(1R,4S,5S)-6-环己基-4-[(1R,2S,5R)-5-甲基-2-异丙基环己氧基]-3-氧杂-6-氮杂双环[3.1.0]-2-己酮的合成及结构表征

环已胺与差向异构体5-[(1R,2S,5R)-5-甲基-2-异丙基环己氧基]-3-溴-2(5H)-呋喃酮发生不对称Mi-chael加成-分子内亲核取代反应,并经柱层析分离,得到一对手性氮杂环丙烷-丁内酯衍生物,其中的标题化合物为首次得到的新手性化合物,产率17%,其结构经IR、1H NMR、13C NMR和HRMS进行了表征。     

3-吲哚乙酸印迹聚合物的制备及其分子识别性能

以IAA为模板分子,4-乙烯基吡啶(4-Vpy)为功能单体,乙腈为致孔剂,采用本体聚合方法,制备了IAA的印迹聚合物P(4-Vpy),用色谱法评价了其分子识别性能,并且与同样条件下以丙烯酰胺(AA)为功能单体合成的IAA印迹聚合物P(AA)进行了比较。结果表明,乙腈为流动相时,P(4-Vpy)比P(AA)对IAA具有更高的印迹效率,对IAA表现出了更好的分子识别能力。流动相对P(4-Vpy)分子识别能力的影响实验证明,静电作用在其分子识别过程中起重要作用。两种不同用量的乙腈为致孔剂制备所得IAA印迹聚合物P(4-Vpy)和P`(4-Vpy)的色谱测定结果表明,致孔剂的加入量对其印迹效率有显著影响。     

“门控制”效应分子印迹传感器测定绿麦隆

在氧化铂电极表面采用化学聚合法制得绿麦隆分子印迹膜传感器。利用"门控制"中"门"的数量变化控制催化性能的强弱,结合氧化铂对过氧化氢的催化放大效应,有效的提高了传感器的灵敏度并建立了对环境中绿麦隆残留的检测方法。研究了氧化铂电极对过氧化氢的催化效果,并对分子印迹膜聚合配比、过氧化氢浓度、洗脱时间、重吸附时间进行优化。在优化条件下,绿麦隆浓度在1.0×10^-88.0×10^-6mol/L范围内与氧化铂电极对过氧化氢的催化电流呈负相关性,检出限为5.4×10^-9moL/L。该传感器成功应用于农田水样的检测,其回收率为98.5%¹02.0%。     

多壁碳纳米管修饰电极分子印迹传感器测定咖啡因

以咖啡因为模板分子,通过电聚合邻苯二胺,在羧基化多壁碳纳米管修饰的玻碳电极表面制备了对咖啡因有特异响应的分子印迹聚合物膜。通过循环伏安法和线性扫描伏安法对传感器的性能进行表征,并优化了检测条件,研究了印迹传感器对模板分子咖啡因及其结构类似物的选择性响应。在最优实验条件下,电化学探针K3[Fe(CN)6]的峰电流与咖啡因浓度在2.0×10-7~2.0×10-5mol·L-1范围内呈良好的线性关系,检出限为4.0×10-8mol·L-1。该传感器应用于铁观音茶叶中咖啡因含量的测定,其回收率为94%~106%。     

定量蛋白质组学新技术新方法研究获新进展

9月3日,中科院大连化学物理研究所邹汉法、叶明亮研究员带领的团队,在定量蛋白质组学新技术新方法方面取得新进展,发展了一种基于胰蛋白酶催化的N端稳定同位素编码的氨基酸标记的相对定量蛋白质组学方法。相关研究成果发表在德国《应用化学》上。蛋白质组学研究的主要内容是蛋白质的表达水平,翻译后修饰,蛋白与蛋白相互作用等,最终的     

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Characterization and Three-dimensional Structural Modeling of Humic Acid via Molecular Mechanics and Molecular Dynamic Simulation

