八元瓜环与1,7-二(2-苯并咪唑)-庚烷的超分子自组装

以氯化1,7-二（2-苯并咪唑）-庚烷（SBHt）为客体,八元瓜环（Q[8]）为主体,利用¹H NMR技术、动态光散射实验、荧光发射光谱、紫外吸收光谱详细探索了其在溶液中的相互作用、超分子自组装过程及作用模式. 首先考察了八元瓜环对客体pKa的影响,确定了研究主客体相互作用的条件,并详细探索了主客体的超分子自组装过程及作用模式. 主体Q[8]与客体SBHt相互作用的¹H NMR谱图表明,主客体相互作用自组装形成1：1超分子聚合物. 这一推断得到动态光散射实验、紫外吸收光谱、荧光发射光谱测定结果的证实,并通过紫外吸收光谱、荧光发射光谱确定其表观稳定常数分别为2.79×10⁵ L/mol及2.48×10⁵ L/mol. 而晶体结构测定表明主体Q[8]与客体SBHt自组装形成1：2的简单包结配合物. 导致Q[8]与SBHt在溶液中和固体状态下形成不同自组装结构可能源于瓜环的外壁作用与包结作用竞争所致.     

多路段元胞自动机交通流模型

在经典单路段元胞自动机交通流模型的基础上,将多个路段视为一个道路系统,提出并研究了多路段条件下的交通流问题.针对多路段道路的特点,通过引入车辆流入规则、路口随机慢化规则和路口车辆流入规则,控制车辆从上一路段流入下一路段.首先提出了"汽车池"的概念,来控制每一路口车辆的流入;然后通过路口随机慢化,来模拟路口对交通的影响;最后,当车辆离开时,依直行率进入下一路段,实现车流的继续流动.同时,通过数值模拟,仿真了不同条件下的交通情况,对重要参数进行了研究.结果表明,出现了混合流这一新的现象,拥堵地段与非拥堵地段间存在明显的界限.拥堵往往最先从路口开始,然后蔓延到整个路段.多路段道路还存在临界突变的特性.随着车辆流入概率的增大,路口对平均速度和车流密度的影响愈加明显.当流入概率超过一定阈值时,车辆缓慢地增加也会引起整体道路通行能力的迅速下降.     

TC21钛合金显微组织对超长寿命疲劳行为的影响

本文主要研究钛合金的网篮尺寸对于超声疲劳行为的影响。研究发现,对于TC21钛合金,高应力下疲劳裂纹萌生于试样表面;低应力下疲劳裂纹萌生于试样亚表面。最大应力-循环次数(S-N)曲线显示,在两段连续下降的曲线之间有一个表面萌生向内部萌生的转变平台。对于网篮尺寸为60μm的钛合金,转变平台对应的应力幅为540MPa,疲劳极限为430MPa。网篮尺寸为40μm的转变平台应力幅为600MPa,疲劳极限为530MPa。分析得知网篮尺寸为60μm的TC21钛合金疲劳性能低于网篮尺寸为40μm的TC21钛合金。     

半晶态聚合物拉伸变形的微观机理

应用大规模分子动力学方法,采用粗粒化聚乙烯醇模型,模拟了晶区与非晶区随机交杂的半晶态聚合物模型系统,研究了半晶态聚合物在单轴拉伸变形过程中的应力-应变行为和微观结构演变.应力-应变曲线表现出4个典型变形阶段:弹性变形、屈服、应变软化和应变强化.在拉伸变形过程中,主要存在晶区折叠链之间的滑移、晶区破坏、非晶区的解缠结,以及分子链沿拉伸方向重新取向等4种主要的微结构演变形式.在屈服点附近,晶区分子链之间排列紧密程度减小而发生滑移,之后晶区变化需要的应力变小,从而形成应变软化现象.随着应变的增大,经各分子链段协同作用使非晶区分子链的解缠结和重新取向行为扩展到相对宏观尺度,导致拉伸应力增大而形成应变强化现象.      

Electrochemical investigation of the interaction of 2,4-D and double stranded DNA using pencil graphite electrodes

2,4-dichlorophenoxyacetic acid (2,4-D) is an auxinic herbicide used to control broadleaf weeds. It is also a threatening factor for not only aquatic life but also human health due to its genotoxicity and endocrine disruptive property. Herein, the interaction between 2,4-D and double stranded DNA was investigated by using single-use pencil graphite electrodes (PGE) in combination with electrochemical techniques. The detection mechanism was based on the monitoring of the changes at the guanine oxidation signal obtained before/after surface-confined interaction of 2,4-D and DNA at the surface of PGE. The electrochemical characterization of the interaction was studied by using microscopic and electrochemical techniques. The response obtained by interaction in the presence of another herbicide, glyphosate, which is widely used with 2,4-D for weed control, was compared to the one occurred in the presence of 2,4-D. Electrochemical monitoring of the interaction between the herbicide whose active molecule was 2,4-D and DNA was also investigated. The detection (LOD) and quantification limits (LOQ) for 2,4-D and the herbicide could be obtained in the linear concentration ranges of 30–70 µg/mL and 10–30 µg/mL, respectively and LOD and LOQ values were found to be 2.85 and 9.50 µg/mL for both 2,4-D and the herbicide. The sensitivity of the biosensor was calculated as 0.087 µA.mL / µg.cm² .This is the first study in literature by means of not only voltammetric detection of 2,4-D and DNA interaction but also the herbicide-DNA interaction at the surface of PGE based on the changes at the guanine signal.     

