载流子迁移率对单层有机发光二极管复合效率的影响

建立了在单层有机发光二极管中电场强度不太大(E≤104Vcm)的情况下,载流子注入、传输和复合的理论模型.通过求解非线性Painleve方程得出了电场强度随坐标变化的解析函数关系式以及电流密度随电压变化关系,给出了电流密度以及器件的复合效率在不同的载流子迁移率情况下随电压变化关系图像.结果表明,复合效率受载流子迁移率影响较大,在器件中多数载流子应具有较低的迁移率,而少数载流子应具有较高的迁移率,这样有利于载流子的注入和传输,从而可提高发光效率.并且得出当空穴迁移率大于电子迁移率时,复合区域偏向阴极,反之亦 关键词： 单层有机发光二极管 复合效率 迁移率     

环境中有机磷污染物碱性的理论研究

有机膦化合物的碱度对深入了解有机膦类污染物的降解有着重要的意义. 发展基于第一性原理的理论方法精确计算有机膦化合物的pKa值有重要意义. 本研究工作发展了精确计算有机膦阳离子化合物pKa值的方法: 用B3LYP/6- 31＋G(d)优化气相结构, PBEPBE计算单点能量, IEFPCM/Bondi (f＝1.0)计算溶剂化能. 理论值与实验值比较, 其平均偏差和均方根差分别为－0.6 pKa单位和0.7 pKa单位. 基于此方法, 我们研究了常见有机膦污染物阳离子的碱性, 定量计算其pKa值. 并进一步讨论了这类化合物的α取代效应和远程取代效应对其碱性的影响, 总结了影响杂环有机膦化合物阳离子酸性的因素.     

羧甲基壳聚糖衍生物及其振动光谱的理论研究

用量子化学从头算STO 3G法研究了羧甲基壳聚糖及其衍生物的结构和稳定性，计算结果表明:1)壳聚糖单体经羧甲基化后，得到2种可能的产物，其中羧甲基在壳聚糖单体2位氨基上的取代产物较6位羟基上的取代产物稳定； 2)以羧甲基壳聚糖为母体经加成反应，得到羧甲基壳聚糖衍生物（2 羟基 3 丁氧基）丙基 羧甲基壳聚糖的2个异构体， 其中构型1更稳定.在优化构型的基础上，计算所得的构型1的振动光谱与实验结果相吻合.     

基于水分散纳米无定形水杨酸甲酯铽配合物的三价铬离子高灵敏荧光传感器

为扩大稀土荧光配合物的应用范围,满足水溶液中微量铬的高灵敏高选择性探测要求,制备了一种基于水分散纳米无定形水杨酸甲酯铽配合物(A-MS-Tb)的高灵敏三价铬离子荧光传感器。结果表明:在水溶液中直接反应合成的配合物A-MS-Tb为无定形的纳米沉淀,其粒子尺度在50～100 nm之间,具有与报道的配合物晶体类似的组成。该配合物在494、549、591和625 nm处呈现出强的荧光发射,归属于铽离子的5D4→7FJ(J=6,5,4,3)能级跃迁。A-MS-Tb与晶体配合物的显著差别在于其在水中的悬浮稳定性和荧光稳定性更好,这对于其作为荧光材料和离子传感器非常重要。尤其突出的是,当将三价铬离子加入到它的水悬浮溶液中后,会减弱配体与铽离子之间的配位作用,导致其绿色荧光被淬灭。据此,构建了一种高灵敏测定溶液中铬离子浓度的荧光探针,并对其分析的选择性、灵敏度和抗干扰能力进行了评价。     

部分可解释机器学习方法的高光谱人参产地识别和分析

人参是传统中药材中的贵重品种,具有较高的经济价值.人参生长的地域性很强,不同产地人参有效成分含量存在差异,人参因"道地"与否,会导致其质量、医学效用和经济价值的差异,因此人参产地识别的意义重大.目前常通过磨粉提取等制备,再采用化学或光学等多种手段检验人参产地,但会造成样本破坏.而基于外观性状或芦头特征的鉴别,因主观性差...     

