致密二茂铁硫醇自组装膜的电化学行为

合成了11-二茂铁基十一烷基-1-硫醇(HS-(CH₂)₁₁-Fc)，利用自组装膜的特点，通过分子设计将二茂铁基团引入到自组装膜中。在金电极表面构筑有序单分子膜，制备出具有电化学活性的修饰层，研究其电化学行为，作为考察复杂电化学动力学的理想模型。进一步探究其电子传递的特点与自组装膜表面覆盖度之间的联系，提出了一种新的电子传递模型，研究电子转移与膜结构的对应关系，为更深层次的分子设计和功能组装提供理论指导。     

硫醇分子链长对氧化还原自组装多层膜电化学行为影响的初步研究(英文)

以烷基硫醇和二茂铁衍生物构建的氧化-还原自组装多层膜为模型体系,研究烷基硫醇分子链长对多层膜电化学行为的影响.实验表明,二茂铁基团和电极之间的电子传递反应速率随两者距离的增加呈现指数级下降的趋势;烷基硫醇分子链长对自组装膜电化学行为的影响于不同情况下表现不同.本实验条件下,当多层膜上的电活性基团与电极比较接近时,长链分子自组装膜呈现较强的电化学响应.而当电极与电活性基团之间的距离较远时,短链烷基硫醇分子自组装膜呈现较强的电化学响应.     

自组装膜技术在电分析化学中的研究与应用

本文对自组膜（ＳＡＭｓ）在电分析化学中的研究和应用进行了比较全面的综述。ＳＡＭｓ是单分子膜化学修饰电极发展的最高形式，本文着重阐述了硫醇／金单分子层自组膜在微电极、生物电化学和生物传感器、液相色谱电化学、电催化、光谱电化学等电分析化学研究领域中的应用，并进行了展望。     

表面活性剂对硫醇单层膜修饰金电极电化学行为的影响

利用自组装方法在金电极表面制备成硫醇单层膜, 循环伏安和交流阻抗实验表明硫醇单层膜与表面活性剂十六烷基三甲基溴化胺作用后, 其电化学行为发生变化, 对于带有不同电荷的探针分子, 表现出一定的选择性响应. 即使是带有相同电荷的探针分子, 由于与表面活性剂的作用方式不同, 也使它们通过硫醇单层膜在电极表面产生电化学响应的程度完全不同.     

β－环糊精含硫衍生物自组单分子膜修饰金电极的选择穿透性研究

β－环糊精含硫衍生物自组单分子膜修饰金电极的选择穿透性研究何品刚，方禹之，铃木，嚴长，哲郎（华东师范大学化学系，上海，２０００６２）（东北大学药学部，仙台９８０，日本国）关键词硫辛酰－β－环糊精衍生物，自组单分子膜，金电极近年来，为在分子水平上控制和...     

一种结构新颖的二茂铁硫醇自组装膜的电化学行为

合成二茂铁乙烯基吡啶硫醇(FcC2′PyC4SH,I)及其还原产物二茂铁乙烷基吡啶硫醇(FcC2′PyC4SH,Ⅱ).再利用分子自组装技术在金电极表面形成二茂铁乙烯基吡啶硫醇单分子膜,通过循环伏安法探讨了这种自组装膜与结构相关的电化学响应.     

流动注射-电化学-表面等离子体激元共振联用技术研究二茂铁硫醇氧化还原结构变化

采用流动注射-电化学-表面等离子体激元共振联用技术研究了11-二茂铁基十一烷基-1-硫醇自组装膜在氧化还原过程中的构型变化.结果表明,二茂铁硫醇在氧化过程中,分子发生了两种结构变化:远离电极表面,烷基链与电极表面的夹角增大;分子上两个平行的戊基环绕着二茂铁-碳轴发生旋转.     

自组装超分子膜修饰电极的研制及分析应用

阐述了自组装超分子膜修饰电极的发展概况及超分子体系形成的理论基础，并对自组装超分子膜修饰电极的特点、电化学行为、功能膜的制备和表征方法以及它在电催化、生物传感器、离子选择性电极等方面的应用进行了综述。     

界面可控硫醇SAMs纳米金修饰金电极的电化学行为研究

在裸金电极上自组装不同比例的4,4’-二甲基联苯硫醇(MTP)和硫辛酸(TA)混合液,形成自组装膜(MTP+TA/Au SAMs),再修饰纳米金,制得纳米金混合巯基修饰金电极(AuNPs/MTP+TA/Au)。研究了纳米金混合巯基修饰金电极的电化学行为和阻抗行为,结果表明电极表面pH值的改变对电极表面的电子转移有重要影响。对葡萄糖传感器的制备条件、测定条件、抗干扰能力等进行了讨论,结果表明修饰电极的微结构和微环境有必要进一步研究。     

