Extraordinary radical scavengers: 4-mercaptostilbenes

In the past decade, there was a great deal of interest and excitement in developing more active antioxidants and cancer chemoprevention agents than resveratrol, a naturally occurring stilbene. In this work, eight resveratrol-directed 4-mercaptostilbenes were constructed based on the inspiration that thiophenol should be a stronger radical scavenger than phenol, and their reaction rates with galvinoxyl (GO(.)) and 2,2-diphenyl-1-picrylhydrazyl (DPPH(.)) radicals in methanol and ethyl acetate were measured by using stopped-flow UV/Vis spectroscopy at 25?°C. Kinetic analysis demonstrates that 4-mercaptostilbenes are extraordinary radical scavengers, and the substitution of the 4-SH group for the 4-OH group in the stilbene scaffold is an important strategy to improve the radical-scavenging activity of resveratrol. Surprisingly, in methanol, some of the 4-mercaptostilbenes are 10(4)-times more active than resveratrol, dozens of times to hundreds of times more effective than known antioxidants (α-tocopherol, ascorbic acid, quercetin, and trolox). The detailed radical-scavenging mechanisms were discussed based on acidified-kinetic analysis. Addition of acetic acid remarkably reduced the GO(.) and DPPH(.) radical-scavenging rates of the 4-mercaptostilbenes in methanol, a solvent that supports ionization, suggesting that the reactions proceed mainly through a sequential proton loss electron transfer mechanism. In contrast, an interesting acid-promoted kinetics was observed for the reactions of the 4-mercaptostilbenes with DPPH(.) in ethyl acetate, a solvent that weakly supports ionization. The increased ratio in rates is closely correlated with the electron-rich environment in the molecules, suggesting that the acceleration could benefit from the contribution of the electron transfer from the 4-mercaptostilbenes and DPPH(.). However, the addition of acetic acid had no influence on the GO(.)-scavenging rates of the 4-mercaptostilbenes in ethyl acetate, due to the occurrence of the direct hydrogen atom transfer. Our results show that the radical-scavenging activity and mechanisms of 4-mercaptostilbenes depends significantly on the molecular structure and acidity, the nature of the attacking radical, and the ionizing capacity of the solvent.     

四方和正交以及单斜相K0.5Na0.5NbO3的结构稳定性和电子结构的第一性原理研究

采用基于密度泛函理论框架下的第一性原理超原胞方法和虚晶近似方法, 在局域密度近似和广义梯度近似下, 对四方和正交以及单斜相K_0.5Na_0.5NbO₃的能量和原子结 构以及电子结构进行了系统的研究. 计算结果表明三种K_0.5Na_0.5NbO₃相的能量差别较小, 这与实验上它们之间容易发生相转化是一致的. 进一步发现单斜相的能量比四方相和正交相低, 说明单斜相结构更加稳定, 并且理论计算的结构参数与实验值符合得很好. 电子结构结果也表明单斜相的键合作用比四方相和正交相键合作用更强, 进一步说明单斜相结构更加稳定. 关键词： 铌酸钾钠 四方相 单斜相 密度泛函理论     

Interaction of quercetin with ovalbumin: Spectroscopic and molecular modeling studies

The binding of quercetin (QCT) to ovalbumin (OVA) in aqueous solution was investigated by molecular spectroscopy and modeling at pH 7.4. The fluorescence, synchronous fluorescence and UV-absorption spectroscopies were employed to study the mode and the mechanism for this interaction. QCT binding is characterized by one high affinity binding site with the association constants of the order of 10⁵. The distance between donor (OVA) and acceptor (QCT) was estimated according to Forster's theory of non-radiation energy transfer. Molecular docking showed that the QCT can bind to the active site of OVA. The binding dynamics was expounded by thermodynamic parameters, molecular modeling and accessible surface area calculation, which entails that hydrophobic interactions, hydrogen bonding and electrostatic forces stabilizes the interaction.     

一维铁磁链中量子孤波的能级和磁矩

使用Hartree近似和一种简化的准离散多标度方法,研究了具有交换作用和经典磁矩相互作用的一维铁磁链中的量子孤波解. 这种一维铁磁链中不仅存在着运动的量子孤波,也存在着静态的量子孤波(即量子内禀局域模).利用所获得的量子孤波解,进一步研究了量子孤波的能级和由量子孤波所携带的磁矩. 研究表明,量子孤波的能量和磁矩都是量子化的,这些结果为正确理解磁性材料中像磁滞回线的量子台阶等宏观量子特性提供了一条可能的途径.     

