聚甲基丙烯酸甲酯Langmuir—Blodgett复合膜及其在光电导体中…

制备了聚甲基丙烯酸甲酯（ＰＭＭＡ）ＬＢ复合膜，将其作为阻挡层首次应用于机能分离型光电导体领域。从π－Ａ曲线发现ＰＭＭＡ单分子膜具有表面压力的各向异性和松弛特性。ＴＥＭ照片显示，ＰＭＭＡ分子链在复合膜中有序排列。转移比、ＵＶ和ＸＰＳ研究表明，复合膜沉积均匀。以ＰＭＭＡ－ＬＢ复合膜作为阻挡层的光电导体表面充电电位Ｖ０＝１５１８Ｖ，光照１ｓ后的光衰百分率△Ｖ１ｓ＝５０．１６％，半衰期ｔ１／２＝０．９３ｓ     

孔雀石绿增感聚苯乙炔的光导体

采用电位放电技术研究孔雀石绿（ＭＧ）增感顺式聚苯乙炔（ｃｔ－ＰＰＡ）光导体的光敏性，发现孔雀石绿是顺式聚苯乙炔新的有效增感剂。以Ａｌ／ｃｔ－ＰＰＡ：ＭＧ：ＰＣ（１００：５：１０）（１～１．５μｍ）／ＰＶＫ：ＴＰＡ：ＰＣ（１０：１０：１）（１５～２０μｍ）构成的光导体显示好的光敏性：表面接受电位，Ｖｍａｘ＞７００Ｖ；残余电位，Ｖｍｉｎ＜５０Ｖ；暗衰速率，ＲＤ＜１０Ｖ／ｓ；光衰放电量，△Ｖｔ＞５０％（１．０ｓ）；半衰时间，Ｔ１２＝０．８７Ｓ；感光灵敏度，Ｓ＝２．３×１０－３（１ｘ．ｓ）－１，较未增感ＰＰＡ光导体有较大的提高。ＭＧ对ＰＰＡ为光谱增感     

C60在卟啉衍生物Langmuir单层膜中的分散状态

研究了Ｃ６０在四苯基卟啉衍生物５，１０，１５，２０－四－对（癸酸α氧基）苯基卟啉（ＴＤＰＰ）及５，１０，１５，２０－四－对（乙酸α氧基）苯基卟啉（ＴＡＰＰ）单层膜中的分散状态。空气／Ｃｄ＾２＋水溶液界面上混合单层膜的π－Ａ等温线、混合膜与花生酸（ＡＡ）形成的交替多层膜的低角Ｘ射线衍射实验及混合单层ＬＢ膜的ＵＶ－Ｖｉｓ光谱表明，在ＴＤＰＰ／Ｃ６０（１：１）的混合单层膜中，Ｃ６０以单分子或（和）聚集体     

酞菁锰-表面活性剂薄膜电极的电化学表征及其对三氯乙酸的电化学催化作用的研究

将酞菁锰（ＭｎＰｃ）掺入阳离子表面活性剂双十二烷基二甲基溴化铵（ＤＤＡＢ）的氯仿溶液，并涂布于热解石墨电极表面，待氯仿挥发后即制得ＭｎＰｃ－ＤＤＡＢ薄膜电极。循环伏安实验表明，在ＫＢｒ溶液中，该薄膜电极有两对还原氧化峰，第一对峰的Ｅｐｃ１＝－０．２７Ｖ，Ｅｐａ１＝０．０１Ｖ；第二对峰的Ｅｐｃ２＝－０．７６Ｖ，Ｅｐａ２＝－０．６２Ｖ（ｖｓ．ＳＣＥ）。本文着重探讨了第二对峰的电化学行为，估计了该体系的电荷传递扩散系数Ｄｃｔ和表观非均相电极反应速率常数Ｋ０′等电化学参数，并可将该薄膜电极用于催化三氯乙酸的电化学还原。     

新型大溶性大π共轭高分子—聚吡咯—{2,5—[双（对二甲氨基苯甲烯）]}？…

该研究合成了一种新型水溶性大π共轭高分子－聚吡咯－｛２,５－〔二（对二甲氨基苯甲烯）〕｝（ＰＰＤＭＡＢ）,它地强酸的水溶液,在１ｍｏｌ／Ｌ的盐酸中溶解度为０．５～１．０g／１００mＬ,通过ＥＡ、ＸＰＳ、ＦＴ－ＩＲ、ＵＶ－Ｖｉｓ－ＮＩＲ、Ｉｎ－ｓｉｔｕＵＶ－Ｖｉｓ－ＮＩＲ对ＰＰＤＭＡＢ进行了结构表征。通过质子化、碘掺杂、浓硫酸（９８％）掺杂等处理,ＰＰＤＭＡＢ的电导率提高２～４个数量组（＆＝１－＾－７     

