含酞菁功能基聚苯乙烯的光电导性能研究

合成了新型含酞菁功能基聚苯乙烯，该聚合物具有优良的溶解性能和成膜能力，同时又有一定的光电导性，对该聚合物的染料增感研究发现结晶紫，孔雀绿对于该聚合物均有增感作用，较大幅度地提高了光电导性．采用ＥＳＲ和荧光光谱的研究表明，该聚合物的光电导机理可能是形成了电荷转移络合物．     

Impact of Charge Transfer Complex on the Dielectric Relaxation Processes in Poly(methyl methacrylate) Polymer

The impact of the charge transfer complex on the dielectric relaxation processes in free poly(methyl methacrylate) (PMMA) polymer sheets was investigated. The frequency dependence of dielectric properties was obtained over the frequency range 0.1 Hz–1 MHz at temperatures ranging between 303 K and 373 K for perylene dye and acceptors (picric acid (PA) and chloranilic acid (CLA)) in an in situ PMMA polymer. The TG/dTG technique was used to investigate the thermal degradation of the synthesized polymeric sheets. Additionally, the kinetic parameters have been assessed using the Coats–Redfern relation. The dielectric relaxation spectroscopy of the synthesized polymeric sheets was analyzed in terms of complex dielectric constant, dielectric loss, electrical modulus, electrical conductivity, and Cole–Cole impedance spectroscopy. α- and β-relaxation processes were detected and discussed. The σ(ω) dispersion curves of the synthesized polymeric sheets show two distinct regions with increasing frequency. The impedance data of the synthesized polymeric sheets can be represented by the equivalent circuit (parallel RC).     

酞菁聚合物薄膜的电场取向和光导性能研究

通过电场取向法成功地制备了酞菁类聚合物(PPc)有序薄膜,并采用偏振荧光和TEM技术对其取向进行了研究.分别以该PPC有序薄膜和腙类作为载流子发生层和载流子传输层制备光电导体,发现其光导性能优于不加电场制备的PPc薄膜,呈现了光导性能提高的材料结构低维化效应.     

有机光电导(OPC)材料分子设计的研究

本文在分析了有机光电导材料的分子结构, 电子分布状态以及电荷转移与光电导性能之间关系的基础上, 进行了有机光电导材料的分子设计, 并以酞菁聚合物的合成和光电导性的研究实施进行了验证。     

工作气氛和偏压对含铁聚合物杂混薄膜制备的影响

采用等离子体增强金属有机化合物化学气相沉积（ＰＥＭＯＣＶＤ）工艺，在氧化性气氛（Ｏ２）和非氧化性气氛（Ｈ２、Ａｒ）中制备了含铁聚合物杂混薄膜。探讨了工作气氛和偏压对膜密度、沉积速率及其分布的影响。     

Sensitization of Photoconductivity in Polymeric Compositions with Fe2O3 and CdS Nanoparticles by an Organic Compound with Intramolecular Charge Transfer

The electric conductivity and photoconductivity of films based on polyvinylbutyral and containing Fe₂O₃ and CdS nanoparticles and an organic compound with intramolecular charge transfer as photoconductivity sensitizer in the visible and near infrared regions were investigated. In the absorption region of the sensitizer the activation energy of the photocurrent is somewhat greater than 0.1 eV and is close to the activation energy of the electric conductivity current.     

Electrical conductivity and photoconductivity of film materials based on heteropolynuclear Cu/Cd complexes and organic polymers

We have studied the characteristic features of the electrical conductivity and photoconductivity of films of composites based on polyvinyl butyral and acrylonitrile butadiene styrene with added heteropolynuclear Cu/Cd complexes having one-dimensional and two-dimensional polymer structures and with added anthracene, epoxypropyl carbazole, and C₆₀ organofullerene molecules. Normal positive and abnormal negative effects of photoconductivity were found. Kinetic model of the photoconductivity was proposed. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 42, No. 2, pp. 107–112, March–April, 2006.     

窄带系聚合物APFO3的激发态光物理特性

化学计算证实了光致激发窄带系聚合物APFO3后,会发生链内电荷转移（ICT）过程,同时这一特性还影响了吸收光谱中的第一吸收带. 瞬态吸收结果再一次表明了当聚合物在单分散体系中确实存在ICT特性,而且这种特性会同振动弛豫竞争. 在聚集态中,受链间相互作用的影响,ICT特性会消失,而且激子弛豫过程将在光致激发后的弛豫过程中占据主导地位. 混有PC61BM的APFO3薄膜的光致激发动力学显示,当PC61BM 的含量超过50%时,激子解离已经达到饱和. 基于此异质节的光伏器件性能显示PC61BM的含量高于50％以后,光电流的增幅也很小．     

表面活性剂对共轭聚合物荧光性质及电荷转移的影响

探讨了表面活性剂存在下, 水溶性阴离子共轭聚合物聚[5-甲氧基-2-(3-磺酰化丙氧基)-1,4-苯撑乙烯](简写为MPS-PPV)的微环境变化对荧光性质及电荷转移的影响. 结果表明, 阳离子表面活性剂及非离子表面活性剂使MPS-PPV荧光增强, 阴离子表面活性剂使其荧光先增强后减弱; 在MPS-PPV/表面活性剂体系中加入电子接受体Pd^2＋, 发现非离子表面活性剂体系的荧光猝灭效率提高, 阴离子及阳离子表面活性剂体系荧光猝灭效率下降. 此研究对研制基于阴离子共聚物的新型生物化学传感器具有一定的指导意义.     

