Electron radiation effects on the structure of ultradisperse polytetrafluoroethylene

Electron radiation effects (40 mrad, 70 mrad, and 100 mrad) on the molecular and supramolecular structure and morphology of ultradisperse polytetrafluoroethylene obtained by the thermogas dynamic (TGD) method were studied by IR and EPR spectroscopy, X-ray phase analysis, and atomic force microscopy. Irradiation of ultradisperse powder in air leads to oxidized polymer forms due to the terminal carbonyl groups and stable peroxide radicals that appear in the structure. Fast electron radiation in doses of up to 100 mrad did not change the polymer crystallinity and particle entity, while thin films on the surface of ultradisperse polytetrafluoroethylene powder decomposed.     

葡萄球菌肠毒素B基因的膜片电极支撑双层类脂膜核酸传感器的研究

本研究用膜片电极支撑双层类脂膜(BLMs)核酸传感器,检测葡萄球菌肠毒素B(SEB)基因。BLMs在膜片钳尖端形成后,传感器的检测电流大小和施加的电压成正比。通过在BLMs上固定针对SEB基因特异的直链十二烷烃链(0～273.65μg/L)修饰的单链寡核苷酸(C12-ssDNA)探针与膜片钳系统一同构建成膜片电极支撑BLMs核酸传感器。电流大小与探针的浓度呈正相关,线性回归方程I=5.49 2.94C;相关系数r=0.9962。SEB基因浓度在20～5000μg/L范围时,检测的电流信号与SEB基因浓度的自然对数呈负相关,线性回归方程I=1103.26-103.62lnC,相关系数r=0.9977;同时,核酸传感器有很好的特异性,与不产SEB的金葡菌属、其它食物中毒菌的基因组DNA和空白对照组反应无明显电信号响应。应用原子力显微镜对BLMs表面微观结构、ssDNA固定于BLMs上和BLMs上杂交洗脱后的表面微观结构进行观察。本研究构建的膜片电极支撑BLMs核酸传感器为SEB基因的检测提供了一种快速、灵敏、特异性强的方法。     

单核锌双卟啉配合物构象平衡的理论研究及光谱分析

合成了一系列以不同长度柔韧链相连的p/p型单核锌双卟啉配合物。选用Tripos力场,利用分子动力学模拟退火和分子力学构象搜索相结合的方法对该系列双卟啉进行了能量优化和构象分析。理论计算结果表明:该类双卟啉稳定存在的最低能量构象为叠合式,最高能量构象为伸展式,并存在一系列的中间能量构象;双卟啉分子内π-π作用和能量转移与双卟啉存在的两种主要构象密切相关;分析了分子内π-π作用的本质。运用不同光谱测试手段验证了理论计算结果: 利用可见和相应二阶导数吸收光谱研究了双卟啉主要存在的叠合式和伸展式构象,通过红外光谱观察了对双卟啉构象和卟啉环间π-π作用较为敏感的吸收谱带;利用荧光光谱计算了双卟啉的分子内能量转移效率。     

Controlling the self-assembly of a deoxiguaninosine on mica

We report a tapping mode scanning force microscopy investigation on the growth from solutions of a lipophilic deoxiguanosine derivative on the basal plane of a muscovite mica surface. By varying the chemical composition of the substrate surface it is possible to drive the self-assembly towards either layered thin films, which are very likely to consist of guanosine quartets, or nanoribbons, comprising hydrogen bonded networks. Both these two architectures, which are peculiar to the guanine base itself, are of notable importance for the fabrication of molecular nanowires. Moreover, the first arrangement provides evidence that the guanosine is able to behave as ionophore, thus, suggesting its utilization in the development of solid-state ion selective sensors.     

On the mechanism of proton transfer in imidazole

The force fields, in-plane vibrations, and relative intensities of Raman spectra have been calculated and analyzed for the N₁H and N₃H tautomers of imidazole, imidazolium cation, and their model structures. The results obtained for the isolated state of imidazole correspond to the intramolecular mechanism of proton transfer.     

On the Rigidity of Polynorbornenes with Dipolar Pendant Groups

A range of polynorbornenes (PNBs) with fused dipolar pendant groups at C‐5,6 positions was synthesized by ring‐opening metathesis polymerization catalyzed by a ruthenium carbene complex (Grubbs I). Photophysical studies, EFISH measurements, and atomic force microscopy images have been used to investigate the structures and morphology of these polymers. These results suggest that the polymers may adopt rigid rod‐like structures. The presence of the double bonds in PNBs appeared to be indispensable for the rigidity of the polymers. Interaction between unsaturated pendant groups may result in coherent alignment leading to a rod‐like structure.     

