nanopores. Pore sizes decreased with increasing amount of PEG block and their dielectric constants decreased from 2.71 ± 0.13 to 2.38 ± 0.11. 相似文献
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Chunmei Wu Tianyi Li Dongju Li Shanshan Jia Jianmei Huang Haimin Lei Mei Zhang 《中国化学快报》2021,32(7):2174-2178
Chinese herbal medicines(CHMs) play an increasingly important role in the field of medicine and affects public health in the world.Although more and more strict has been employed to ensure the quality and safety of CHMs,pesticide residues in CHMs remain a serious issue and are the bottleneck for the global development of CHMs.In this work,we applied molecularly imprinted membrane electrospray mass spectrometry(MIM-ESI MS) for rapid detecting 4 classes of pesticide residues in CHMs,including organophosphorus(OPP),carbamates,pyrethroids and neonicotinoids in CHMs.Compared with our previous ambient ionization method MESI,MIM-ESI is capable of achieving a ~50-fold increase in the detection limit of conventional analytical methods owing to the specificity recognition and unique enrichment of MIM.The optimal experimental conditions were determined,and the method was further validated for its sensitivity and specificity.Our data showed that MIM-ESI MS is applicable for the direct quantitation of pesticide residues in CHMs.This detection technology may help to ensure the quality of CHMs in the future. 相似文献
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Peng Liu Jianqiang Liu Dongju Zhang Changqiao Zhang 《International journal of quantum chemistry》2010,110(9):1583-1593
A very recent laser ablation‐molecular beam experiment shows that an Al+ ion can react with a single methylamine (MA, CH3NH2) or dimethylamine (DMA, (CH3)2NH) molecule to form a 1:1 ion–molecule complex Al+[CH3NH2] or Al+[(CH3)2NH)], whereas a dehydrogenated complex ion Cu+[CH3N] or Cu+[C2H5N] is detected, respectively, in the similar reaction for a Cu+ ion. Here, we show a comparative density functional theory study for the reactivities of the Al+ and Cu+ ions toward MA and DMA to reveal the intrinsic mechanism. It is found that the interactions of the Al+ ion with MA and DMA are mostly electrostatic, leading to the direct ion–molecule complexes, Al+? NH2CH3 and Al+? NH( CH3)2, in contrast to the non‐negligible covalent character in the corresponding Cu+‐containing complexes, Cu+? NH2CH3 and Cu+? NH( CH3)2. The general dehydrogenation mechanism for MA and DMA promoted by the Cu+ ion has been shown, and the preponderant structures contributing to the mass spectra of the product ions Cu+[CH3N] and Cu+[C2H5N] are rationalized as Cu+? NHCH2 and Cu+? N( CH2)( CH3). The presumed dehydrogenation reactions are also discussed for the Al+‐containing systems. However, the involved barriers are found to be too high to be overcome at low energy conditions. These results have rationalized all the experimental observations well. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010 相似文献
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FengHui Tian ChengBu Liu Dongju Zhang Aiping Fu Yunbo Duan Shuping Yuan Jimmy C. Yu 《Chemphyschem》2010,11(15):3269-3272
Plane‐wave‐based pseudopotential density functional theory (DFT) calculations are used to elucidate the origin of the high photocatalytic efficiency of carbonate‐doped TiO2. Two geometrically possible doping positions are considered, including interstitial and substitutional carbon atoms on Ti sites. From the optical absorption properties calculations, we believe that the formation of carbonates after doping with interstitial carbon atoms is crucial, whereas the contribution from the cationic doping on Ti sites is negligible. The carbonate species doped TiO2 exhibits excellent absorption in the visible‐light region of 400–800 nm, in good agreement with experimental observations. Electronic structure analysis shows that the carbonate species introduce an impurity state from Ti 3d below the conduction band. Excitations from the impurity state to the conduction band may be responsible for the high visible‐light activity of the carbon doped TiO2 materials. 相似文献
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中国区域稳定工程地质学产生与发展 总被引:4,自引:0,他引:4
区域稳定工程地质学是在中国产生、发展和壮大起来的。自50年代产生以来,历经几代工程地质工作者的不懈努力,现已形成了具有系统理论和系统研究方法、在国民经济建设中正发挥着显着作用的新兴学科。回顾该学科的产生与发展过程,对促进该学科的思维方法、学科理论和进一步发挥学科作用具有重要的意义。 相似文献
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On the basis of computational considerations, using metastable four-membered rings as building blocks, we propose novel synthetic routes toward well-defined stoichiometric silica nanofullerenes and nanotubes. The viability of the routes has been demonstrated by performing high-level density functional calculations, and the so-formed nanoarchitectures were proved to be energetically and structurally stable. Such nanostructures, if synthesized, are expected to have potential application in nanotechnology. 相似文献