聚并苯和取代聚并苯电子性质的量子化学研究

准一维聚并苯体系是一类典型的梯形结构有机导体材料．采用量子化学一维紧束缚自洽场晶体轨道ＣＮＤＯ／２　方法，研究了顺、反式聚并苯和取代聚并苯的结构、能量和电子布居．计算了甲基、甲氧基、氯和羟基取代聚并苯的电子能带，与聚并苯进行了分析比较．结果表明：（１）单取代使对称性明显降低，对聚并苯的能带结构影响较大，使能隙值普遍增大，导电性能降低．（２）双取代虽使电荷重新分布，但基本保持聚并苯自身结构特征．取代聚并苯与聚并苯比较能隙值变化不大．对于不同的取代基影响规律不同．对位双取代与间位双取代也表现出差异．（３）顺式和反式结构聚并苯的电子性质略有差异，取代后变化较大．     

聚并苯的链间作用对其导电能力的影响

采用量子化学晶体轨道ＣＮＤＯ／ ２ 方法,在考虑聚并苯链间作用的基础上对聚并苯双链模型的电子结构进行计算和讨论．结果表明：聚并苯链处于不同相对位置的链间作用对聚并苯的电荷分布规律及能带结构均有一定影响,位置不同,影响不同．从聚并苯的能带结构可以得出：聚并苯是有较小能隙、良好本征导电性能的半导体材料,考虑链间作用,对能带结构特征未有大的改变,能隙等值略有修正,导电能力有所加强．利用此模型讨论,更接近于晶体的真实结构,对进行聚并苯导电材料的性能改进将有一定帮助．     

ClO~4^-在聚并苯分子表面的吸附行为及其电子性质

采用量子化学CNDO/2法, 从理论上探讨了ClO~4^-在聚并苯表面的吸附行为。ClO~4^-在聚并苯分子中C=C双键、C-C单键中点上方为稳定吸附位, 前者吸附能最大。在其它位置吸附的ClO~4^-极易向该点迁移。EHMO-CO能带结构计算指出:ClO~4^-掺杂聚并苯中, ClO~4^-处在洞位、双键桥位及氢键位时, 体系的导电性能较好, 而作为电极材料, 洞位可能是吸附与脱附的最佳位置。     

两亲嵌段树枝状分子Gx-PBE-b-Gx-PMPA(OH)x2的合成及多重氢键作用

合成了1~3代的嵌段树枝状分子聚苄醚-聚脂肪酯(Gx-PBE-b-Gx-PMPA, x=1,2,3)和两亲嵌段树枝状分子聚苄醚-周边含羟基的聚脂肪酯[Gx-PBE-b-Gx-PMPA(OH)x2, x=1,2,3]. PMPA(OH)x2-树枝片(Dendron)段周边的羟基数目分别是2, 4和8. 通过1H NMR, 13C NMR, FTIR和基质辅助激光解吸附电离飞行时间质谱(MALDI-TOF)(或场解析电离质谱)技术表征了Gx-PBE-b-Gx-PMPA和Gx-PBE-b-Gx-PMPA(OH)x2的结构. 同时, 采用变温FTIR光谱研究了在两亲嵌段树枝状分子中形成的氢键模式. 结果表明, 随着树枝片代数的增加, 两亲嵌段树枝状分子内趋向于形成作用较弱的分子内氢键, 说明形成3代两亲嵌段树枝状分子的三维结构削弱了羟基形成分子间氢键的能力.     

硫化聚并苯导电材料结构的理论化学研究

采用量子化学从头算方法和AM1半经验方法,探讨了聚并苯导电聚合物硫掺杂前后结构和电子性质的变化,提出了硫化聚并苯导电材料的“双层夹心”分子结构模型.研究表明,硫化后的聚并苯材料,S原子位于两层聚并苯分子平面中间,并与两个聚并苯分子平面中相应的两个C原子相键合,形成C—S—C“桥式”共价单键;并解释了硫化聚并苯导电材料比本征态聚并苯材料作电极时可逆容量增大的原因.     

聚并苯和聚并吡啶类化合物非线性光学性质及其分子材料设计

选取聚并苯、聚并吡啶和聚并吡嗪的 3种共振结构为基体 ,计算不同共轭单体齐聚物的结构及被取代后的聚合物二阶和三阶非线性光学系数 .结果表明 ,聚合物的二阶非线性光学系数与其单体相比有显著增大 ,被—NH2 和 NO2 取代后的聚并苯、聚并吡啶和聚并吡嗪的非线性光学系数又在聚合物的基础上进一步大幅度增加 ,有的增加 2～ 3个数量级 .在非取代的聚合物中 ,聚吡啶各种结构的二阶非线性光学系数均较大 ;取代聚合物中 ,单—NH2 和—NO2 取代的聚并苯 ,尤其是反式共振结构聚并苯的二位— NH2 和五位—NO2 取代结构的聚合物二阶非线性光学系数高达 3 .2 7× 1 0 - 2 7esu,说明这种— NH2 和 -NO2 取代后的聚并苯是一种很好的非线性光学材料 .     

