等离子体聚合膜的电学性质研究：Ⅰ.TCNQ聚合膜的结构和电学性质

本文采用内部电极、电容耦合式钟罩型射频等离子体聚合装置,首次进行了四氰代对二次甲基苯醌(TCNQ)的等离子体聚合,得到了电导率为10~(-8)～10~(-6)Scm~(-1)的聚合物半导体薄膜。由这些聚合物薄膜制备的Al/聚合膜/ITO(铟锡氧化物透明电极)夹层元件显示出整流特性和光生伏打效应。这种聚合物薄膜还具有光电导性质。红外光谱(IR)、紫外光谱(UV)的研究结果表明,优良的半导体特性归因于聚合膜中存在有较大范围的π电子共轭结构。     

Conductive Organic Complex Salt TTF‐TCNQ as a Mediator for Biosensors. An Overview

Preparation and application of a conductive organic salt complex of tetrathiafulvalene‐tetracyanoquinodimethane (TTF‐TCNQ) for analytical bioelectrochemistry as a mediator is overviewed in this work. The third‐generation biosensors based on this charge transfer salt are very promising for biosensors applied in vivo. Such mediated biosensors have been studied mainly for glucose determination, but at present other substrates are being applied in this system more and more often.     

平板双层磷脂膜中伏安行为的研究

未经修饰的双层类脂膜（BLM）是很好的绝缘体，不能进行离子和电子传导。但是，经过适当的修饰，如嵌入碘分子或者富含π-电子的有机化合物（四氰代二甲基苯醌TCNQ，四硫富瓦烯TTF），BLM显示出双偶电极的行为，也就是BLM一侧是进行氧化还原反应的阴极，另一侧是进行氧化还原反     

蛋白质与四氰代二甲基苯醌荷移反应的研究

用分光光度法研究了蛋白质与四氰代二甲基苯酪(TCNQ)之间的荷移反应．通过 对影响反应因素的研究，确立了以形成荷移(CT)配合物测定蛋白质的最佳反应条件 ，在V(丙酮)：V(水)＝1：4，pH＝9．8的溶液中，配合物在425nm处有最大吸收， BSA在0—40ug/mL及50—300ug/mL符合朗伯—比尔定律，摩尔吸光系数分别为2． 43×10^5L．mol^-1.cm^-1和2．90×10^5L.mol^-1.cm^-1。分别用平衡透析法、双 波长法和摩尔比法研究了蛋白质与TCNQ的结合方式并测定了最大结合数．当TCNQ浓 度较小时，与蛋白质的结合符合Scatchard规则，存在两类结合方式，具有不同结 合常数；TCNQ浓度较高时，符合Plasvento相分配模型，分配常数为一定值．用拟 合的方法测定了人血清样品中的蛋白质，与考马斯亮蓝法测定结果吻合，回收率为 98％—104。     

Kinetics of formation of charge transfer complexes of poly(vinyl pyridines) with iodine, 7,7′8,8′-tetracyanoquinodimethane and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone by electronic spectroscopic studies

The kinetics of formation of charge transfer complexes of poly(4-vinyl pyridine), poly(2-vinyl pyridine), and poly(2-vinyl pyridine-co-styrene) with iodine, 7,7′,8,8′-tetracyanoquinodimethane and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone has been studied using electronic absorption spectroscopy. The charge transfer complexes of analogous low molecular weight donors, namely 2- and 4-picolines with the same set of acceptors have also been investigated for comparison. The composition and the equilibrium constants of the charge transfer complexes have been obtained. The equilibrium constant of the polymeric complexes is found to be higher than that of analogous complexes of the low molecular weight donors. A new method for determining the rate constants of the association and dissociation of the equilibrium involving the charge transfer complex formation has been proposed. The rate constants vary with the concentration of the acceptor. It indicates that the charge transfer complexes undergo a further reaction and hence the observed rate constants are not true but apparent rate constants. The charge transfer complexes have also been investigated by electron paramagnetic resonance spectroscopy.     

