有机磷农药气相色谱保留值与其化学结构关系的研究

对23种有机磷农药的气相色谱相对保留值与其化学结构的关系进行了探讨.参照图论法对分子中各种基团进行了分类.采用多元线性拟合法,求出了农药分子中各种基团的个数与其气相色谱保留值关系的回归方程,能得到方程的预测值与实验测定的色谱相对保留值一致的结果.     

单分子中心定位精度与信噪比关系及中心定位算法改进研究

本文从理论和实验两个角度研究单荧光分子中心定位精度与信噪比的关系,提供了一种相对简单的方法来确定基于单分子中心定位技术的超高分辨显微成像系统的分辨率。特别是,本文给出一种提高定位精度的像素重建算法,在信噪比等条件不变的情况下,该算法可有效改善单分子定位精度,从而提高超高分辨成像系统的分辨率。     

电致发光类湿法小分子材料研究进展

经过20年的发展,真空蒸镀和溶液法制备有机发光二极管的方法已经取得了巨大的进步。相对于依赖真空蒸镀成膜的有机小分子材料,可溶液法加工的小分子材料能够降低器件制作成本,适合于制作大面积光电器件。同时,小分子材料可以较为明确的给出分子结构与光电性能的构效关系,因此湿法成膜制备的小分子OLEDs越来越受到人们关注。综述了近期可湿法成膜的小分子材料设计理念、合成方法以及具体应用,讨论了实现全湿法小分子OLEDs所面临的挑战以及解决方法。     

盖子环替换及定点突变提高菜豆环氧化物水解酶对邻甲基苯基缩水甘油醚的催化性能

菜豆环氧化物水解酶1和2（PvEH1、PvEH2）能够动力学拆分外消旋邻甲基苯基缩水甘油醚（rac-oMGE）,从而保留(R)-oMGE。基于对PvEH1和PvEH2结构的同源模拟和分析,发现二者分子中的盖子环差异较大,故本文选择盖子环作为研究目标。经融合聚合酶链式反应（FPCR）,获得了PvEH2的盖子环区域被PvEH1对应区域替换的杂合酶Pv2Pv1。用全细胞酶E. coli/pv2pv1催化rac-oMGE,当(S)-oMGE刚好水解完全时,产物(S)-3-邻甲苯基-1,2-丙二醇（(S)-oTPD）的ee_p由PvEH2的58.3%提高至75.5%。为进一步提高酶的性质,在Pv2Pv1中选取11个氨基酸位点进行丙氨酸(A)突变,获得最优突变子E. coli/pv2pv1^K176A,活性为E. coli/pv2pv1（4.2U/g）的2.1倍,且当S构型的底物刚好完全水解时,(S)-oTPD的ee_p进一步提高为80.3%。分子对接分析发现,盖子环替换和K176位点突变为A,均使(R)-oMGE环氧环中的C_α更易受到酶中D101位点的攻击。利用E. coli/pv2pv1^K176A催化150mmol/L rac-oMGE水解制备(R)-oMGE（ee_s＞99%）和(S)-oTPD（ee_p=80.4%）,二者的产率Y_S和Y_P分别为32.7%和60.1%,时空产率STY_S和STY_P为1.6g/(L·h)和3.3g/(L·h)。本实验为改善EH的催化性质提供了一种有效策略。     

煤表面对氧分子物理吸附的微观机理

应用量子化学的理论和方法研究煤这种非晶体物质的物理吸附机理,从微观上揭示其吸附机理和吸附过程,定量研究煤对氧分子发生物理吸附过程中吸附量和放出热量的关系,从而揭示煤炭氧化自燃初始反应的本质.从煤表面对多个氧分子吸附优化后的平衡几何构型可以看出,煤表面吸附5个以下的氧分子时,1个氧分子在煤表面含氮的侧链吸附,其余的氧分子被苯环所吸附.煤表面吸附6个氧分子以上时,苯环对氧分子的吸附减弱,被吸附的氧分子偏向侧链端,在煤表面侧链部位吸附了大量的氧分子,这也证明了在煤的氧化自燃过程中侧链首先被氧化的结论的正确性.煤表面对氧分子的吸附量与吸附能呈线性关系.     