牛血清白蛋白与十二烷基硫酸钠作用的机理

利用电动势法得到了牛血清白蛋白(BSA)与十二烷基硫酸钠(SDS)相互作用的结合等温线. 通过四阶导数紫外光谱法和荧光光谱法研究了相互作用过程中芳香族氨基酸残基微环境极性的变化. 通过研究发现, 随着SDS浓度的逐渐增大, SDS在BSA上的平均结合数(v)逐渐增大, 色氨酸(Trp)残基所处微环境的极性在减弱后保持基本不变, 酪氨酸残基所处微环境的极性在明显增强后稍有减弱, 苯丙氨酸残基所处微环境的极性略有增强. 结果表明, 当v由0增大到14时, SDS主要结合在BSA的Trp-213附近并逐渐形成聚集体, 从而诱导BSA由结构域ⅡA 开始逐渐展开. 此后, SDS呈正协同作用的特点与BSA 结合, v急剧增大. 当v约为302 时, SDS在BSA上的结合基本达到饱和, BSA的构象趋于稳定.     

牛血清白蛋白与十二烷基硫酸钠作用的机理

利用电动势法得到了牛血清白蛋白(BSA)与十二烷基硫酸钠(SDS)相互作用的结合等温线. 通过四阶导数紫外光谱法和荧光光谱法研究了相互作用过程中芳香族氨基酸残基微环境极性的变化. 通过研究发现, 随着SDS浓度的逐渐增大, SDS在BSA上的平均结合数(v)逐渐增大, 色氨酸(Trp)残基所处微环境的极性在减弱后保持基本不变, 酪氨酸残基所处微环境的极性在明显增强后稍有减弱, 苯丙氨酸残基所处微环境的极性略有增强. 结果表明, 当v由0增大到14时, SDS主要结合在BSA的Trp-213附近并逐渐形成聚集体, 从而诱导BSA由结构域ⅡA 开始逐渐展开. 此后, SDS呈正协同作用的特点与BSA 结合, v急剧增大. 当v约为302 时, SDS在BSA上的结合基本达到饱和, BSA的构象趋于稳定.     

牛血清白蛋白与十二烷基硫酸钠作用的机理

利用电动势法得到了牛血清白蛋白(BSA)与十二烷基硫酸钠(SDS)相互作用的结合等温线. 通过四阶导数紫外光谱法和荧光光谱法研究了相互作用过程中芳香族氨基酸残基微环境极性的变化. 通过研究发现, 随着SDS浓度的逐渐增大, SDS在BSA上的平均结合数(v)逐渐增大, 色氨酸(Trp)残基所处微环境的极性在减弱后保持基本不变, 酪氨酸残基所处微环境的极性在明显增强后稍有减弱, 苯丙氨酸残基所处微环境的极性略有增强. 结果表明, 当v由0增大到14时, SDS主要结合在BSA的Trp-213附近并逐渐形成聚集体, 从而诱导BSA由结构域ⅡA 开始逐渐展开. 此后, SDS呈正协同作用的特点与BSA 结合, v急剧增大. 当v约为302 时, SDS在BSA上的结合基本达到饱和, BSA的构象趋于稳定.     

Catalytic wet air oxidation of oleic acid on ceria-supported platinum catalyst.effect of pH

Summary Catalytic wet air oxidation (CWAO) of oleic acid was carried out in a batch reactor on platinum supported ceria catalyst (Pt/CeO₂). Oleic acid is a water insoluble linear unsaturated fatty acid of 18 carbon atoms. To increase the homogeneity of the solution by saponification, the influence of NaOH additions in oleic acid CWAO mechanism and catalyst performances have been investigated. The oxidation of such molecule occurs by two types of mechanisms: successive carboxy-decarboxylation which leads essentially to CO₂and/or C-C bonds splitting in the alkyl chain inducing a high formation of acetic acid. With or without NaOH, the 5%Pt/CeO₂catalyst is active in the conversion of oleic acid and selective to carbon dioxide. In alkaline medium, oleic acid is initially saponified which increases the solubility of the reactant before it to be oxidized. Finally the oxidation is slightly delayed by the presence of NaOH. The catalyst characterizations show no significant difference before and after reaction.</o:p>