Nanostructures of conducting polymers and their composites

导电聚合物是人工合成的具有类似半导体、金属导电性，同时具有传统聚合物材料的特点的一种新型材料。由于导电聚合物特殊的掺杂机理、较高的环境友好性和稳定性、易加工性以及廉价的优点，在化学、生物传感器，发光二极管，分子、电子、光学器件等领域中的潜在应用前景，引起了广泛的研究热潮。近来，纳米科学技术的发展以及导电聚合物本身的性质和应用前景，纳米导电聚合物的可控合成以及相关的纳米复合材料的制备已经得到了研究人员越来越多的重视。纳米结构导电聚合物的制备途径主要包括“硬模板”法、“软模板”法和“无模板”法。同时，制备导电聚合物的纳米复合材料是改善导电聚合物性能和应用潜力的重要方法。本论文从导电聚合物中常见的聚...Conducting polymers, which possess semiconducting or metallic conductivities and traditional characteristics of polymer, are synthesized as novel materials. Owning to the special doping mechanism, well environment-friendly and environmental stability, facile preparation and cheap, also the potential applications in chemical and biological sensors, light-emitting diodes, molecular electronic optics...学位：理学博士院系专业：化学化工学院化学系_物理化学(含化学物理)学号：2052006015326

聚苯胺纳米点的氧化还原态与其库仑台阶效应

应用电化学恒电位法结合模板法制备聚苯胺纳米点阵列,导电原子力显微镜研究处于不同氧化还原态的聚苯胺纳米点的I～V特性,发现只有处于部分氧化态(导电态)的聚苯胺纳米点才出现库仑台阶效应,还原和全氧化态聚苯胺纳米点不显示库仑台阶.初步探讨了上述现象

自组装金团簇电极库仑台阶现象和电化学阻抗谱研究

采用示差脉冲伏安法研究了自组装单层保护金纳米团簇(C8AuMPC)在常温下二氯甲烷溶液中的量子化电容充电效应.研究结果表明,该团簇在-0.8~0.8V电位范围内有4对明显的量子化电容充电峰.同时采用电化学阻抗谱对C8AuMPC修饰金电极体系的界面结构进行了表征,研究结果表明,MPC自组装层存在两个界面,即金电极-MPC层界面和MPC层-溶液界面;这两个界面的界面电容在MPC的零电荷电位(ca.-0.2V)附近均基本保持不变,随着电位正移或负移到一定程度,界面电容发生变化.进一步利用双隧道结金属岛库仑阻塞效应理论讨论了已有报道中对MPC量子化电容充电的理论分析结果,并证明电化学阻抗谱也是研究MPC量子化电容充电效应的有效方法.另外,用示差脉冲伏安法及循环伏安法研究了电活性物种二茂铁对C8AuMPC量子化电容充电的影响,发现溶液中的电活性物种对MPC层-溶液界面的电子传递的贡献可以忽略,表明该界面的电子传递主要发生在纳米粒子之间

多级树状纳米结构聚苯胺的电化学制备

建立一种无模板的恒电位电聚合方法,可在室温下制备对甲基苯磺酸(p-TSA)掺杂的多级树状纳米结构聚苯胺(PANI).根据电聚合曲线分析了PANI的聚合机理.扫描电镜(SEM)、透射电镜(TEM)观察表明制备的PANI具有均匀的多级树状纳米结构.紫外可见吸收光谱(UV-Vis)和红外光谱(FTIR)则显示所制备的PANI为掺杂态.该电沉积方法具有简便、易操作的特点,还可应用于其它纳米结构导电聚合物的可控制备

手性聚苯胺纳米纤维的电化学制备

采用恒电位电聚合法制备了樟脑磺酸(CSA)掺杂的旋光异构性聚苯胺(PANI)纳米纤维.用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、紫外-可见吸收光谱(UV-Vis)和圆二色光谱(CD)对PANI纳米纤维的形貌和光学性质进行表征,结合电聚合溶液胶束平均粒径和ζ电位的测定,研究了具有旋光异构性PANI纳米纤维的形成机理和具有增强旋光异构性的原因.所制备的PANI纳米纤维具有无双螺旋结构,其形貌不随着苯胺浓度的改变而变化.不同手性樟脑磺酸掺杂制备的PANI纳米纤维具有镜像对称的旋光异构性,且具有较高的椭圆偏振率.这种手性PANI纳米纤维的颜色和旋光性均可通过化学掺杂/去掺杂或电化学掺杂改变氧化还原态而呈现可逆变化

