Specific interactions in complexes formed by polythiophene derivatives bearing polar side groups and plasmid DNA

The interaction between plasmid DNA and polythiophene derivatives bearing substituents with polar groups has been examined using electrophoresis assays, and both UV-Vis and CD spectroscopies. Results clearly indicate that such conducting polymers form stable adducts with DNA, even although the interactions strongly depend on the chemical constitution of the polymers. Furthermore, digestion assays with EcoRI and BamHI evidence that the polymers form specific interactions with the DNA, protecting the target nucleotide sequences of these restriction enzymes. On the other hand, UV-Vis and CD spectra show that the interactions induce a fast and very significant exposition of the nitrogen bases, which is consequence of the structural alterations induced in the circular DNA. These results have been compared with those previously reported for polypyrrole, poly(3,4-ethylenedioxythiophene) and poly(3-methylthiophene). Finally, a model based on the intercalation of the conducting polymer between the two DNA strands has been proposed.     

Synthesis and characterization of a dye-functionalized polythiophene with different chromic properties

As a preliminary study aiming to possible applications, a polythiophene derivative with an azobenzene moiety (polyazothiophene) was synthesized and characterized by FTIR, ¹H NMR, DSC and HPSEC. Some aspects on the thermo- and solvatochromic properties of polyazothiophene, such as the influence of different solvents and solution concentration on the thermochromic effect, and the use of a large polarity range of solvents as well as an acid media in the solvatochromic effect were explored. Reversible thermochromic properties of dimethylformamide and toluene solutions were analyzed in the temperature range of 10-70 °C showing a blue-shift spectrum variation with temperature increase. Solvatochromic properties were observed for pure solvents and THF/hexane mixtures. Another chromic effect was achieved upon the addition of a protonic acid to the azothiophene polymer solution as result of the side- and main-chain protonation.     

Fabrication of polythiophene patterns through blending of a thermally curable polythiophene with poly(methyl methacrylate) and selective thermal curation

In this study, we demonstrate a novel method for fabricating polythiophene patterns, i.e., cylindrical holes and cylinders, through blending of a thermally curable polythiophene carrying with tertiary ester groups (PT-tert-ESTER) and poly(methyl methacrylate) (PMMA), followed by thermal conversion of the PT-tert-ESTER to an insoluble polythiophene via low-temperature cleavage of the tertiary ester groups and removal of the PMMA component via ultraviolet degradation. We show that the surface polarity of substrates, the mass ratio of PT-tert-ESTER to PMMA in the blend solutions as well as the concentration of the blend solutions strongly influence the formation of the polythiophene patterns. Cylindrical holes are more readily formed on less polar substrates when a PT-tert-ESTER dominated blend solution is used, while cylinders are more readily formed on more polar substrates when a PMMA dominated blend solution is used. Moreover, the diameters of both the cylindrical holes and the cylinders decrease as the PT-tert-ESTER concentration is increased in the respective ranges of the PT-tert-ESTER/PMMA ratios where the patterns are formed. Grazing incident X-ray diffraction data have indicated that the patterning of the PT-tert-ESTER component in the blend films improves the crystallinity of PT-tert-ESTER as well as the molecular packing of the insoluble polythiophene in the resultant patterned polythiophene films.     

Strong two-photon-induced fluorescence from a highly soluble polythiophene

Two-photon-induced fluorescence from a soluble polythiophene containing urethane side groups has been investigated using femto-second laser pulses at 800 nm. Strong two-photon fluorescence was measured in polymer solution. The quadratic dependence of the fluorescence on the excitation laser intensity confirmed the two-photon process. The measured two-photon absorption cross-section is larger as compared to those of other reported polythiophenes. This polymer can be readily hydrolyzed to yield a water soluble polythiophene which could be useful in biological imaging.     

Effect of side groups on two-photon absorption of soluble polythiophenes

The effect of pendant side groups on two-photon absorption cross-section in a number of soluble fluorescent polythiophenes was investigated. Different side groups lead to different planarity and conformation of the polymer. As the side-group-induced planarity of the polymer chain increases, the two-photon absorption cross-section also increases. The increased delocalization of the π-electrons along the polymer backbone enhances the third-order optical nonlinearity. The aggregation of the polymer chain in solution lowers the quantum efficiency of fluorescence and decreases the two-photon absorption cross-section. This study demonstrates a novel method of enhancing the two-photon absorption cross-section by tuning the pendant side group.     

Fluorescence Quenching of Substituted Polyperylene with Functionalized Polythiophenes

The present investigation focuses the influence of polythiophene i) containing hetero aromatic structures and ii) containing mesogenic groups towards the photoluminescence properties of substituted polyperylene (PPE). The structural contribution towards the optical properties was individually discussed. The photoluminescence of PPE was quenched to the maximum level (30%) when it was blended with polythiophene with mesogenic groups containing longer alkyl spacer. Results of the same blend in solid-state shows 85% of PL quenching.     