末端硫醇化的甲氧基聚乙二醇分子自组装膜电极对碘离子的电化学分析研究

碘离子的测量方法有化学法和电化学方法等多种,电化学方法有离子选择性电极、阴极溶出伏安法等［１,２］,但以上方法易受共存离子的干扰．自组装膜修饰电极具有分子识别功能,因而可用于特定物质的检测［３］．末端硫醇化的聚乙二醇分子在金电极表面形成自组装膜后具有分子识别特性［４］,碘离子和聚乙二醇膜有较好的相容性,可以进入膜内进而到达电极表面进行反应,而其它干扰离子较难进入．因而,该膜电极能用于碘离子测定,检测下限低,并具有较强的抗干扰能力．１　实验部分１．１　试剂及仪器　甲氧基聚乙二醇（ＭＷ＝５０００）等…     

Synthesis and redox properties of racemic electroactive polymers containing axially chiral adamantyl segments

A method of introducing chirality directly into a polymer backbone has been developed that employs the dissymmetry of an adamantane derivative with axial chirality. This new chiral adamantane building block was readily functionalized with electroactive thiophene rings using palladium-catalyzed cross-coupling methodology. The two resulting electroactive monomers were electropolymerized to create racemic electroactive polymers containing phenyl-capped oligothiophene segments alternating with chiral adamantyl segments. Synthesis, electrochemistry, and spectroelectrochemistry studies are reported.     

Potential‐Driven Chirality Manifestations and Impressive Enantioselectivity by Inherently Chiral Electroactive Organic Films

The typical design of chiral electroactive materials involves attaching chiral pendants to an electroactive polyconjugated backbone and generally results in modest chirality manifestations. Discussed herein are electroactive chiral poly‐heterocycles, where chirality is not external to the electroactive backbone but inherent to it, and results from a torsion generated by the periodic presence of atropisomeric, conjugatively active biheteroaromatic scaffolds, (3,3′‐bithianaphthene). As the stereogenic element coincides with the electroactive one, films of impressive chiroptical activity and outstanding enantiodiscrimination properties are obtained. Moreover, chirality manifestations can be finely and reversibly tuned by the electric potential, as progressive injection of holes forces the two thianaphthene rings to co‐planarize to favor delocalization. Such deformations, revealed by CD spectroelectrochemistry, are elastic and reversible, thus suggesting a breathing system.     

The Phenomenon of Mutual Media in Polypyrrole with Electroactive Ions

The dependence of the differential capacitance of polypyrrole doped with several typical dopants on potential is presented, which shows that the differential capacitance varies with the potential, the doped polypyrroles with electroactive ions give the largest capacitance near their formal potentials, which is attributed to the mutual media for electron transfer between polypyrrole and electroactive dopants. The existence of two conducting phases was observed in the complex capacitance plots. The electroactive anions act as an intra-conducting-phase medium for electron transfer, the electroactive cations act as an inter-conducting phase medium for electron transfer. The mutual media between polypyrrole and redox dopants lead to the increase of the discharging time.     

用氧化偶联聚合法合成新型电活性聚酰胺及其结构表征

使用氧化偶联聚合的方法, 合成了一种新的电活性聚酰胺, 使其同时具有聚酰胺和聚苯胺性质. 该反应操作简便易行, 室温下即可进行. 通过红外光谱和核磁共振谱对其结构进行了表征, 用紫外-可见光谱和循环伏安法研究了氧化还原性质和电活性, 并测试了导电率.     

Functional Janus dendrimers containing carbazole with liquid crystalline,optical and electrochemical properties

ABSTRACT

Novel liquid crystalline Janus dendrimers that combine a mesogenic block and an electroactive block have been synthesised. The mesogenic block is based on two third-generation Percec-type dendrons bearing six or eight terminal dodecyloxy alkyl chains, whereas the electroactive blocks are formed by one or two carbazole units. The liquid crystal behaviour was investigated by polarised-light optical microscopy, differential scanning microscopy and X-ray diffraction. The Janus dendrimers with one electroactive unit exhibited cubic or columnar liquid crystal phases, whereas the Janus dendrimers with two electroactive units did not show liquid crystalline behaviour. The UV-vis absorption and emission properties of the Janus dendrimers were investigated. The spectra suggested the existence of π-π stacking and the formation of aggregates in the solid state. Electrodeposition of the carbazole-containing dendrimers afforded semi-globular particles in which the number of electropolymerizable units and the flexible or rigid character of the linker have a decisive influence in the particle size.     