含氮杂环并苯类高聚物结构与能带规律的从头算和半经验量子化学研究

采用从头算ＨＦ和半经验量子化学方法,对含氮杂环并苯类高聚物体系进行几何结构优化．比较不同方法下它们的电子性质的差异,揭示聚并苯、聚并吡啶、聚并吡嗪的能带分布特征和规律．为深入研究导电、发光等功能材料及能带匹配器件的分子设计提供依据．     

聚乙烯/聚并苯复合材料室温电阻率变化规律研究

以新型导电材料聚并苯替代碳黑作为导电填料制备聚乙烯/聚并苯复合物.确定了复合物渗流转变区,并解释渗流转变现象的产生机理.从聚并苯含量和热处理过程,对聚乙烯/聚并苯复合物室温电阻率变化规律进行讨论.结果表明,聚并苯质量分数在20%～40%之间是聚乙烯/聚并苯复合物渗流转变区;热处理有利于聚乙烯晶区完善排列,也有利于导电链形成;以聚并苯作为导电填料所制备的复合物具有较高的PTC强度;辐射交联可以提高聚乙烯/聚并苯复合物PTC强度,抑制NTC效应.     

聚并苯纳米颗粒与聚丙烯复合制备新型抗静电阻燃材料

用聚并苯纳米颗粒作为新型导电填料代替导电炭黑和石墨等, 制备出具有抗静电阻燃性能的纳米聚并苯/聚丙烯复合材料. 测定了复合材料的渗流转变区, 讨论了纳米聚并苯含量对复合材料体积电阻率和表面电阻率的影响. 实验结果表明, 所制备复合材料的渗流转变发生在纳米聚并苯质量分数为16.7%-28.6%范围内, 当纳米聚并苯含量为28.6%时, 体积电阻率下降至2.09×107 Ω·cm. 另外, 阻燃性能研究结果表明, 当纳米聚并苯质量分数为23.1%时, 复合材料在空气中可以自熄, 因而可应用于矿井中抗静电阻燃塑料管道.     

乙烯-乙烯醇共聚物氢键相互作用与链结构关系的变温溶液氢谱研究

用变温溶液核磁共振氢谱研究了不同组成的乙烯-乙烯醇共聚物在二甲亚砜溶液中的氢键相互作用.结果表明,乙烯醇单元中羟基的信号随温度升高而线性地向高场位移,且不同的三单元组中羟基信号的位移速率不同,表明羟基形成的氢键强度与链结构间存在相关性.     

Buffer-induced changes of purple membrane surface electric properties: an electro-optical study

Buffer-induced alteration of the purple membrane electric dipole moments and electrokinetic charge was studied by electric light scattering and microelectrophoresis. The permanent dipole moment and electrophoretic mobility of purple membranes change in opposite direction in presence of 'P'- and 'N'-type buffer molecules, shown to produce 'positive' and 'negative' additional components to the bR light-induced charge displacement current. It is concluded that the two types buffer molecules distribute differently on the membrane surfaces, depending on their protonation state, as a result of different interaction with the membrane cytoplasmic and extracellular surfaces.     

WO3/TiO2 catalysts: Morphological and structural properties

Titania-supported tungsten oxide catalysts with different W loadings up to 9 wt. % and calcined at different temperatures have been prepared and characterized. It is found that W hinders the initial sintering of anatase, providing thermal stability. The interaction of W with TiO₂ and the amount of hydroxy groups present on the surface can limit diffusion, thus reducing the sintering rate.     

Functions of key residues in the ligand-binding pocket of vitamin D receptor: Fragment molecular orbital–interfragment interaction energy analysis

Fragment molecular orbital–interfragment interaction energy calculations of the vitamin D receptor (VDR)/1,25-dihydroxyvitamin D₃ complex were utilized to assign functions of key residues of the VDR. Only one residue forms a significant interaction with the corresponding hydroxy group of the ligand, although two residues are located around each hydroxy group. The degradation of binding affinity for derivatives upon removal of a hydroxy group is closely related to the trend in the strength of the hydrogen bonds. Type II hereditary rickets due to an Arg274 point mutation is caused by the lack of the strongest hydrogen bond.     