可循环使用的Sn-TiO2/聚噻吩纳米杂化材料用于可见光下降解有机污染物

采用改进的溶胶-凝胶法在低温制备了Sn-TiO2/聚噻吩纳米杂化材料(SPNH),运用X射线衍射(XRD)、扫描电镜、X射线光电子能谱(XPS)、红外光谱(IR)、紫外-可见光漫反射光谱(UV-DRS)和BET比表面积分析对所制样品进行了表征。 XRD结果证实聚噻吩(PTh)对TiO2晶相结构没有影响。 IR和UV-DRS结果表明,在掺杂的金属氧化物与PTh的纳米杂化和结合过程中, PTh表面与金属氧化物之间存在相互作用(类似核壳结构)。 XPS结果显示,纳米杂化材料中存在Sn4+以及PTh与TiO2各自所含的元素。催化剂表面吸附污染物结果发现, SPNH的吸附容量高于Sn-TiO2纳米粒子(STN)。在可见光下降解有机污染物硝基苯(NB)和孔雀绿(MG)的反应中, SPNH表现出比单纯STN更高的光催化活性和稳定性。由于STN上存在聚噻吩,使得样品表面吸附NB(24%)和MG(21%)的能力增加,从而导致更高的光催化收率。考察了该光催化剂在可见光下重复使用5次时的光催化活性,未见PTh的消耗和降解。这些高光催化活性的SPNH材料有望在工业水净化中用作光催化剂。     

In situ UV/VIS Spectroscopy of Electrochemically Synthesized SelenopheneThiophene Copolymers

In situ UV/VIS spectroscopy of selenophene? thiophene homo‐ and copolymer films had been investigated. λ corresponding to the π→π* interband transition was determined. The optical transition with λ from the valence band into the higher bipolaron band was also allocated. Besides, band gap energy (E_g) of the individual homopolymer and the obtained copolymer films from a direct interband transition was estimated as well, and the values were between 1.91–2.10 eV. The influence of applied polymerization potential and monomer feed ratio on the optical properties of the copolymers is discussed.     

Synthesis, characterization and photovoltaic properties of thiophene copolymers containing conjugated side-chain

Five side-chain conjugated polythiophene derivatives, P1-P5, were synthesized by Stille coupling reaction. The effects of side-chain structures, bearing CC double bond, CC triple bond as well as different number of methoxy substituents on the benzene ring of the side-chains, on the optical, electrochemical, and photovoltaic properties of the polymers were investigated. From P1 to P3, the effect of CC triple bond and CC double bond was compared. The results indicate that the content of the thiophene units with the CC triple bond in their conjugated side-chains not only influences the absorption shape and intensity, but also influences the energy bandgap and the photovoltaic properties of the polymers. From P3 to P5, the effect of methoxy substituents on the benzene ring of the conjugated side-chains was compared. On increasing the number of the methoxy groups on the benzene ring of the conjugated side chains, the visible π-π^∗ absorption of the conjugated polymer backbone become stronger both in solution and in film. Electron-donating ability of the methoxy groups decreased the bandgap of the polymers. The best polymer solar cell based on P5 with a structure of ITO/PEDOT:PSS/Polymer:PCBM (1:1 wt/wt)/Mg/Al showed a power conversion efficiency of 1.45% under the illumination of AM1.5, 80 mW/cm².     

新型光学活性含氰基三联苯液晶聚噻吩合成与分子构象

合成了一种含有长柔性间隔基和氰基三联苯液晶基元的发光性聚噻吩衍生物{—[thiopheneyl—CH2—COO—(CH2)6—O—terphenyl—CN]n—, PT(6)TPhCN}. 利用傅里叶变换红外(FT-IR)光谱、核磁共振(1HNMR)、差示扫描量热(DSC)仪、偏光显微镜(POM)、紫外-可见(UV-Vis)吸收光谱和荧光(PL)光谱对单体和聚合物的结构及性质进行了表征. 单体都呈现出良好的液晶性能, 由于长间隔基的存在, 聚合物PT(6)TPhCN也呈现出良好SmAd相. 氰基三联苯的存在还赋予了聚合物良好的光致发光性能, 同时, 长间隔基也有效地降低了分子间的相互作用, 进一步增强了聚合物的发光性能. 另外, 研究发现, 在未引入任何手性元素的情况下, 聚合物主链在圆二色(CD)光谱中还呈现出明显的Cotton 效应, 这可能是由于大体积液晶基元的位阻效应和取向作用, 液晶基元环绕主链进行取向的同时诱导聚噻吩主链在长程范围内呈螺旋取向.