UV–vis and fluorescence detection by receptors based on an isophthalamide bearing a phenylethynyl group

We have successfully prepared 5-(2-phenylethynyl)isophathalilc acid as a signaling unit and the corresponding derivatives for an anion receptor 2 and a barbiturate receptor 4. Receptor 2 showed characteristic UV–vis changes and dramatic fluorescence quenching upon the addition of anions and receptor 4 showed UV–vis and an OFF-ON fluorescence changes upon the addition of dibutylbarbituric acid based on the diphenylethyne moiety.     

A superhydrophobic magnetic elastomer actuator for droplet motion control

For the fast droplet transportation on an open surface, a new magnetic elastomer with a superhydrophobic surface has been developed. Because the surface is superhydrophobic, the water droplet can easily roll off on the surface. The movement of the droplet was controlled by a deliberate local deformation of the surface of the elastomer induced by magnetic actuation. The direction and speed of the droplet motion was easily controlled by changing the surface topography using magnetic force. We also demonstrate the applicability of the devices as a new type of open‐surface digital microfluidics using a simple chemical reaction. Copyright © 2013 John Wiley & Sons, Ltd.     

Core/Shell Structured PCM Nanocapsules Obtained by Resin Fortified Emulsion Process

Phase change material (PCM, octadecane) nanocapsules were successfully prepared by resin fortified emulsion (RFE) polymerization using the alkali soluble resin (ASR) of poly(ethylene‐co‐acrylic acid) (EAA) and poly(styrene‐co‐acrylic acid) (SAA). Stable PCM nanocapsules were obtained by resin fortified emulsion polymerization, which could be attributed to the prevention of Ostwald ripening due to PCM being hydrophobic. Analysis of online FTIR measurements throughout the reaction confirmed that the nanocapsules contained octadecane as a PCM. TEM imaging of the PCM nanocapsules showed spherical and core/shell morphology. The characteristics of PCM nanocapsules can be controlled by process parameters. As a result, the particle size and particle size distribution (i.e., polydispersity index (Dw/Dn)) of the PCM nanocapsules were created by adjusting manufacturing conditions. The PCM nanocapsules exhibited thermal energy storage (～49.8 J/g) and release (～47.9 J/g) behavior.     

反应温度对加氢残渣油四组分含量和结构的影响

以沙轻减渣为原料,在高压釜内研究了不同反应温度下加氢反应前后渣油的四组分含量及其结构组成变化。结果表明,加氢残渣油中的饱和分含量明显增加,而芳香分和胶质的含量均降低,四组分含量随反应温度的升高均呈现规律性变化。加氢后四组分的H/C摩尔比和平均相对分子质量均降低,芳碳分率增加。随反应温度升高,四组分的H/C摩尔比和平均相对分子质量降低,烷基碳分率降低;芳香分、胶质和沥青质的芳碳分率增加;胶质和沥青质的总环数和芳环数均降低。渣油加氢过程中四组分都发生了明显的氢解和脱烷基反应。加氢反应中,胶质和沥青质结构单元间的各种桥键可发生明显地断裂,导致其结构单元数减少,且结构单元数随反应温度的升高而减少。     

Li+掺杂对Y2SiO5:Pr3+上转换发光性能影响

采用溶胶-凝胶法制备Li+掺杂改性的Y2SiO5:Pr3+上转换发光材料,考察了Li+掺杂对样品晶型及发光性能的影响。采用XRD,DSC-TGA,FS对所制备的材料进行表征,结果表明Li+掺入浓度在7%～8%(摩尔分数)之间会引起Y2SiO5晶体类型由X1型转变为X2型,且Li+掺入后样品转晶型温度由950℃降至800℃;样品经800℃煅烧处理后以X1型Y2SiO5为主相,850℃煅烧处理后以X2型Y2SiO5为主相;Li+掺入同时会提高Y2SiO5:Pr3+材料的上转换发光强度,Li+最佳掺杂浓度为10%,对于双掺杂Pr3+,Li+:Y2SiO5体系中Pr3+最佳掺杂浓度为1.2%。     

Estimation of rating classes and default probabilities in credit risk models with dependencies

Let Y = m(X) + ε be a regression model with a dichotomous output Y and a one‐step regression function m . In the literature, estimators for the three parameters of m , that is, the breakpoint θ and the levels a and b , are proposed for independent and identically distributed (i.i.d.) observations. We show that these standard estimators also work in a non‐i.i.d. framework, that is, that they are strongly consistent under mild conditions. For that purpose, we use a linear one‐factor model for the input X and a Bernoulli mixture model for the output Y . The estimators for the split point and the risk levels are applied to a problem arising in credit rating systems. In particular, we divide the range of individuals' creditworthiness into two groups. The first group has a higher probability of default and the second group has a lower one. We also stress connections between the standard estimator for the cutoff θ and concepts prevalent in credit risk modeling, for example, receiver operating characteristic. Copyright © 2014 John Wiley & Sons, Ltd.     