FTIR-ATR与显微成像法结合观察NaNO3气溶胶结晶过程

阶梯状改变环境湿度, 利用FTIR-ATR(Attenuated Total Reflection)技术以及显微成像技术观察NaNO3气溶胶微粒的结晶动力学。多次实验证实NaNO3液滴在饱和点74.5%RH之后开始陆续风化, 至风化点53%RH之后结晶速率明显增快, 但并不是相对湿度越低, 结晶速率越快, 而是相对湿度的变化率越大, 结晶速率越快。对数据进行非线性拟合发现在湿度下降处结晶速率呈指数关系, 在湿度稳定時结晶速率呈线性关系。并且通过显微镜观察到尽管样品NaNO3液滴的直径在同一个数量级上, 仍能看出结晶速率与液滴半径关系紧密, 半径越大越易结晶, 结晶的相对湿度越高。     

A reliable and efficient first principles-based method for predicting pKa values. III. Adding explicit water molecules: Can the theoretical slope be reproduced and pKa values predicted more accurately?

A popular method for predicting pK(a) values for organic molecules in aqueous solution is to establish empirical linear least-squares fits between calculated deprotonation energies and known experimental pK(a) values. In virtually all such calculations, the empirically observed slope of the pK(a) vs. ΔE fit is significantly less than the theoretical value, 1/(2.303RT) (which is 0.73 mol/kcal at room temperature). In our own continuum solvation calculations (Zhang et al., J Phys Chem A 2010, 114, 432), the empirical slope for carboxylic acids was only 0.23 mol/kcal, despite the excellent fit to the experimental pK(a) values. There has been much speculation about the reason for this phenomenon. Although the ΔE - pK(a) relation neglects entropic effects, these are expected to largely cancel. The most likely cause for the strange behavior of the fitted slope is explicit solute-solvent (water) interactions, especially involving the ions, which cannot be described accurately by continuum solvation models. We used our previously developed pK(a) protocol (OLYP/6-311+G(d,p)//3-21G(d) with the COSMO solvation model) to investigate the effect of adding one or two explicit water molecules to the system. The slopes for organic acids (especially carboxylic acids) are much closer to the theoretical value when explicit water molecules are added to both the neutral molecule and the anion. However, explicit water molecules have almost no effect on the slopes for organic bases. Adding explicit water molecules to the ions only produces intermediate results. Unfortunately, linear fits involving explicit water molecules have much larger errors than with continuum solvation models alone and are also much more expensive. Consequently, they are not suitable for large-scale pK(a) calculations. The results compared with literature values showed that our predicted pK(a) s are more accurate.     

混浊介质多光子激发显微成像的快速模型

将二维点扩散函数（PSF）和蒙特卡罗方法相结合,引入了一种研究混浊介质显微成像的快速仿真模型,将该模型用于混浊介质的多光子激发（MPE）显微成像研究,极大地提高了模拟效率,与直接蒙特卡罗方法计算结果的比较证实了该方法的正确性和有效性,此外,一个计算实例说明了混混介质的多光子激发显微成像具有比共焦荧光显微成像更优的横向分辨率。     

石油基电流变液中链结构的显微观察

利用显微观察技术连续记录了直流与交流电场下石油基电流变液中的显微结构变化,比较了两种电场下成链、链生长、断链的差异,这种差异包括颗粒的运动、链的形状以及断链时有无崩裂现象,并且分析了造成这种差异的原因,认为交流场下出现的链崩裂现象是由约翰逊-拉贝克效应造成的,通过石油基电流变液在直流、20Hz、50Hz三种电场条件下显微链结构的对比,得出结论横跨两极的链总的横截面积是影响剪应力大小的一个重要因素。     

Universal properties of lamellar systems under weak shear

We have observed that different lamellar phases (thermotropic, lyotropic of surfactants or blockcopolymers) share the same rheological properties = A(T)σ^m, m = 1.67±0.1, independently of their chemical nature, in a range of shear rates , shear stresses σ, and temperatures T, where the flow is stationary. It is argued that the key phenomenon is the appearance of screw dislocations whose glide under an applied shear counterbalances plastically the applied vorticity, and stabilizes the layers, whose slip past each other is thus made more feasible. The theory, which makes use in other respects of the high-temperature creep model in solids, reproduces correctly the power law behavior and the values of A(T). Received 18 April 2001 and Received in final form 25 October 2001