包结拆分在手性药物分离中的机理与应用

对外消旋体药物进行分离拆分是获取手性药物的重要方法。探讨了环糊精体系包结拆分法的机理，并对运用其机理于手性药物分离中的应用作了探讨。     

非热等离子体催化转化C1分子及其催化剂研究进展

非热等离子体催化具有反应条件温和、启动快和反应器结构紧凑等特点,在C₁分子催化转化领域（如CO₂加氢、甲烷活化、水煤气变换反应和甲醇重整制氢）有着广阔的应用前景。具体来说,等离子体特有的高能电子可在气相中快速活化稳定性极强的C₁分子并生成活性物质,接着与催化剂结合发生表面化学反应,从而实现常温常压下C₁分子的高效转化。然而,等离子体与催化剂之间的协同作用机制以及催化机理极为复杂,仍有待进一步研究。本综述简单介绍了非热等离子体催化转化C₁分子的近期研究进展,重点探讨了适用于非热等离子 体的催化剂研究以及催化机理的高级原位表征。最后,提出了非热等离子体催化转化C₁分子的未来发展方向：①设计并构筑适用于非热等离子体催化的高效催化剂,并研究其构效关系;②发展高级原位表征技术,揭示活性物质的作用机理以及催化机理;③设计并构建高效的等离子体催化反应器,并建立反应器的理论模型和数值模拟方法,科学指导等离子体反应器的设计、优化和放大。     

Nitrosation and Nitration of Tetraacetyldibenzylhexaazaisowurtzitane

Tetraacetyldibenzylhitane (TADBIW) was subjected to debenzylation by nitrosating with inorganic materials available commercially to synthesize tetraacetyldinitrosohexaazaisowurtzitane (TADNSIW). TADNSIW was purified, and its structure was determined by FTIR, 1H NMR, MS and element analysis. The debenzylation reaction of TADBIW gave quantitative benzaldehyde as a by-product. This indicates that the reaction produces an imine cation as an intermediate. Hexanitrohexaazaisowurtzitane (HNIW) was prepared from unpurified TADNSIW with the yield over 96.0 % and the purity more than 98.0 %. And the mechanism of the reaction from TADNSIW to HNIW is proposed to be oxidation of nitroso and nitration of acetyl on the molecule of TADNSIW, This reaction system involved is simple, and the reaction can complete within a short time and under mild conditions. The product can be easily to separate and the waste disposed readily.     

Fluid Mixing for Low‐Power ‘Digital Microfluidics’ Using Electroactive Molecular Monolayers

A switchable electrode, which relies on an indium‐tin oxide conductive substrate coated with a self‐assembled monolayer terminated with an anthraquinone group (AQ), is reported as an electrowetting system. AQ electrochemical features confer the capability of yielding a significant modulation of surface wettability as high as 26° when its redox state is switched. Hence, an array of planar electrodes for droplets actuation is fabricated and integrated in a microfluidic device to perform mixing and dispensing on sub‐nanoliter scale. Vehiculation of cells across microfluidic compartments is made possible by taking full advantage of surface electrowetting in culture medium.     

Nanopore Biosensors: Monitoring of an ATP‐Binding Aptamer and its Conformational Changes Using an α‐Hemolysin Nanopore (Small 1/2011)

An aptamer is a specific oligonucleotide sequence that spontaneously forms a secondary structure capable of selectively binding an analyte. An aptamer’s conformation is the key to specific binding of a target molecule, even in the case of very closely related targets. Nanopores are a sensitive tool for the single‐molecule analysis of DNA, peptides, and proteins transporting through the pore. Herein, a single α‐hemolysin natural nanopore is utilized to sense the conformational changes of an adenosine 5’‐triphosphate (ATP)‐binding aptamer (ABA). The known DNA sequence of the ABA is used as a model to develop real‐time monitoring of molecular conformational changes that occur by binding targets. The native, folded ABA structure has a nanopore unfolding time of 4.17 ms, compared with 0.29 ms for the ABA:ATP complex. A complementary 14‐mer strand, which binds the ABA sequence in the key nucleic acids responsible for folding, forms linear duplex DNA, resulting in a nanopore transit time of 0.50 ms and a higher capture probability than that of the folded ABA oligomer. Competition assays between the ABA:ATP and ABA:reporter complexes are carried out, and the results suggest that the ABA:ATP complex is formed preferentially. The nanopore allows for the detection of an ABA in its folded, ATP‐bound, and linear conformations.