侧链调控在有机光电高分子材料中的应用研究进展

有机光电聚合物材料是由共轭主链与柔性侧链组成,具有制备简单、成本低廉、重量轻及可制成柔性器件等突出优点,近年来成为国内外研究的前沿和热点.目前对聚合物材料主链结构的优化研究较多,基于侧链调控的报道则相对较少.对主链共轭高分子光电材料侧链调控的目的主要是改善材料的溶解性能,然而,侧链修饰的影响远非如此.研究发现,侧链修饰后聚合物材料的吸收光谱、能级分布、载流子迁移率、器件共混膜形貌以及界面形态等光电性能方面可发生不同程度的变化.此类研究成果无疑将对设计与优化有机聚合物材料分子结构、活性层形貌与界面形态以及器件制备方法和加工工艺具有指导意义.同时,随着器件制备方法的不断改进以及加工工艺的不断发展,为进一步改善器件效率,提高纳米活性材料的形貌调控与界面形态优化能力,基于有机光电高分子材料侧链调控的研究价值日益突显.因此,结合高分子光电材料应用领域的研究现状,以聚合物分子侧链结构优化设计为出发点,基于侧链调控为主题,以不同的修饰侧链为研究对象,对光电高分子材料侧链调控中拟解决的问题及本实验室的相关工作做主要综述.     

金纳米粒子表面能量转移法测定水中的铅离子

荧光素修饰的凝血酶适配体(5’-FAM-GGT TGG TGT GGT TGG-3’)可与Pb2+选择性地形成G-四链体,这一构象变化能改变作为能量供体的荧光染料和作为能量受体的金纳米粒子之间的距离,使体系的荧光强度与Pb2+浓度具有一定的相关性,从而建立了一种基于纳米材料表面能量转移灵敏检测水溶液中Pb2+的分析方法。研究表明,在Pb2+浓度为12.5~100 nmol/L范围内,荧光恢复效率(F/F0)与Pb2+浓度间呈良好的线性关系,线性回归方程为y=0.910+0.007c(R2=0.997),检出限为10 nmol/L。用本方法检测自来水中Pb2+,结果令人满意。     

A New Cadmium（II） Coordination Polymer Constructed by 2-（2-Chloro-6-fluorophenyl）-lH-imidazo[4,5-f] [1, 10]phenanthroline and 1,2,3-Benzenecarboxylate： Synthesis,Structure and Luminescence

A new Cd（II） coordination polymer, namely, [Cd3（1,2,3-BTC）2（L）2]·2.25H2O （1, L = 2-（2-chloro-6-fluorophenyl）-1H-imidazo[4,5-A][1,10]phenanthroline and 1,2,3-BTC = 1,2,3-ben- zenetricarboxylate）, has been synthesized under hydrothermal conditions. The compound was characterized by single-crystal X-ray diffraction. It crystallizes in triclinic, space group Pī with α = 11.650（2）, b = 12.240（2）, c = 19.760（4） A, α = 72.01（3）, β = 77.11（3）, γ = 83.48（3）°, V = 2609.4（9） A3, Z = 2, C56H31Cd3Cl2F2N8O14.25, Mr = 1489.99, Dc = 1.896 g/cm3, F（000） = 1466, μ（MoKa） = 1.401 mm^-1, R = 0.0401 and wR = 0.1104. Compound 1 shows a 1D chain structure, and the neigh- boring 1D chains of 1 are joined together by π···π interactions to result in a 2D supramolecular layer. In addition, the luminescent property of 1 has been studied in the solid state at room temperature.     

Efficient side-chain modification of dextran via base-catalyzed epoxide ring-opening and thiol-ene click chemistry in aqueous media

In this study, a novel approach by combining base-catalyzed epoxide ring-opening and thiol-ene click chemistry is presented for the side-chain modification of dextran. The vinyl-modified dextran is prepared by a basic epoxide ring opening reaction of allyl glycidyl ether in 0.1 mol/L NaOH, followed by thiol-addition click reaction of three model sulfhydryl compounds using water-soluble Irgacure 2959 as the photoinitiator, leading to side-chain functionalized dextran modified with carboxyl, bidentate dicarboxyl or amino groups. This is the first example of combining epoxide ring-opening and thiol- ene click chemistry for side-chain modification of dextran in aqueous media. Importantly, it may also be extended as a convenient and efficient method for the side-chain modification of other polysaccharides.     

