纳米Fe/C复合材料的原位合成

在石油渣油中加入二茂铁，通过热缩聚反的位合成纳米级铁粒子均匀分散于炭基体中的新型复合材料，研究了在420℃热缩聚时停时间和二茂铁添加量对Fe/C形成的影响，并用TEM和XRD观测和分析了Fe/C的形态和结构，结果表明，在基体中铁粒子的粒径为25－50nm，在一定条件下，二茂铁添加量的增加和停留时间的延长均使Fe/C产率提高，停留时间对热缩聚反应的影响遵循一级反应动力学，二茂铁的添加能显著提高反应速率常数k值。     

Effect of functional group of ferrocene redox substance on the transport properties of newly designed ion exchange membrane prepared from polymer gel

A different newly designed cationic exchange polymer membrane and anionic exchange polymer membrane were introduced, and also the transport properties of these polymeric membranes were investigated in this study. The transport properties of these polymer membranes in contact with ferrocene redox derivatives were estimated by using electrochemical techniques such as cyclicvoltammetry, chronopotentiometry, and chronoamperometry techniques, respectively. The used ferrocene redox substances, which have different functional groups, were (Ferrocenylmethyl) trimethylamonium iodide, FcMA, Ferrocenedimethanol, FcDM, and Ferrocene carboxylic acid, FcCA. It indicated that the performance of a membrane depended on the content of polymer gel, anionic exchange polymer site (20 wt % and 50 wt %) or cationic polymer exchange site (20 wt % and 50 wt %), and the efficiency of the functional groups of cationic and anionic exchange polymer site as well. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of liquid crystalline polymers containing aromatic ester mesogen and a nonmesogenic ferrocene unit in the spacer

A new series of liquid crystalline polymers containing aromatic triad ester mesogen and 1,1′‐disubstituted ferrocene as a nonmesogenic unit along with polymethylene spacer was synthesized. The polymer was synthesized by a room temperature polycondensation reaction between bis(4‐chloroformyl phenyloxy alkyl ferrocene dicarboxylate) and quinol. The alkyl groups have been varied by an even number of methylene groups with a range from two to ten groups. All the polymers were found to possess liquid crystalline properties. The identification of the mesophase is more transparent with an increase in the spacer. The thermal characteristics were studied using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The results reveal that the thermal stability of the polymers was decreased with increasing spacer length. The T_g, T_m, and T_i of the polymers decreased with increasing methylene groups. The incorporation of the ferrocene moiety also has a considerable effect on the glass transition temperature. The char yield of the polymer decreases with an increasing methylene chain length. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3494–3501, 2002     

Fabrication of Fe3O4 Dots Embedded in 3D Honeycomb‐Like Carbon Based on Metallo–Organic Molecule with Superior Lithium Storage Performance

A novel metallo–organic molecule, ferrocene, is selected as building block to construct Fe₃O₄ dots embedded in 3D honeycomb‐like carbon (Fe₃O₄ dots/3DHC) by using SiO₂ nanospheres as template. Unlike previously used inorganic Fe₃O₄ sources, ferrocene simultaneously contains organic cyclopentadienyl groups and inorganic Fe atoms, which can be converted to carbon and Fe₃O₄, respectively. Atomic‐scale Fe distribution in started building block leads to the formation of ultrasmall Fe₃O₄ dots (≈3 nm). In addition, by well controlling the feed amount of ferrocene, Fe₃O₄ dots/3DHC with well‐defined honeycomb‐like meso/macropore structure and ultrathin carbon wall can be obtained. Owing to unique structural features, Fe₃O₄ dots/3DHC presents impressive lithium storage performance. The initial discharge and reversible capacities can reach 2047 and 1280 mAh g^?1 at 0.05 A g^?1. With increasing the current density to 1 and 3 A g^?1, remarkable capacities of 963 and 731 mAh g^?1 remain. Moreover, Fe₃O₄ dots/3DHC also has superior cycling stability, after a long‐term charge/discharge for 200 times, a high capacity of 1082 mAh g^?1 can be maintained (80% against the capacity of the 2nd cycle).     

二茂铁功能化石墨烯复合材料的制备及其电催化多巴胺性质研究

利用氧化石墨烯片边缘的羧基和表面的环氧基团共价修饰的方法制备了二茂铁功能化石墨烯的复合材料,通过FT-IR、TEM等测试方法对复合材料的结构和形貌进行了表征,二茂铁共价修饰石墨烯复合材料呈现出了良好的稳定性。我们进一步利用二茂铁功能化石墨烯修饰电极对多巴胺电化学催化性质进行研究,该修饰电极对多巴胺显示出良好的催化活性,并推测出可能的催化反应机理,当信噪比为3时,检测限达到0.01μM。     

DDI-microFIA--A readily configurable microarray-fluorescence immunoassay based on DNA-directed immobilization of proteins

