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991.
运用量子化学密度泛函B3LYP方法,在6-311++G(d,p)基组水平上对邻位和间位取代1-氯葸醌的分子内卤键进行了研究.用电子定域函数和“分子中的原子,,理论对分子内卤键的性质进行了电子密度拓扑分析.通过对计算得到的密度矩阵进行σ-π兀分离,得到了π-键的键径和分子图,并讨论了。电荷密度和兀电荷密度对卤键的影响.结果表明,键鞍点和环鞍点处的电子密度拓扑性质均可作为衡量分子内卤键强度的量度.键鞍点和环鞍点处的电荷密度P越大,键鞍点与环鞍点的距离越大,卤键强度越大.除σ电荷密度外,π电荷密度对分子内卤键的性质也有明显影响. 相似文献
992.
The interaction between[Hg(SCN)4]2- and hemoglobin(Hb) under conditions that simulate a physiological environment was investigated by UV-vis spectroscopy,fluorescence spectroscopy,resonance Rayleigh scattering(RRS) spectroscopy and circular dichroism(CD) spectroscopy.The results obtained from the change of UV-vis and CD spectra,the quenching of Hb fluorescence and the enhancement of RRS intensity proved that a 10:1 type complex was formed between[Hg(SCN)4]2- and Hb.The possible mechanism suggested for the interaction was that ten Hg(SCN)4]2- anions entered the four subunits of a Hb molecule to react with some residues to form an adduct by coordination and electrostatic forces.The coordination of[Hg(SCN)4]2- with Trp was the major cause of the fluorescence quenching of Hb. 相似文献
993.
H Fu C Qin Y Lu ZM Zhang YG Li ZM Su WL Li EB Wang 《Angewandte Chemie (International ed. in English)》2012,51(32):7985-7989
Pretty porous POMs: Ionothermal synthesis was applied to prepare porous POM-based open frameworks. The structural integrity remains unchanged until 300?°C; most importantly, the bulky tetrabutylammonium cations within their nanosized channels can be replaced by transition-metal ions through a cation-exchange process, and subsequent gas adsorption measurements confirm their permanent porosity. 相似文献
994.
A commercially-available sulfonphthalein derivative was demonstrated to be a chemodosimeter for Fe2+ and its sensing behavior was further investigated by UV-vis spectroscopy in aqueous media under the optimum conditions. In the presence of chlorophenol red (CPR) and H2O2, the absorption maximum at 435 nm decreased upon addition of Fe2+, resulting in a significant color change of the CPR solution from yellow to colorless. The chemosensor system did not show significant responses to a series of other metal ions including Al3+, Zn2+, Cd2+, Hg2+, Mn2+, Co2+, Fe3+, Ni2+, Cu2+, La3+, Ce4+, Th4+, Pd2+, Pb2+, Sb3+, Cr3+, Au3+, Ag+, Nd3+, Sm3+, alkali and alkaline earth metal cations, allowing for highly selective naked-eye detection of Fe2+. Quantitative analysis was carried out kinetically for practicable the Fe2+ assay when either fixed time method or the initial rate method was applied. When the detecting time was set, the decrease of absorbance signal was linear with Fe2+ concentration in the range of 0 to 7.50 × 10?5 mol L?1 and the regression equation was ΔA = 0.00759 + 0.00593C Fe with a correlation coefficient r = 0.9953. The chemodosimetric system has employed an irreversible Fenton reagent-promoted oxidation of the CPR free chromophore and the hydroxyl radicals were generated in the presence of both Fe2+ and hydrogen peroxide. The mechanistic interpretation of the signaling process was partially confirmed by the radical scavenging experiment and the FT-IR analysis of the intermediates formed at different reaction periods. 相似文献
995.
Yue W Gao J Li Y Jiang W Di Motta S Negri F Wang Z 《Journal of the American Chemical Society》2011,133(45):18054-18057
Tetracene tetracarboxylic diimides have been synthesized based on direct double ring extension of electron-deficient naphthalene diimides involving metallacyclopentadienes. Atomic structure and electronic transitions responsible for their NIR absorption spectra are investigated with quantum-chemical calculations. In light of their unique structure and admirable photophysical and electronic properties, this new molecular skeleton is promising candidate for n-type semiconductors. 相似文献
996.
Electromagnetic mechanism of deep ultraviolet tip-enhanced Raman scattering (DUV-TERS) is investigated theoretically with the finite-difference time-domain (FDTD) method, stimulated by recent DUV-TERS experimental reports. FDTD results reveal that the strongest electromagnetic enhancement factor for DUV-TERS is as high as 7 orders in the optimal geometry. 相似文献
997.
Recent advances in molecular imprinting technology: current status, challenges and highlighted applications 总被引:5,自引:0,他引:5
Molecular imprinting technology (MIT) concerns formation of selective sites in a polymer matrix with the memory of a template. Recently, molecularly imprinted polymers (MIPs) have aroused extensive attention and been widely applied in many fields, such as solid-phase extraction, chemical sensors and artificial antibodies owing to their desired selectivity, physical robustness, thermal stability, as well as low cost and easy preparation. With the rapid development of MIT as a research hotspot, it faces a number of challenges, involving biological macromolecule imprinting, heterogeneous binding sites, template leakage, incompatibility with aqueous media, low binding capacity and slow mass transfer, which restricts its applications in various aspects. This critical review briefly reviews the current status of MIT, particular emphasis on significant progresses of novel imprinting methods, some challenges and effective strategies for MIT, and highlighted applications of MIPs. Finally, some significant attempts in further developing MIT are also proposed (236 references). 相似文献
998.
Sun YX Huang YX Li FL Wang HY Fan C Bao YL Sun LG Ma ZQ Kong J Li YX 《Chemistry Central journal》2012,6(1):2
Background
The virtual screening (VS) of lead compounds using molecular docking and pharmacophore detection is now an important tool in drug discovery. VS tasks typically require a combination of several software tools and a molecular graphics system. Thus, the integration of all the requisite tools in a single operating environment could reduce the complexity of running VS experiments. However, only a few freely available integrated software platforms have been developed. 相似文献999.
1000.