Microstructure characterization of short-chain branching polyethylene with differential scanning calorimetry and successive selfnucleation/annealing thermal fractionation

A series of the copolymers of ethylene with 1-hexene(M1–M9) synthesized by metallocene catalyst Et[Ind]2ZrCl2/MAO was studied by differential scanning calorimetry and successive self-nucleation and annealing(SSA) thermal fractionation. The distribution of methylene sequence length(MSL) in the different copolymers was determined using the SSA method. The comonomer contents of samples M4 and M5 are 2.04 mol% and 2.78 mol%, respectively. Both M4 and M5 have low comonomer content and their MSL distribution profiles exhibit a monotonous increase trend with their MSL. The longest MSL of M5 is 167, and its corresponding molar percent is 43.95%, which is higher than that of M4. Moreover, the melting temperature(Tm) of M5 is also higher than that of M4. The comonomer contents of samples M7, M8, and M9 are 8.73 mol%, 14.18 mol% and 15.05 mol%, respectively. M7, M8, and M9 have high comonomer contents, and their MSL distribution profiles display unimodality. M7 has a lower peak value of 33 and a narrow MSL distribution, resulting in a Tm lower than that of M8 and M9. The MSL and its distribution are also key points that influence the melting behavior of copolymers. Sometimes, MSL and its distribution of copolymers have a greater impact on it than the total comonomer contents, which is different from traditional views.     

关于一类择优增长系统的度分布的注记

本文研究文[1]中提出的一类择优增长系统,说明文[1]中利用主方程法求解系统的平均度分布及稳态度分布是值得商榷的,然后通过考虑系统中空团体的存在的可能性,对系统进行修正,并证明空团体存在的必要性。     

应用RJMCMC方法识别线性模型异常点

传统线性模型异常点识别方法容易发生误判:正常点被归为异常点或者异常点被归为正常点.为解决此类问题,提出了应用逆跳马尔科夫蒙特卡洛方法识别异常点的思想,同时将其应用于实际数据加以检验,识别效果明显好于传统方法.     

基于出行目的链的出行生成—分布组合模型分析

目前,我国城市轨道交通客流预测大多采用交通产生、吸引、出行分布、出行方式划分四阶段模型,其中出行生成与分布是方式划分和交通分配的前提,是模型重要的组成部分.在对传统的四阶段模型的分析基础上,结合非集计模型的优点,论文提出了基于出行目的链的出行生成—分布组合模型.模型充分考虑了居民出行链、出行目的等对客流预测的影响,在完善我国轨道交通客流预测理论和方法,提高预测精度等方面具有一定的理论价值和实际意义.     

几类典型随机非线性系统的辨识

考察实际中常见的三类典型随机非线性系统(即Wiener、Hammerstein和NARX系统)的辨识,首先概述了现有的递推和非递推辨识算法,然后介绍这三类系统的一个统一辨识框架:利用系统所确定的过程的马氏性及混合型,将辨识转化为求函数零点的问题,基于扩张截尾的随机逼近算法,得到了递推、强一致的辨识结果,并给出了数值模拟验证辨识算法收敛到真值.     

RBNS的线性预测模型

传统的准备金方法都是基于聚合数据的,聚合数据是个体数据的汇总,它们丢失了许多有用信息,影响了准备金预测的准确性.本文提出了一个基于个体数据的线性预测模型,该模型不需要对数据的矩的具体形式进行假设,更不需要对数据的分布进行假设,而只需假设个体索赔数据的前两阶矩存在,具有适用范围广,简单易操作等特点.在文章的最后,通过随机模拟把提出的方法与著名的链梯法进行了对比,模拟结果显示,本文提出的方法是行之有效的.