基于共轭高分子复合物能量转移的非标记DNA检测

非标记DNA检测是一种高灵敏度、高选择性的DNA检测方法, 具有重要的科学和社会意义. 本文采用交叉偶联法制备了水溶性阳离子共轭聚合物: 聚(9,9-双(6'-N,N,N-三甲胺盐-己烷基)-芴亚苯基)(PFP); 利用氧化加成聚合反应制备了水溶性阴离子共轭聚合物: 聚(3-噻吩乙酸钠)(P3TSA). 通过核磁共振氢谱(¹H NMR)、傅立叶变换红外光谱(FTIR)等对其结构进行了表征. PFP与P3TSA通过静电相互作用形成稳定的高分子复合物. 利用紫外-可见光谱(UV-vis)和荧光发射光谱证明共轭高分子复合物能够发生能量转移. 保持PFP的浓度不变, 高分子复合物能量转移效率(ETEF)随着P3TSA浓度的增加而逐渐增大. 选取ETEF较高的样品, 考察了DNA探针用量对高分子复合物ETEF的影响. 随着DNA探针浓度的增加, ETEF逐渐减弱. 最后, 利用0.2 nmol DNA探针进行了DNA杂交配对检测. 实验结果表明, 这种检测方法可以明显区分完全互补配对、双碱基错配和非完全互补配对的目标DNA. 简而言之, 我们成功发展了一种基于共轭高分子复合物能量转移、具有高选择性的非标记DNA检测方法.     

一种新型的荧光探针化合物用于研究水溶性高分子的构象问题

本工作合成了一种聚合的分子内电荷转移化合物，作为荧光探针。利用荧光探针技术来研究水溶性高聚物在水溶液中的构象变化，进一步证实了在聚甲基丙烯酸的水溶液中存在着疏水微区。     

酞菁铜与四氰代二甲基苯醌电荷转移反应的测定

用红外光谱、紫外可见光谱、循环伏安法等研究了三．（２，４－二特戊基苯氧基）－８－喹淋氧基酞菁铜（简称酞菁铜）和２－十八烷基－７，７，８，８－四氰二甲基苯醌（简称Ｃ１８－ＴＣＮＱ）在Ｌａｎｇ－ｍｕｉｒ－Ｂｌｏｄｇｅｔｔ（ＬＢ）膜中的电荷转移。实验结果表明，在交替和混合ＬＢ膜中，酞菁铜和Ｃ１８－ＴＣ－ＮＱ分子之间均发生了电荷转移，其中酞菁铜为给体分子，ＴＣＮＱ为受体分子。在混合ＬＢ膜中，电荷转移程度较大。电导率测量表明荷移反应使ＬＢ膜的电导率较纯酞菁铜ＬＢ膜提高了３个数量级。     

高分子微球在电化学领域的应用

本文综述了近几年来高分子微球在电化学领域应用的研究进展。分别介绍了电场作用下微球悬浮液反射光谱的变化,包覆导电聚合物高分子微球的振荡电流和循环伏安特征和二茂铁基高分子微球电极反应的粒径效应,并对各类微球悬浮液的电化学行为及电极反应模型进行阐述。综述表明高分子微球电化学具有广阔的应用前景。     

铜离子印迹聚合物的制备及性能研究

在乙醇溶液中,以Cu(Ⅱ)为模板分子,二甲基丙烯酸乙二醇酯为交联剂采用分散聚合法制备铜离子印迹聚合物(Cu~(2+)-IIP),并通过傅里叶变换红外光谱、紫外光谱对聚合物的结构及性能进行了表征。考察了吸附时间、溶液初始浓度、pH值等因素对聚合物吸附性能的影响。实验表明,室温条件下,在pH=6,90min吸附达到平衡,其最大吸附量为1.42mmol/g;与非印迹聚合物相比,印迹聚合物有较大的吸附量及较好的选择性。因此,印迹聚合物在固相萃取、水处理等方面具有很好的应用前景。     

Facile Synthesis of Free‐Standing Polymer Brush Films Based on a Colorless Polydopamine Thin Layer

A free‐standing polymer brush film with tailored thicknesses based on a colorless polydopamine (PDA) thin layer is prepared and characterized. The surface‐initiated atom transfer radical polymerization (ATRP) of 2‐hydroxyethyl methacrylate (HEMA) is performed on a PDA layer with thickness of ca. 6 nm, which generated an optically transparent and colorless free‐standing PHEMA brush film (1.5 cm × 1.5 cm). Because the cross‐linked PDA layer is used as the base for the polymer brushes, the reported method does not require cross‐linking the polymer brushes. The free‐standing film thicknesses of ≈16–75 nm are controlled by simply changing the ATRP reaction time. The results show that the free‐standing PHEMA brush film transferred onto a plate exhibits a relatively smooth surface and is stable in any solvent.