乙烯基聚硅氧烷共聚反应竞聚率的测定及其对复合粒子形态的影响

用Ｆｉｍｅｍａｎ－Ｒｏｓｓ法处理数据，测定了乙烯基聚硅氧烷（ＳＶ）与苯乙烯（ＳＴ）、甲基丙烯酸甲酯（ＭＭＡ）和甲基丙烯酸正丁酯（ｎ－ＢＭＡ）的共聚反应的竞聚率，结果为ｒＳＴ＝１．４５和ｒＳＶ＝１．０８，ｒＭＭＡ＝０．７８和ｒＳＶ＝２．０１，ｒｎ－ＢＭＡ＝０．４６和ｒＳＶ＝３．４９．以含ＳＶ的乳液作为种子进行烯类单体的乳液聚合，单体和ＳＶ共聚反应对复合粒子的形态有很大影响。     

新型水溶性大π共轭高分子——聚吡咯｛2,5-[双(对二甲氨基苯甲烯)]｝的合成

该研究合成了一种新型水溶性大π共轭高分子———聚吡咯 ｛２ ,５ ［ 二（ 对二甲氨基苯甲烯）］｝（ＰＰＤＭＡＢ） ,它能溶于强酸的水溶液,在１ｍｏｌ／Ｌ 的盐酸中溶解度为０－５ ～１－０ｇ／１００ｍＬ．通过ＥＡ、ＸＰＳ、ＦＴ ＩＲ、ＵＶ Ｖｉｓ ＮＩＲ、Ｉｎ ｓｉｔｕ ＵＶ Ｖｉｓ ＮＩＲ 对ＰＰＤＭＡＢ进行了结构表征．通过质子化、碘掺杂、浓硫酸（９８ ％ ） 掺杂等处理,ＰＰＤＭＡＢ的电导率提高２～４ 个数量级（δ＝ １０ － ７ ～１０－ ５Ｓ／ｃｍ） ．在质子化、去质子化的过程中ＰＰＤＭＡＢ发生了可逆的颜色变化,本征态（ 综色） 质子态（ 墨兰色） ．     

抗癌药物博莱霉素伏安行为及其反应机理研究

博莱霉素（ＢＬＥＯ）Ａ５在０．０５ｍｏｌ／Ｌ Ｈ２ＳＯ４溶液中出现两个还原波，峰电位分别为ＥＰ１＝－０．８３Ｖ和ＥＰ２＝－１．０９Ｖ（ｖｓ．，Ａｇ／ＡｇＣｌ）。用线性扫描与循环伏安法、恒电位库仑法、脉冲极谱、交流极谱等手段研究体系的伏安行为及反应机理。实验表明，Ｐ１为ＢＬＥＯＡ５分子中嘧啶环第一步两电子还原的吸附波，Ｐ２为嘧啶环第二、三步还原和催化氢还原的具有吸附性的重叠波。     

聚酰胺修饰碳糊电极测定槲皮素的研究

用聚酰胺修饰碳糊电极在ｐＨ３６０的Ｂｒｉｔｏｎ－Ｒｏｂｉｎｓｏｎ缓冲溶液中，将槲皮素开路富集一定时间后，从０４５Ｖ（ｖｓ．Ａｇ／ＡｇＣｌ）向阴极化扫描至－０５５Ｖ获得Ｉ－Ｅ曲线。槲皮素的峰电位为０１８Ｖ。峰电流与槲皮素浓度在１０～４００μｍｏｌ／Ｌ范围内呈良好的线性关系。所拟定方法用于芦丁水解产物测定，结果满意。     

吸附络合物体系的示波分析

Ｉｎ（Ⅲ）在ｐＨ４５７ＨＡｃＮａＡｃ０．１％ＶＣ０．０６％ＨＣｕＰ溶液中，用示波计时电位法可获得良好示波图，其切口电位为Ｅ＝０９０（Ｖｓ．ＳＣＥ），切口高度与Ｉｎ（Ⅲ）浓度在８００×１０－７～１４×１０－５ｍｏｌ／Ｌ范围内成正比，检出限可达５０×１０－７ｍｏｌ／Ｌ吸附络合物组成为Ｉｎ（Ⅲ）：铜铁试剂（ＨＣｕｐ）＝１∶１，条件稳定常数为５９×１０３     

聚甲基丙烯酸甲酯Langmuir-Blodgett复合膜及其在光电导体中的应用

制备了聚甲基丙烯酸甲酯(PMMA)LB复合膜,将其作为阻挡层首次应用于机能分离型光电导体领域。从π-A曲线发现PMMA单分子膜具有表面压力的各向异性和松弛特性。TEM照片显示,PMMA分子链在复合膜中有序排列。转移比、UV和XPS研究表明,复合膜沉积均匀。以PMMA-LB复合膜作为阻挡层的光电导体表面充电电位V₀=1518V,光照1s后的光衰百分率△V_1a=50.16%,半衰期t_1/2=0.93s.     