Bioelectronic modulation of single-wavelength localized surface plasmon resonance (LSPR) for the detection of electroactive biomolecules

The simplification of localized surface plasmon resonance (LSPR) detection can further promote the development of optical biosensing application in point-of-care testing. In this study, we proposed a simple light emitting diode (LED) based single-wavelength LSPR sensor modulated with bio-electron transfers for the detection of electroactive biomolecules. Indium tin oxide electrode loaded with nanocomposites of polyaniline coated gold nanorod was used as LSPR chip, and the applied electric potential was scanned at the LSPR chip for single-wavelength LSPR biosensing. Under the scanning of applied potentials, biological electron transfer of redox reaction was employed to demonstrate the bioelectronic modulation of single-wavelength LSPR for selective electroactive biomolecule detection. Without any additional recognition material, electroactive biomolecules uric acid and dopamine were detected directly with a sensitivity of 5.05 μmol/L and 7.11 μmol/L at their specific oxidation potentials, respectively. With the simplified optical configuration and selective bioelectronic modulation, the single-wavelength LSPR sensor is promising for the development of simple, low-cost, and high specificity optical biosensor for point-of-care testing of electroactive biomolecules.     

Electroactive shape memory cyanate/polybutadiene epoxy composites filled with carbon black

Electroactive shape memory composites were synthesized using polybutadiene epoxy(PBEP) and bisphenol A type cyanate ester(BACE) filled with different contents of carbon black(CB). Dynamic mechanical analysis(DMA), scanning electron microscopy(SEM), electrical performance and electroactive shape memory behavior were systematically investigated. It is found that the volume resistivity decreased due to excellent electrical conductivity of CB, in turn resulting in good electroactive shape memory properties. The content of CB and applied voltage had significant influence on electroactive shape memory effect of developed BACE/PBEP/CB composites. Shape recovery can be observed within a few seconds with the CB content of 5 wt% and voltage of 60 V. Shape recovery time decreased with increasing content of CB and voltage. The infrared thermometer revealed that the temperature rises above the glass transition temperature faster with the increase of voltage and the decrease of resistance.     

Electron transfer reactions to electroactive polymers

In the electrochemical reduction of an electroactive polymer several thousand electrons may be transferred to a single molecule. For polymers with noninteracting centers, recently developed theory indicates that the current—potential response would be identical with that of the corresponding molecule solvation, structural change, and variation in ionic environment, and may be used to probe these factors. A series of model compound of poly(vinylbenzophenone) and of poly(vinylbenzophenone-co-styrene) were prepared and investigated. In this study samples of various constant chain length with differing spacing of electroactive centers were employed. The current—potential measurements corresponded to the ideal theoretical case. This indicates that the behavior of the electroactive groups attached to the polymer chain was not influenced by the macromolecular environment or by neighboring group interaction.     

Multilayer electrodes: Fully electroactive cyt c on gold as a part of a DNA/protein architecture

The construction of new mediator-free and fully electroactive protein multilayer electrodes based on DNA and cyt c is demonstrated. The assembly is characterized by a rather high stability, effective electron transfer, and a tunability of the electroactive protein amount by the number of deposited cyt c layers.     

Label-free oligonucleotide detection method based on a new L-cysteine-dihydroartemisinin complex electroactive indicator

A novel base-mismatched oligonucleotide assay method based on label-free electrochemical biosensor was developed, in which the L-cysteine (Cys)-dihydroartemisinin (DHA) complex was used as a new electroactive indicator. In DNA sensor, Cys-DHA complex was initially formed on electrode surface by cathodic scanning, and target oligonucleotide was conjugated with Cys-terminated DHA indicator through electrostatic interaction under optimal pH. The subsequent sequence assay was responsive to hybridization recognition, which target oligonucleotide was captured by the surface-anchored DNA/Cys-DHA probe. The electrochemical signals of biosensor before and after hybridization were compared basing the measurements of semi-derivative linear scan voltammetry (SDLSV) and electrochemical impedance spectroscopy (EIS). On the basis of signal amplification of electroactive indicator and specific recognition of DNA probe, five target oligonucleotides with different mismatched bases were assayed, and a detection limit reached 0.3 nM. Furthermore, atomic force microscopy (AFM) was used to visually characterize specific recognition spots of biosensor at nanoscale. This study demonstrated a new electroactive molecule-based, biomolecule-involved electroactive indicator and its application in recognition and detection of complementary and base-mismatched oligonucleotide.