固态聚苯胺电致变色器件的制备和性能

采用CeO2-TiO2复合物薄膜作为聚苯胺电致变色器件的对电极,选用聚合物固态电解质(PE:PMMA-PC-EC-L iC lO4),构筑了新型双层结构(Dual-type)聚苯胺(PANI)固态电致变色(EC)器件.用电化学现场紫外-可见光谱法表征了该EC器件(ITO|PANI||PE||CeO2-TiO2|ITO)的电致变色性能,并与单层结构(S ingle-type)EC器件(ITO|PANI||PE||ITO)进行了比较.研究结果表明,双层结构EC器件比单层结构EC器件的电致变色性能好,如响应速度快,循环寿命长.同时,考察了电解质组分对聚苯胺电致变色稳定性的影响.EC器件(ITO|PANI||PE||CeO2-TiO2|ITO)的颜色呈现由透明的黄色(-1.5 V,PANIvs.CeO2-TiO2)到蓝色(1.0 V)的可逆变化,在700 nm处的透射率由42.19%变到13.35%,经过150个循环,其透射率差仍保持不变,着色效率为152.1 cm2/C

Comparative Study on Improvement of Diabetic Model Rats between SBA-15/GLZ and SBA-16/GLZ

目的:通过建立Sd大鼠2型糖尿病模型的方法,研究不同的介孔材料SAb-15与SAb-16分别载药格列齐特(glz),释放速率的作用,以筛选出最佳的载药系统,为临床制剂提供参考。方法:考察SAb-15/glz、SAb-16/glz的载药、释药性能,建立大鼠糖尿病模型,分别检测灌胃给药前(0H)和给药后各时间点(3 H,6 H,9 H,12 H,24 H,27 H,30 H,48 H)各组大鼠血糖浓度的变化。结果:1载药系统的热重分析,SbA-15/glz、SbA-16/glz在200~700℃均有显著的失重,分别是14.3%和15.4%,且SbA-16/glz失重高于SbA-15/glz;2fTIr分析中,在红外光谱中500 CM-1~2000 CM-1波数范围内两种材料载药均出现了4个吸收强度较大的特征峰,二者波数范围相同,波峰相似,且与glz的分布趋势大致一致,且SbA-16/glz的吸收强度略高于SbA-15/glz;3载药系统的结构性质,与SbA-15比较,SbA-15/glz在比表面积、孔隙容积上均减小(P<0.01),与SbA-16比较,SbA-16/glz比表面积、孔隙容积上均减小,且SbA-16/glz的比表面积、孔隙容积均显著小于SbA-15/glz(P<0.01);4释放速率:SbA-15/glz内格列齐特有一个迅速的释放过程,12 H即达90%以上,24 H后缓释量逐渐趋于平缓,48 H释放量即达到95%以上,最终缓释量约在97%水平;而SbA-16/glz内格列齐特的缓释相对平缓,12 H之内释放了80%左右,显著低于同等时间点SbA-15对格列齐特释放(P<0.05),48 H最终缓释量约在90%的水平;5血糖变化,在0 H测得的血糖结果中,模型组及各给药组的血糖均显著升高,且≥13.8 MMO l/l,说明造模成功;12 H的血糖值最低,随着时间的推移,glz组的血糖变化梯度最大,SbA-15/glz次之,SbA-16/glz血糖值的变化曲线较平坦,说明介孔材料能有效载药、平稳缓释、在动物模型体内平稳持续释药并发挥作用,避免血糖浓度忽高忽低,SbA-16/glz缓释效果显著优于SbA-15/glz。结论:SAb-16介孔材料的载药量高于SAb-15,缓释持续时间长。Objective: This paper was to research on different mesoporous materials SAB-15 and SAB-16 respectively,the drug loaded Zig Leo Te( GLZ) release rate effect by the method of establishing model of SD rats with type 2 diabetes,and to screen out the best drug carrier-system for clinical use.Methods: Diabetic rat model was established,then to investigate the effect of SAB-15 /GLZ,SBA-16 / GLZ and detect the blood glucose,plasma insulin at the point of 0 h,3 h,6 h,9 h,12 h,24 h,27 h,30 h,48 h.Results: 1The weight analysis system loaded with heat showed that,SBA-15 / GLZ and SBA-16 / GLZ in 200 ~ 700 ℃ showed a significant weight loss,respectively 14.3% and 15.4%,and SBA-16 / G LZ weight loss was higher than that of SBA-15 / GLZ; 2The FTIR analysis,in the IR spectra of 500 cm-1~ 2000 cm-1,wave number range material drug carrier appeared 4 absorption intensity of characteristic peak,and the two peak wave number range is similar,and generally consistent with the distribution of GLZ and SBA-16 / GLZ,the absorption intensity is slightly higher than that of SBA-15 / GLZ; 3The structure properties of the drug carrier system,compared with SBA-15,SBA-15 / GLZ specific surface area,pore volume were reduced( P < 0.01); that compared with SBA-16,SBA-16 / GLZ surface area and porevolume decreased,and the SBA-16 / GLZ specific surface area and pore volume were significantly less than SBA-15 / GLZ( P < 0.01); 4Release rate: SBA-15 to GLZ procedure of a quick release and he quantity achieved above90% at the 12 th h,the rate slowed down after 24 h,at the 48 th h the quantity achieced above 95%,eventually slow release quantity was about 97%.The SBA-16 / GLZ sustained-release relatively flat,within 12 h released by about 80%,significantly lower than SBA-15 at the same point in time( P < 0.05),eventually slow release quantity was about 90%.5The changes of blood glucose showed that,measured at 0thh blood glucose results in the model group and the drug group blood sugar were significantly increased,and was higher than 13.8mmo L / L,indicating a successful model; The glucose concentration of each group at 12 thh was the lowest,and blood glucose in GLZ group change gradient was the biggest,SBA-15 / GLZ group change gradient was less than GLZ group,the curve of change with SBA-16 / GLZ group curve was flat as time went by.Which indicated that be effective,sustained release drug carrier,and played a role in the animal model in vivo sustained drug release and smooth,prevent blood glucose concentration fluctuat,SBA-16 sustained release effect was superior to that of SBA-15.Conclusion: The description of the drug loading of SBA-16 mesoporous material is better than SBA-15 which with releasing of long duration.南京军区医药卫生科研基金(编号:08MA115