The humic acid（HA） sample obtained from the alluvial soil was characterized by elemental composition, pyrolysis gas chromatography-mass spectrometry（Py-GC-MS） and solid-state 13C nuclear magnetic resonance （13C NMR） spectroscopy. There is high fat content and a few nitrogen-containing functional groups in HA. Py-GC-MS demonstrates the characterization and structural identification of HA. One long list of identified pyrolysis products was proposed for the construction of conceptual model of HA. Solid-state 13C NMR data indicate there are higher values of alkyl-C, O-alkyl-C and aryl-C in HA. The elemental composition, structural carbon distribution and L3C NMR spectroscopy of simulated HA are consistent with those of experimental HA. HyperChem was used to simulate the three-dimensional molecular structure of the monomer, which was optimized by the molecular mechanics of the optimized potential for liquid simulations（OPLS） force field and molecular dynamics simulation to get the stable and balanced conformation. The deprotonation process study depicts that the degree of ionization of HA gets deeper, while the electronegativity of HA and the energy of van der Waals（vdW） increase. Moreover, the 3D structure of humic acid with -4 charges is the most stable. The deprotonation process is an endothermic process.     

雾霾中检出大量含氮有机物 被指最危险信号

中国科学院不久前公布了该院"大气灰霾追因与控制"专项组的最新研究结果,研究认为,最近的强雾霾事件,是异常天气形势造成中东部大气稳定、人为污染排放、浮尘和丰富水汽共同作用的结果,是一次自然因素和人为因素共同作     

Theoretical Insights into Intermolecular Hydrogen-Bonding Strengthening in Fluorenone-Methanol Complexes Induced by Electronic Excitation and Bulk Solvent Effect

This work presents a theoretical insight into the variation of the site-specific intermolecular hydrogen-bonding （HB）, formed between C=O group of fluorenone （FN） and O-H groups of methanol （MeOL） molecules, induced by both the electronic excitation and the bulk solvent effect. Through the calculation of molecular ground- and excited-state properties, we not only demonstrate the characters of HB strengthening induced by electronic excitation and the bulk solvent effect but also reveal the underlying physical mechanism which leads to the HB variation. The strengthening of the intermolecular HB in electronically excited states and in liquid solution is characterized by the reduced HB bond-lengths and the red-shift IR spectra accompanied by the increasing intensities of IR absorption corresponding to the characteristic vibrational modes of the O-H and C--O stretching. The HB strengthening in the excited electronic states and in solution mainly arises from the charge redistribution of the FN molecule induced by the electronic excitation and bulk solvent instead of the intermolecular charge transfer. The charge redistribution of the solute molecule increases the partial dipole moment of FN molecule and the FN-MeOL intermolecular interaction, which subsequently leads to the HB strengthening. With the bulk solvent effect getting involved, the theoretical IR spectra of HBed FN-MeOL complexes agree much better with the experiments than those of gas-phase FN-MeOL dimer. All the calculations are carried out based on our developed analytical approaches for the first and second energy derivatives of excited electronic state within the time-dependent density functional theory.     

ABEEMσπ和OPLS-AA力场对蛋白质GA88/GB88的分子动力学模拟

将原子与键电负性均衡方法融入分子力学方法,即利用ABEEMσπ浮动电荷力场与ABEEM-7P水模型相结合的方法及OPLS-AA固定电荷力场方法,对GA88和GB88蛋白进行了水溶液(温度295 K)和真空中的分子动力学模拟.比较两种方法得到的两个蛋白质的结构与实验结构的均方根偏差,分析了两种方法得到的两个蛋白质的回旋半径、氢键分布、径向分布及电荷分布情况.结果表明,ABEEMσπ和OPLS-AA力场均能正确模拟蛋白质结构,得到的各项偏差值接近,但从各偏差的波动大小可见,ABEEMσπ力场的模拟更稳定;回旋半径模拟很好地体现了蛋白质的"电致紧缩"现象;氢键分布、径向分布及电荷分布表明,与OPLS-AA固定电荷力场相比,ABEEMσπ浮动电荷力场能更好地体现蛋白质和周围水分子的极化效应.