     

富勒烯稠合体与共轭聚合物作为有机太阳能电池材料的研究进展

介绍了有关富勒烯与共轭聚合物超快光诱导电子的研究状况和三种不同光敏层材料制备的太阳能电池的组装和性能,包括:(1)以共轭聚合物/C60或C60衍生物的主体异介质为光敏层,(2)分子水平上的主体异介质:D-A双功能聚合物,(3)单纯以富勒烯稠合体为光敏层,以及国内外这三种太阳能电池研究的进展情况及存在的问题.     

聚合物熔体膜在基体表面的润湿和铺展行为

聚合物熔体膜在基体表面上的润湿和铺展行为受铺展系数和Hamaker常数影响。对于不能在基体表面上铺展的聚合物膜,当处于其玻璃化温度以上时,聚合物熔体膜将破裂,出现非连续区域。随着体系处于聚合物玻璃化温度以上时间的延长,非连续部分尺寸不断增长,增长速率与表面张力、聚合物粘度、聚合物液滴在基体表面的平衡接触角等因素有关,平衡后聚合物以液滴的形式在基体表面稳定存在。将带功能端基聚合物加入不能在基体表面上铺展的聚合物中,通过修饰聚合物与基体界面或改变聚合物熔体膜的表面张力,可以使原来不能在基体表面铺展的聚合物保持稳定。本文综述了聚合物熔体膜的铺展和润湿动力学研究进展,并归纳了使聚合物熔体膜稳定的方法。     

表面分子印迹高分子膜修饰硅胶用于血清中茶碱的固相萃取

采用表面引发可逆加成-断裂链转移自由基聚合反应,在硅胶表面修饰了分子印迹高分子膜(MIP-silica)。以元素分析和氮吸附分析对修饰的分子印迹高分子膜进行了表征。与传统采用本体聚合合成的分子印迹高分子相比,MIP-silica具有更好的传质能力。本文合成的茶碱印迹MIP-silica可以作为选择性固相萃取材料从血清中富集、检测微量的茶碱,该法合成的MIP-silica还可用于高效液相色谱和毛细管电色谱等领域。     

Charge redistribution effect on the properties of charge transfer complexes HnR⋅XY and HnR⋅X2 (X,Y = F,Cl, Br,I; R = O,S, N,P)

Systematic studies on structures, energies, charge transfer, dipole moments, and ionic character of a series of weakly bonded charge transfer (CT) complexes (D⋅AB, D = H₂O, H₂S, NH₃, PH₃, AB = F₂, Cl₂, Br₂, I₂, BrCl, IBr, ClF, ICl, BrF, IF) have been carried out by the hybrid Hartree–Fock density functional theory (HF‐DFT) method, where those results are validated by available experimental and theoretical investigations. Employing the Hohenberg–Kohn theorem, the property of a multicomponent system is formulated with contributions from both component properties and the charge redistribution (CR) effect, which describes the electronic coupling between components. For any property of a multicomponent system, provided that the intercomponent coupling is weak enough, the first‐order approximation can be applied, which yields a linear correlation of the component contribution to the CR effect. In fact, this kind of linear relationship can be evidenced by all the studied properties including the geometry, energy, charge transfer, dipole moment, and ionic character of all 40 complexes. This approximation quantitatively describes the relative contribution of the components to a given property, which shows the same tendency in a series of complexes. Based on the investigations of the CT effect on the intermolecular bond energy and the total dipole moment, it has been found that the principal bonding character of the title complexes was ascertained to be ionic with the exception of the F₂ complexes, which agrees well with the calculated ionic character. The CT effect, though small in a quantitative aspect, is directly connected to various kinds of system properties. The effectiveness and consistency of the present type of calculations in multicomponent systems may allow their wider applications in the study of intermolecular interactions. © 2001 John Wiley & Sons, Inc. J Comput Chem 22: 327–338, 2001     

表面自由基链转移反应制备超萍聚合物膜

研究了通过自由基链转移反应原位接枝聚合物膜。所得聚合物膜经红外（FT- IR）、X射线光电子能谱（XPS）、原子力显微镜（AFM）、接触角及椭圆偏光测量 进行了表征。两种单体如苯乙烯/甲基丙烯酸甲酯共聚合时,改变单体对的组成, 可以得到不同亲水亲油性质的表面。