Optical Study of Interactions of Glass Beads ER Particles

The amount of ER effect is determined by the difference of dielectric constants of ER particles base liquid.The intensity of ER fluids can be characterized by the interaction of two particles. A double optical tweezers system suitable to study particle interaction is used to measure the particle aggregation time, and it is found that the particle aggregation time is proportional to the square of the electric field. This is the first time to directly measure the interaction of the electric dipoles of ER particles. A method is developed to use high speed CCD in measuring diffusing-wave spectroscopy (DWS), and, for the first time, the auto-correlation functions of nonegordic system of particle structure are measured to study the ER mechanism. Structure response time and force response time are obtained for glass beads ER fluid, and the time variation of characteristic decay times of system correlation functions under different electric fields is also measured. Diffusing coefficients under different fields imply that the interaction is proportional to the square of fields.     

Antioxidant effects of hydroxybenzalacetones on peroxynitrite-induced lipid peroxidation in red blood cell membrane ghost and SOS response in Salmonella typhimurium TA4107/pSK1002

Antioxidant activity of a series of hydroxybenzalacetones was determined against peroxynitrite-induced lipid peroxidation in red blood cell membrane and SOS response through DNA damage in bacterial cells. Hydroxybenzalacetone derivatives with hydroxy, methoxy, ethoxy or methyl substitution were analyzed and found to be more effective than the water-soluble vitamin E analogue Trolox. The inhibitory effect against lipid peroxidation correlated well to that against the SOS response, which is dependent on decomposition of peroxynitrite by hydroxybenzalacetones outside of the cell membrane. The antioxidant activity was shown to correlate well with the electric parameter sigma+. Electron-donating substituents with more negative sigma+ values increased the potencies. The result suggests that hydroxybenzalacetones with more electron-donating substituents will protect tissue more effectively against oxidative stress.     

Separation behaviors of xylenol isomers by gas chromatography with helps of hydrogen bonding

Summary Xylenol isomers can be resolved on most polyols (sugars or sugar alcohols) and polyethers (polyethylene glycol or polypropylene glycol) with hydrogen-bonding interaction. They are separated on vinical polyols which have more hydroxy hydrogen than tetrol, and even on vicinal triol when its hydroxy hydrogen is acidic (stronger proton donor). The stronger is the hydrogen bonding interaction between xylenols and the liquid phase, the better is the separation of 2,4- and 2,5-xylenol, and the poorer the separation of 2,4-and 2,3-xylenol.     

N-H and alpha(C-H) bond dissociation enthalpies of aliphatic amines

Bond dissociation enthalpies (BDEs) of a large series of aliphatic amines (21) were measured by means of photoacoustic calorimetry. Despite the different structures studied in the primary, secondary, and tertiary amine series, the alpha(C-H) BDEs were found to be very similar for unconstrained amines with values very close to 91 kcal/mol. alphaC- and N-alkylation or introduction of an hydroxy group only slightly affect the BDEs, a fact in perfect agreement with calculations performed at different CBS levels. This demonstrates the predominance of the two-orbital-three-electron interaction involving the N and alphaC(*) orbitals. On the other hand, the N-H BDE decreases when going from primary to secondary amines. This result is interpreted in term of a hyperconjugation in sigmaC-C bonds, which leads to a stabilization of the aminyl radical. For cyclized amines, the BDEs depend on the relative geometry of the singly occupied alphaC(*) orbital with respect to that of the N atom, disfavoring the two-orbital-three-electron interaction. However, such structures can exhibit through-bond interaction. For a crowded structure such as triisopropylamine, for which the alphaC(*) orbital is not coplanar with the nitrogen one, the relaxation of a strain energy allows the BDE to be comparable to flexible structures.     

人顶体酶活性腔性质及与抑制剂的结合模式

顶体酶是目前抗生育药物的一个潜在靶点. 在前期同源模建人顶体酶三维结构复合物的基础上, 采用多重拷贝同时搜寻(MCSS)等方法对人顶体酶活性腔进行分析. 结果显示, 活性腔的P1,P2和G 3个区域均具有较大极性, 且P1对抑制剂结合尤为重要. 另外, G和P1边缘及P2底部还具有一定疏水性, 且其中的部分重要残基还能与配体形成氢键作用和静电作用. MCSS计算结果确定的关键配体结合位点与人顶体酶复合物结构和定点突变实验结果相吻合. 在此基础上用分子对接方法将6个人顶体酶代表性抑制剂对接入活性腔, 阐明其结合模式, 确定与配体结合相关的关键残基.