适合倍频光波导的多层LB膜结构研究

制备非中心对称的NMOB/CdA交替Y型累积LB膜,测量了它的二阶非线性光学特性.为了改善多层膜的有序性,研究在拉制NMOB/CdA多层膜时提高膜均匀性的两种方法,增强了它的二阶非线性光学特性.最后,制备光栅耦合的NMOB/CdA多层膜光波导,测量了它的Cerenkov相位匹配光学二次谐波产生.     

用三硝基芴酮高浓度掺杂树脂做电荷传输层的正充电有机光导体

本研究采用三硝基芴酮(TNF)高浓度掺杂的高分子树脂作为电荷传输层(CTL)、ε-CuPc的高分子分散体系作为电荷产生层(CGL)制作了电子传输型正充电有机光导体。TNF质量分数为10～50%的高分子树脂薄膜在80℃下干燥8h,再在常温下保存近半年仍然处于完全透明状态,表明该掺杂体系比较好地解决了通常TNF与高分子之间相容性差,难以实现高浓度掺杂的问题。实验结果表明这种光导体具有良好的表面电荷保持能力,在所考察的掺杂浓度范围内饱和电压一般都在+950V以上;通过调节CGL的高分子材料暗衰减速度可以控制在3.3V/s;光导体在整个可见光范围内表现出良好的感光度,特别在550、650和750nm处感光度出现峰值,在750nm处半衰曝光量为1.93μJ/cm²,在800nm处为2.8μJ/cm²。     

Spectroscopic consideration of the surface potential built across phthalocyanine thin films on a metal electrode

The nonlinear optical properties of tert-butyl phthalocyanine copper Langmuir-Blodgett (CuttbPc LB) films and vacuum-evaporated phthalocyanine copper (CuPc) films deposited on a metal surface were investigated by second-harmonic generation (SHG) spectroscopy. At the organic/metal interface, a space charge field is formed due to the presence of excess charge injected from a metal electrode to the organic layer. Since the Pc molecule has D4h symmetry, an inversion center is present and the optical SH process is not allowed under the electric-dipole approximation. However, the space charge field at the interface directly influences the symmetric structure of the electrons in the Pc molecule. We investigated the contributions of the surface potential to the SHG using Pc LB and vacuum-evaporated films deposited on aluminum (Al) and gold (Au) metal electrodes, where a distinctive difference in the spectrum for the Pc films on the Al and Au surfaces was observed. The contribution of the surface potential was revealed based on the resonant conditions of the SH process, taking into account the electric-quadrupole transition and dc-field-induced electric-dipole transition.     

High photosensitivity in cis-polyphenylacetylene films irradiated with 60Co γ-ray

This paper reports that ⁶⁰Co γ-ray irradiation can convert cis-polyphenylacetylene (cis-PPA) films prepared with rare-earth coordination catalysts to highly photosensitive materials. The dependence of the photosensitivity on irradiation dose, preparation methods, and microstructure of the PPA films has been investigated by means of a potential discharge technique. The photosensitivity was enhanced with increasing irradiation dose. The critical dose to produce a light response was 5 × 10³ Gy. The maximum surface potential discharge rate was 618 V/s, and the dark decay was approximately 2 V/s for cis-PPA films irradiated with ⁶⁰Co γ-ray (dose: 2 × 10⁵ Gy). The cis-transoidal-PPA and an electrophotographic photoreceptor device incorporating cis-PPA showed a higher irradiation effect. The structure and properties of ⁶⁰Co γ-ray irradiated rare-earth PPA films are similar to the unirradiated films.     

Fabrication of electrochemical transistor based on pi-conjugate polymer Langmuir-Blodgett film

We fabricated an efficient organic electrochemical transistor (OECT) composed of polymer Langmuir-Blodgett (LB) film. The pi-conjugated polymer LB film, which was constructed from a poly(N-dodecylacrylamide) (pDDA) and poly(3-hexylthiophene) (PHT) mixture, was used as a conduction channel layer to connect source and drain electrodes. The mixed-polymer LB film was characterized using UV-vis spectroscopy, X-ray diffraction (XRD), atomic force microscopy (AFM), and cyclic voltammetry. Subsequent UV spectra measurements, XRD measurements, and AFM measurements show that PHT forms a crystalline lamellar domain in the layered structure of pDDA. The OECT included 10 layers of the mixed-polymer LB film as the conduction channel layer. The OECT showed an on/off ratio of 1.1x10(4) and mobility of 7.5x10(-2) cm2 V(-1) s(-1) at low gate (VG=-1.2 V) and source-drain voltages (VDS=-0.5 V). Moreover, the necessary charge to operate the OECT was 1.1x10(-9) mol of e(-1) cm(-2), which was 2 orders smaller than the value reported using a similar device structure. The relatively high on/off ratio and low charge consumption suggest that this OECT, which is fabricated from pi-conjugated polymer LB films, is applicable to macroelectronic devices.     