聚β-羟基丁酸酯接枝顺丁烯二酸酐的研究

接枝共聚反应;聚β-羟基丁酸酯接枝顺丁烯二酸酐的研究     

Rational Molecular Design towards Vis/NIR Absorption and Fluorescence by using Pyrrolopyrrole aza‐BODIPY and its Highly Conjugated Structures for Organic Photovoltaics

Pyrrolopyrrole aza‐BODIPY (PPAB) developed in our recent study from diketopyrrolopyrrole by titanium tetrachloride‐mediated Schiff‐base formation reaction with heteroaromatic amines is a highly potential chromophore due to its intense absorption and fluorescence in the visible region and high fluorescence quantum yield, which is greater than 0.8. To control the absorption and fluorescence of PPAB, particularly in the near‐infrared (NIR) region, further molecular design was performed using DFT calculations. This results in the postulation that the HOMO–LUMO gap of PPAB is perturbed by the heteroaromatic moieties and the aryl‐substituents. Based on this molecular design, a series of new PPAB molecules was synthesized, in which the largest redshifts of the absorption and fluorescence maxima up to 803 and 850 nm, respectively, were achieved for a PPAB consisting of benzothiazole rings and terthienyl substituents. In contrast to the sharp absorption of PPAB, a PPAB dimer, which was prepared by a cross‐coupling reaction of PPAB monomers, exhibited panchromatic absorption across the UV/Vis/NIR regions. With this series of PPAB chromophores in hand, a potential application of PPAB as an optoelectronic material was investigated. After identifying a suitable PPAB molecule for application in organic photovoltaic cells based on evaluation using time‐resolved microwave conductivity measurements, a maximized power conversion efficiency of 1.27 % was achieved.     

Dual‐signal amplification strategy for ultrasensitive chemiluminescence detection of PDGF–BB in capillary electrophoresis

Many efforts have been made toward the achievement of high sensitivity in capillary electrophoresis coupled with chemiluminescence detection (CE‐CL). This work describes a novel dual‐signal amplification strategy for highly specific and ultrasensitive CL detection of human platelet‐derived growth factor–BB (PDGF–BB) using both aptamer and horseradish peroxidase (HRP) modified gold nanoparticles (HRP–AuNPs–aptamer) as nanoprobes in CE. Both AuNPs and HRP in the nanoprobes could amplify the CL signals in the luminol–H₂O₂ CL system, owing to the excellent catalytic behavior of AuNPs and HRP in the CL system. Meanwhile, the high affinity of aptamer modified on the AuNPs allows detection with high specificity. As proof‐of‐concept, the proposed method was employed to quantify the concentration of PDGF–BB from 0.50 to 250 fm with a detection limit of 0.21 fm. The applicability of the assay was further demonstrated in the analysis of PDGF–BB in human serum samples with acceptable accuracy and reliability. The result of this study exhibits distinct advantages, such as high sensitivity, good specificity, simplicity, and very small sample consumption. The good performances of the proposed strategy provide a powerful avenue for ultrasensitive detection of rare proteins in biological sample, showing great promise in biochemical analysis. Copyright © 2015 John Wiley & Sons, Ltd.     

DFT mechanistic study of the H2‐assisted chain transfer copolymerization of propylene and p‐methylstyrene catalyzed by zirconocene complex

DFT computations have been performed to investigate the mechanism of H₂‐assisted chain transfer strategy to functionalize polypropylene via Zr‐catalyzed copolymerization of propylene and p‐methylstyrene (pMS). The study unveils the following: (i) propylene prefers 1,2‐insertion over 2,1‐insertion both kinetically and thermodynamically, explaining the observed 1,2‐insertion regioselectivity for propylene insertion. (ii) The 2,1‐inserion of pMS is kinetically less favorable but thermodynamically more favorable than 1,2‐insertion. The observation of 2,1‐insertion pMS at the end of polymer chain is due to thermodynamic control and that the barrier difference between the two insertion modes become smaller as the chain length becomes longer. (iii) The pMS insertion results in much higher barriers for subsequent either propylene or pMS insertion, which causes deactivation of the catalytic system. (iv) Small H₂ can react with the deactivated [Zr]?pMS?PP_n facilely, which displace functionalized pMS?PP_n chain and regenerate [Zr]? H active catalyst to continue copolymerization. The effects of counterions are also discussed. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 576–585     

HgMnTe磁性二维电子气自旋-轨道和交换相互作用研究

通过分析不同温度下HgMnTe磁性二维电子气Shubnikov-de Hass（SdH）振荡的拍频现象，研究了量子阱中电子自旋 轨道相互作用和spd交换相互作用.结果表明：（1）在零磁场下，电子的自旋 轨道相互作用导致电子发生零场自旋分裂；（2）在弱磁场下，电子的自旋-轨道相互作用占主导地位，并受Landau分裂和Zeeman分裂的影响，电子的自旋分裂随磁场增加而减小；（3）在高磁场下，电子的spd交换相互作用达到饱和，电子的自旋分裂主要表现为Zeeman分裂.实验证明了当电子的Zeeman分裂能量与零场 关键词： 磁性二维电子气 Zeeman分裂 Rashba自旋分裂