Electrochemical Immunosensor Based on Chitosan/CNT Modified Electrode for the Detection of α-fetoprotein(AFP)

目的构建壳聚糖/碳纳米管(CnT)修饰电极电化学免疫传感器用于甲胎蛋白(AfP)检测的新技术。方法采用壳聚糖/CnT复合物修饰玻碳电极,通过共价键合方式将AfP抗体固定在修饰电极表面,固定抗体的电极与AfP、辣根过氧化物酶(HrP)标记的AfP抗体反应,构筑夹心型免疫复合结构。HrP催化TMb底物产生电流信号,电流信号大小与AfP浓度成正相关,实现对AfP的高灵敏检测。结果该电化学免疫传感器可以准确检测AfP标准样品,也可用于检测血清中AfP的浓度。结论壳聚糖/CnT修饰电极构建的用于AfP检测的电化学免疫传感器具有较高的灵敏度和准确性。Objective Construction of novel technology of electrochemical immunosensor based on chitosan/CNT modified electrode for the detection ofα-fetoprotein(AFP).MethodChitosan/CNT composites were used to modify the glassy carbon electrode,and then the AFP antibody was immobilized on the surface of modified electrode via covalent bonding via the glutaraldehyde.The fixed AFP antibody reacted with the AFP and HRP conjugated AFP antibody to form sandwich-type immunoassay structure.The high sensitive determination of AFP was measured from the electrochemical signal generated from the HRP catalyzed TMB substrate,and the current signals were positively related to the concentrations of AFP.ResultThe electrochemical immunosensor can be applied to accurately detect the AFP samples and can also be used for the detection of serum AFP concentration.ConclusionThe constructed electrochemical immunosensor based on Chitosan/CNT modified electrode for the detection of AFP shows high sensitivity and accuracy.福建省自然科学基金(2011J05023);福建医科大学博士启动基金(2010BS006);厦门大学固体表面物理化学国家重点实验室开放课题(201010

Size Effect of Conductivities of Polyaniline Nanowires

The study of size effect of conductivity of conducting polymer nanowires can be significant not only in the instruction of fabrication of the devices with nanodimension but also in basic research of inherence of nanomaterials. PANI nanowires was fabricated in AAO templates by potentiostatic method. A new strategy of chemical modification of AAO template was introduced to prepare nanowires with smaller diameter. FTIR and contact angle measurements were used to characterize the modification. Tunneling Electron Microscopy results showed that the smaller PANI nanowires in diameter can be obtained in surfactant modified AAO templates. Conductivity of single PANI nanowire had been measured by Conductive Atomic Force Microscopy. The results displayed that the conductivity of PANI nanowire increase while the decrease of the diameter of PANI nanowires, which was called size effect of conductivity of PANI nanowires. The size effect had been attributed to order polymer chains orientation of PANI nanowire, which had been confirmed by electron diffraction diagrams.国家自然科学基金(批准号:20433040,20173044)资

Redox State of Polyaniline Nanodot and its Coulomb Staircase Effect

应用电化学恒电位法结合模板法制备聚苯胺纳米点阵列,导电原子力显微镜研究处于不同氧化还原态的聚苯胺纳米点的I～V特性,发现只有处于部分氧化态(导电态)的聚苯胺纳米点才出现库仑台阶效应,还原和全氧化态聚苯胺纳米点不显示库仑台阶.初步探讨了上述现象.Polyaniline nanodot array had been fabricated in AAO template with potentiostatic method and the I~V characteristics of nanodots with different redox states were measured by conducting atomic force microscope (C-AFM) in atmosphere at room temperature. We found that only nanodots in partial oxidation state exhibit coulomb staircase in the I~V curves,while those in the full oxidation state and reduced state do not. The above phenomena were discussed preliminarily.作者联系地址：厦门大学固体表面物理化学国家重点实验室,化学化工学院;Author's Address: State Key Laboratory of Physical Chemistry of the Solid Surface and Department of Chemistry,College of Chemistry and Chemical Engineering,Xiamen University,Xiamen 361005,Fujian,Chin