We describe a chip-based immunoassay for multiplex antigen detection, based on the self-assembly of semi-synthetic DNA-protein conjugates to generate an easily configurable protein microarray. The general principle of this microarray-fluorescence immunoassay (microFIA) is similar to that of a two-sided (sandwich) immunoassay. However, covalent single-stranded DNA-streptavidin conjugates are employed for the efficient immobilization of biotinylated capture antibodies through hybridization to complementary surface-bound DNA oligomers. In a model system, we use the DNA-directed immobilization (DDI) of antibodies to generate an antibody microarray for the parallel detection of the tumor marker human carcinoembryonic antigen (CEA), recombinant mistletoe lectin rViscumin (rVis), ceruloplasmin (CEP), and complement-1-inactivator (C1A) in human blood serum samples. Detection limits down to 400 pg mL(-1) are reached. In addition, we describe a method for the internal standardization of protein microarray analyses, based on the simultaneous measurement of constant amounts of the blood proteins CEP and C1 A, intrinsically present in human serum, to compensate for interexperimental variations usually occurring in microarray analyses. The standardization leads to a significantly higher data reliability and reproducibility in intra- and interassay measurements. We further demonstrate that the DDI-microFIA can also be carried out in a single step by tagging of the analyte simultaneously with both capture and detection antibody and subsequent immobilization of the immunocomplex formed, on the DNA microarray capture matrix. This protocol significantly reduces handling time and costs of analysis.     

纳米金与二茂铁在葡萄糖传感器中的相互作用

针对纳米金颗粒修饰的葡萄糖生物传感器对葡萄糖的响应电流随着工作电压的下降快速下降的问题,进一步利用电子媒介体二茂铁对其进行修饰,并选用丝网印刷电极研究了纳米金颗粒和二茂铁之间的相互作用。实验结果表明:二茂铁有效地降低了纳米金颗粒修饰的葡萄糖生物传感器响应电流的下降值,纳米金颗粒降低了电子媒介体二茂铁的氧化还原反应电位,并且,纳米金颗粒与电子媒介体二茂铁在葡萄糖生物传感器中表现协同增效效应。     

Electrical conduction mechanism in solution grown doped polyvinyl pyrrolidone films

A detailed study of electrical conduction mechanism in bimetallized ferrocene-doped polyvinyl pyrrolidone films was carried out. The measurements were carried out on films of about 20 μm thick, in the field range of (2.0–8.0) x 10⁴ V/cm at temperatures ranging from 363 to 423 K. An investigation of the effect of impurity such as ferrocene in the polymer matrix was undertaken. Lowering of activation energy and increase in current due to doping were observed. The results showed that the charge carriers were generated by field-assisted lowering of coulombic barriers at the traps and were conducted through the bulk of the material by a hopping process between the localized states by a Jonscher-Ansari modified Poole-Frenkel mechanism. The dependence of current and activation energy on the ferrocene concentration is explained on the basis of charge transfer type of interaction between dopant and polymeric material.     

含二茂铁和双噻唑的聚合席夫碱的合成与性能研究

以丁二酮、液溴和硫脲为原料经过有机合成反应制得2,2′-二氨基-4,4′-联噻唑（DABT）;利用合成的DABT和二茂铁甲醛通过缩合反应得到小分子二茂铁席夫碱,利用傅列德尔-克拉夫茨反应原理制备了聚合二茂铁席夫碱;再将金属铁、镍和铜的硫酸盐掺杂聚合物得到其金属配合物,利用红外、^1H核磁表征了产物的结构,用四探针测试仪和古埃磁天平测试了产物的电导率和磁性能。实验结果表明：合成产物是聚合二茂铁基席夫碱,其电导率为1.61×10^-6S·cm^-1,处于半导体范围;掺杂有Fe^2＋,Ni^2＋和Cu^2＋的硫酸盐配合物的磁增重均比未掺杂的聚合物有明显的提高,其中掺杂Cu^2＋金属离子的配合物性能最好,这暗示它可作为一类新型的有机功能电磁材料。     

对称型席夫碱类二茂铁衍生物的合成与性能研究

以二茂铁甲醇为原料,经Wittig反应后与2,6-(双胺基)-苯并[1,2-d-4,5-d′]双三唑-4,8(2H,6H)-二酮缩合,合成了一个D-π-A-π-D结构的二茂铁席夫碱类金属有机三阶非线性光学材料。化合物结构经1H NMR,MS表征确认。测定了该化合物的紫外-可见吸收光谱,用简并四波混频(DFWM)检测了其三阶非线性参数,检测波长为800 nm;脉冲宽度为80 fs。该化合物的三阶非线性极化率χ(3)值为3.67×10-13esu(静电单位),分子二阶超极化率γ值为3.49×10-31esu,表明该化合物具有良好的三阶非线性光学性能,优于现有的二茂铁类金属有机材料。探讨了分子结构对三阶非线性光学性能的影响,长共轭链、强电子离域能可提高分子三阶非线性光学性能。