Layer-by-layer electrostatic self-assembly of single-wall carbon nanotube polyelectrolytes

We have used anionic and cationic single-wall carbon nanotube polyelectrolytes (SWNT-PEs), prepared by the noncovalent adsorption of ionic naphthalene or pyrene derivatives on nanotube sidewalls, for the layer-by-layer self-assembly to prepare multilayers from carbon nanotubes with polycations, such as poly(diallyldimethylammonium) or poly(allylamine hydrochloride) (PDADMA or PAH, respectively), and polyanions (poly(styrenesulfonate), PSS). This is a general and powerful technique for the fabrication of thin carbon nanotube films of arbitrary composition and architecture and allows also an easy preparation of all-SWNT (SWNT/SWNT) multilayers. The multilayers were characterized with vis-near-IR spectroscopy, X-ray photoelectron spectroscopy (XPS), surface plasmon resonance (SPR) measurements, atomic force microscopy (AFM), and imaging ellipsometry. The charge compensation in multilayers is mainly intrinsic, which shows the electrostatic nature of the self-assembly process. The multilayer growth is linear after the initial layers, and in SWNT/polyelectrolyte films it can be greatly accelerated by increasing the ionic strength in the SWNT solution. However, SWNT/SWNT multilayers are much more inert to the effect of added electrolyte. In SWNT/SWNT multilayers, the adsorption results in the deposition of 1-3 theoretical nanotube monolayers per adsorbed layer, whereas the nominal SWNT layer thickness is 2-3 times higher in SWNT/polyelectrolyte films prepared with added electrolyte. AFM images show that the multilayers contain a random network of nanotube bundles lying on the surface. Flexible polyelectrolytes (e.g., PDADMA, PSS) probably surround the nanotubes and bind them together. On macroscopic scale, the surface roughness of the multilayers depends on the components and increases with the film thickness.     

A Novel Amphiphilic Push-pull Ferrocene Derivative: Langmuir-Blodgett Films and Second-order Optical Nonlinearity

We investigated Langmuir-Blodgett(LB) films built from the mixture of an amphiphilic push-pull ferrocene derivative(P) and behenic acid. Langmuir films of P diluted by behenic acid exhibit a very good cohesion, and the mixed films can easily be transferred onto solid substrates. Linear dichroism UV-visible and IR spectroscopy measurements of the mixed LB multilayers confirm that the molecules(P) are oriented to the substrate. The nonlinear optical experiments on the mixed monolayer deposited on the CaF₂ slide showed that P displays efficient optical second harmonic generation(SHG) with a molecular hyperpolarizability (β)h, high as 6.0×10^-29e. s. u..     

8-羟基喹啉镧两亲性配合物LB膜的双层电致发光器件

以具有不同层数的两亲配合物二[2-(N-十六烷基氨基甲酰基)-8-羟基喹啉]合镧[La(HQ)₂Cl]的LB膜为发光层,PBD为电子传输层,制备了双层结构的电致发光(EL)器件:ITO/LB膜/PBD/Al.器件产生黄绿色注入式发光.LB膜的层数和沉积压对器件的性能具有重要影响.在16V激发电压下,5,11和21层LB膜双层EL器件的电流密度分别为48,29和16.4mA/cm²,启亮电压阀值为7.5,8.5和9.5V.器件的亮度随电流密度和驱动电压的增加而增加.在相同偏压下,21层LB膜EL器件的亮度大于5和11层LB膜的器件.在25mN/m沉积的LB膜制备的EL器件具有较高的亮度(1219cd/m₂)和击穿电压.     

LB膜中聚集体的时间分辨荧光研究

利用吸收，稳态和时间分辨荧光方法研究了苯腙（ＰＤ）和半花菁（ＤＡＥＰ）分子在Ｚ型ＬＢ多层膜中的聚集性质，苯腙和半花菁吸收光谱的红移和兰移，说明它们分别以Ｊ和Ｈ型聚集体形式存在于ＬＢ膜中，苯腙和半花菁ＬＢ膜的荧光发射带分别在５６０ｎｍ和５８４ｎｍ处，亦分别对于它们溶液的荧光谱呈示出红移和兰移的特征，它们的荧光衰减曲线能很好地用双指数模拟拟合，在苯腙和半花菁ＬＢ多层膜中主要存在着荧光寿命分别在ｎｓ和１