Application of a screened INDO model (INDO/S) to spectroscopic properties of TCNQ and its anions

Theoretical Chemistry Accounts - An INDO model Hamiltonian, incorporating screening within the π-system and parametrized particularly to describe dynamical properties (photoemission and...     

NADH Electrocatalytic Oxidation on Gold Nanoparticle‐Modified PVC/TTF‐TCNQ Composite Electrode. Application as Amperometric Sensor

We herein report on the electrocatalytic activity towards the oxidation of NADH of a PVC/TTF‐TCNQ composite electrode modified with gold nanoparticles. This electrocatalytic property allows proposing this system as a new alternative for amperometric determination of NADH, without need to add another mediator. The sensor shows a linear response to NADH over a concentration range from 5.0×10^?6 M up to 5.0×10^?4 M, with a sensitivity of 11.22±0.5 mA M^?1 and a detection limit (S/N=3) of 4.0×10^?6 M for measurements in batch and similar data in FIA.     

Single‐Chain Magnetic Behavior in a Hetero‐Tri‐Spin Complex Mediated by Supramolecular Interactions with TCNQF.− Radicals

The self‐assembly of organic TCNQF^.? radicals (2‐fluoro‐7,7,8,8‐tetracyano‐p‐quinodimethane) and the anisotropic [Tb(valpn)Cu]³⁺ dinuclear cations produced a single‐chain magnet (SCM) involving stacking interactions of TCNQF^.? radicals (H₂valpn is the Schiff base from the condensation of o‐vanillin with 1,3‐diaminopropane). Static and dynamic magnetic characterizations reveal that the effective energy barrier for the reversal of the magnetization in this hetero‐tri‐spin SCM is significantly larger than the barrier of the isolated single‐molecule magnet based on the {TbCu} dinuclear core.     

Enhanced stability of low temperature processed perovskite solar cells via augmented polaronic intensity of hole transporting layer

The commercial mass production of perovskite solar cells requires full compatibility with roll‐to‐roll processing with enhanced device stability. In line with this, the present work addresses following issues simultaneously from multiple fronts: (i) low temperature processed (140 °C) ZnO is used as electron transport layer (ETL) for fabricating the mixed organic cation based perovskite solar cells, (ii) the expensive hole transporting layer (HTL) spiro‐OMeTAD is replaced with F4TCNQ doped P3HT and (iii) the fabrication method does not incorporate the dopant TBP which is known to induce degradation processes in perovskite layer. All the devices under study were fabricated in ambient conditions. The F4TCNQ doped P3HT (HTL) based devices exhibits 14 times higher device stability compared to the conventional Li‐TFSI/TBP doped P3HT devices. The underlying mechanism behind the enhanced device lifetime in F4TCNQ doped P3HT (HTL) based devices was investigated via in‐depth electronic, ionic and polaronic characterization. The enhanced polaronic property in F4TCNQ doped P3HT HTL device ascertains its superior hole extraction and electron blocking capability; and consequently higher stability retained even after a month of ageing.

     

外电场下TCNQ的激发与光谱性质研究

采用密度泛函B3PLY方法优化了不同外电场下TCNQ分子的基态稳定构型、电偶极矩和分子的总能量，并且分析了TCNQ分子的HOMO-2到LUMO+2轨道的能量变化。然后利用杂化CIS-DFT方法在同样的基组下计算了外电场下TCNQ分子的前9个激发态的激发能、波长和振子强度，结果表明在没有外电场的情况下，TCNQ分子只有一个激发态能够激发，从基态跃迁到第1激发态。在有外电场的作用下，总能量随外电场的增加而逐渐减少，偶极矩随外电场的增加而不断增加。其前线轨道的能量也随外电场的增加不断减少，轨道分布也受外电场很大的影响。另外，外电场对TCNQ分子的激发波长也产生了一定影响。