Local Heating Effect of Flow Past a Circular Cylinder

Heating effects of air flows past a two-dimensional circular cylinder at low Reynolds numbers and low Mach numbers are investigated by numerical simulation. The cylinder wall is heated partially rather than heated on the whole surface as with previous researches. The heating effects are completely different for various heating locations on the cylinder surface. Heating either windward or leeward side stabilizes the flow and reduces or completely suppresses vortex shedding from the cylinder at supercritical Reynolds numbers, which is consistent with previous results of heating on the whole surface of the cylinder. However, as the lateral sides of the cylinder （perpendicular to the stream-wise direction） are heated, an adverse effect is found for the first time in that the flow is destabilized and vortex shedding can be excited at subcritical Reynolds numbers. As the lateral sides of the cylinder are cooled, the flow is stabilized.     

多晶铂电极表面硫吸附物种的原位表面增强拉曼光谱研究(英文)

本工作首次报道了在酸性或碱性电解质中高粗糙度多晶铂电极表面硫物种的吸附、电氧化过程的原位表面增强拉曼光谱研究.分别在两种情况下采集了粗糙铂电极的表面增强拉曼光谱:(a)循环伏安处理后控制一定电位(0.2V)下;(b)逐步控制不同电位.酸性电解质条件下,两种情况均观察到位于300cm-1的Pt—S振动.Pt—S键较强,阻止了氢在铂电极表面的吸附,需多次循环伏安处理才能完全将表面吸附的硫去除.同时还观察到位于470cm-1处的少量多聚S物种(S8或者其他类型).这些多聚S物种仅仅微弱地键合在铂电极的表面,可以容易地除去.在碱性电解质中,同样也在(a)和(b)情况下观察到位于310cm-1的Pt—S振动吸收.本工作了获得了有关硫在粗糙多晶铂电极表面吸附和电氧化重要信息,证明了原位表面增强拉曼光谱在研究铂表面的适用性.     

CdS/ZnO异质结构材料的光生电荷性质

本文制备了CdS/ZnO异质结构材料, 并以此为模型体系, 利用表面光伏技术研究了其光电性质, 结果表明, 利用表面光伏相位谱和瞬态光伏技术可以更进一步了解异质界面的光生电荷行为.     

偏振光作用下金红石型TiO2单晶(001)面的表面光电压谱研究

TiO2是一种优异的光电功能材料,被广泛用于有机污染物光降解及太阳能光电转换[1～3].近年来的研究表明,表面原子排布对TiO2光电效能有决定性的影响.如Lowckamp[3]的研究表明,TiO2的(101)晶面与其它晶面相比具有高的光化学还原Ag+的能力.本文结合偏振光技术与表面光电压谱技术对金红石型TiO2单晶(001)面的光伏响应特性进行了研究,通过对TiO2不同晶面的电子跃迁形式的区分及其对偏振光的不同响应,揭示了表面原子排布与TiO2光电性质之间的关系,实现了对材料功能特性的调控.     

取代基对偶氮类颜料光伏特性的影响

偶氮类材料由于其具有成本低、来源丰富、易于加工以及可以通过接不同性质的取代基得到不同性能的光电导体等优点 ,作为光接受器材料 ,其导电类型、光生电荷及传输过程以及光照后表面电荷的种类在静电复印、激光打印中起着决定性的作用 [1～ 3] .由于取代基会影响偶氮类材料的费米能级 (电子填充水平 ) ,从而影响其导电类型 .如何判断其导电类型以及光照后表面电荷的种类还是一个难题 .本文首次利用 SPS(表面光电压谱 )和 FISPS(场诱导表面光电压谱 )技术对几种具有不同取代基的双偶氮类有机颜料的光伏特性进行了研究 ,发现取代基对它们…     

TiO2纳米粒子包覆聚苯乙烯球的结晶性能与表面光电压特性

TiO2具有很高的光催化活性，同时TiO2纳米粒子具有耐酸碱和耐光化学腐蚀、低成本、无毒等性质，在许多领域引起广泛关注．据报道，TiO2的锐钛矿晶型比金红石晶型具有更好的光催化活性．由于金红石是TiO2的热力学稳定相，而锐钛矿是亚稳相，通常锐钛矿相在550-800℃温度范围内形成金红石相，从而降低其催化活性，限制了其应用．