Use of the Bell–Evans–Polanyi Principle to predict regioselectivity of nucleophilic aromatic photosubstitution reactions

Regioselectivity of nucleophilic aromatic photosubstitution has been shown experimentally to depend upon activation energies of the competing transition states. Computational means of determining relative activation energies were sought, therefore, in order to predict regioselectivity. Optimization of the three triplet transition states of 2-chloro-4-nitroanisole with hydroxide ion gave energies of insufficient accuracy to predict regioselectivity. Computed enthalpy changes from the first triplet transition state to the triplet σ-complexes correlated precisely with the experimental activation energies. This exemplifies the Bell–Evans–Polanyi Principle, and it provides an accurate means of assessing regioselectivity.     

碱性电解液中K3[Fe(CN)6]在锌阳极上的自发还原和吸附延长锌镍电池的循环寿命

采用K₃[Fe(CN)₆]作为锌镍电池的电解液添加剂,克服了锌阳极的变形。此外,通过一系列实验设计和表征,探索了电解液中金属锌与K₃[Fe(CN)₆]的反应机理。通过XRD (X-ray diffraction)和XPS (X-ray photo-electron spectroscopy)测试,我们发现金属锌在KOH水溶液中能够与K₃[Fe(CN)₆]反应,将[Fe(CN)₆]^3–还原为[Fe(CN)₆]⁴⁻。添加K₃[Fe(CN)₆]的锌镍电池实现了更长的循环寿命,比不添加K₃[Fe(CN)₆]的锌镍电池长3倍以上。在相同循环次数下,改性电解质中锌阳极循环不仅形状变化较小,而且没有出现“死”锌现象,电极添加剂和粘结剂也没有发生偏析。此外,不同于一般的有机添加剂,K₃[Fe(CN)₆]的加入不仅不会增大电极的极化,还能够提高锌镍电池的放电容量和倍率性能。因此,考虑到这一改性策略有着较高的可行性和较低的成本,K₃[Fe(CN)₆]添加剂在锌镍电池的实际应用中具有极大的推广潜力。     

基于快速热释放功能的相变偶氮苯/织物复合材料

针对偶氮基光敏分子存在放热速率慢和温度难以控制的难点,在分子结构设计基础上,采用氧化偶合法制备了具有固-液相变功能的4,4′-对-二正己基偶氮苯(AZO-L6).由于分子间作用力较低,偶氮苯分子呈现低熔、快异构化的特点,在发生反-顺异构化转变时大幅降低分子的熔点.固-液相变过程实现了光热能和相变焓的存储,在结构回复时同时放出储存的能量(231.8 kJ/kg),并将相变偶氮苯应用于可穿戴聚合物复合织物中.结果显示储能后的相变偶氮苯分子在蓝光(440 nm)刺激下在60 s内可将材料温度提升0.8℃,获得了具有自加热功能的可穿戴复合织物,为探索多功能自保温可穿戴装置提供了研究思路.     

应用于相变存储器的Cu-Ge3Sb2Te5薄膜的结构及相变特性研究

采用磁控溅射法制备了不同Cu含量的Cu-Ge₃Sb₂Te₅薄膜, 原位测试了薄膜电阻与温度的关系, 并利用X射线衍射仪、透射电镜、透过和拉曼光谱仪分别研究了 Cu-Ge₃Sb₂Te₅薄膜的晶体结构、微结构、禁带宽度及成键情况. 结果表明, Cu-Ge₃Sb₂Te₅薄膜的结晶温度和结晶活化能随着Cu含量的增加而增大, Cu的加入有效改善Ge₃Sb₂Te₅薄膜的热稳定性和10年数据保持力. 随着Cu含量的增加, 非晶态Cu-Ge₃Sb₂Te₅薄膜的禁带宽度逐渐减小. 同时, 拉曼峰从129 cm^-1向127 cm^-1处移动, 这是由于Cu–Te极性键振动增强的缘故. Cu-Ge₃Sb₂Te₅结晶为均匀、相互嵌套的六方Cu₂Te和Ge₂Sb₂Te₅相.