Thiophenes acetate

Thus, many polymers with different conductivity were synthesized. To cite a few, these are polythiophene [158], 3-methylthiophene [159], polymers of 3-thiophene-acetic acid and methyl 3-thiophene-acetate [160], poly(2,5-thienylenevinylene) [161], poly(benzo[h]-thiophene) [162], poly(naphto[2,3-c]thio-phene) [163], poly(dithieno[3,2-h 2, 3 -fii]-thiophene) [164], poly(3- -hexylthiophene)... 

Polythiophenes functionalized with monosaccharides have been evaluated for their ability to detect the influenza virus and E. coli (Baek et al. 2000). Copolymers of thiophene acetic acid 10 and carbohydrate-modified thiophenes 11 have been prepared via iron(III) chloride mediated polymerization. Addition of influenza virus to a sialic acid containing copolymer resulted in a blue shift of the polymer absorption maximum, resulting in an orange to red chromatic transition. Mannose-containing polythiophenes underwent color changes upon the addition of the lectin ConA or E. coli cells that contain cell surface mannose-binding receptors. A similar biotinylated pol5hhiophene afforded a streptavidin responsive material (Paid and Leclerc 1996). 

Similar polymer/Au nanoparticle multilayer thin films were made by Wu et al. in a study of pH-sensitive dissociation behavior of poly (3-thiophene acetic acid) (PTA A) and PAA in a LbL film (of 8 bilayers).50 Unlike the pure polymer LbL film, the Au nanoparticles-containing LbL films were difficult to be released from the substrate by varying the pH. It was suggested that the gold particles act as a cross-linker in between the multilayers, thus further enhancing the stability of the LbL films. 

A systematic study of the effects of solvent on the reaction showed that for the first-order decomposition of the chlorosulfite the stereochemistry varies from complete retention in dioxane to complete inversion in toluene. Tetrahydropyran, tetrahydrofuran, dioxolane, ethylene chloride and ethylene bromide as solvents, in this order, led to decreasing degrees of retention. Saturated hydrocarbons, acetonitrile, cyclohexanone, thiophene, acetal and acetophenone as solvents led to low yields of predominantly, but not completely inverted chloride. The results are in accordance with the mechanistic scheme... 

Procedure. The thiophene is mixed with 1600 ml. of acetic acid and cooled to 10°. The bromine is mixed with the remaining acetic acid, cooled to 10°, and added slowly to the thiophene-acetic acid solution. The cooling bath is removed and the mixture stirred until the solution is... 

The most advanced method to determine the polymer structure is solid-state NMR spectroscopy. For the details of this method one must refer to the special literature. As an example, the application of double quantum magical angel spinning (DQ MAS) NMR spectroscopy to determine the structure of copolymers of 3-methylthiophene and ethyl-3-thiophene acetate (ETA) will be described. ... 

Peak assignment and relative peak intensities of poly-(3-methylthiophene) (PMT), poly-(ethyl-3-thiophene acetate) (PETA), and of the corresponding copolymer... 

The spectra are not ideal because the structure of these polymers is very irregular. Nevertheless, the spectra provide extremely good evidence for a structure of pairs of methyl-3-thiophene (MT) and ethyl-3-thiophene acetate (ETA). Moreover, the results show that the acetate group is still active, which is a prerequisite for using these polymers as a basis for complex modifications, e.g., with enzymes and is in agreement with the results of Welzel et al ... 

We have previously shown that when PPV is self-assembled with specific electronically active polyanions such as poly(thiophene acetic acid) (PTAA) or sulfonated fiillerenes (S-C60 )(7), the photoluminescence of the PPV is essentially completely quenched by the polyanion. The mechanism of this quenching is believed to be due to a photoinduc electron transfer process taking place between the excited PPV and the adjacent electroactive polyanion molecules. The quenching process, in this case, is not associated with a Forster type energy transfer since in both cases, the required spectral overlap of a donor emission band with an acceptor absorption band is not fulfilled. In addition, photo-induced electron transfer processes have previously been confirmed in PPV/C60 systems and can be exploited to fabricate thin film photovoltaic devices (77). In order to mediate this electron transfer process, we have constructed multilayer heterostructures in which the PPV donor and the polyanion electron acceptor are separated from each other with electronically inert spacer layers of known thickness. In addition to allowing studies of the electron transfer process, such structures provide important insights into the thermal stability of the multilayer structure. The "spacers" used in this study were bilayers of SPS/PAH with an experimentally determined bilayer thickness of 30 +/-5 A. 

Albery et al. [39, 49] prepared poly(3-thiopheneacetic acid) and its copolymer with thiophene by electrochemical polymerization. Bartlett et al. [50] electrochemically synthesized conducting poly(3-thiophene-acetic acid) films in dry acetonitrile containing tetraethyl ammonium tetrafluoroborate. These films are redox active in acetonitrile, however, stability was reportedly poor in comparison with poly(3-methylthio-phene) and poly(methyl 3-thiopheneacetate) due to traces of water. In dry acetonitrile, the polymer can be electrochemically oxidized and reduced. Upon oxidation in water and methanol, poly(3-thiopheneacetic acid) film converted into a passive film. Based on the electrochemistry and an FT-IR study, Bartlett et al. postulate the mechanism for the electrochemical passivation shown in the Figure 4.33. In the mechanism, passivation of the polymer involves the formation of an intermediate cyclic lactone and subsequent breakdown by reaction with solvent. This process does not destroy the conductivity of the polymer so the process can continue until all the monomer units within the film are converted to a lactone form (Figure 4.33, IV). The electrochemical passivation is not observed... 

Ferrocene dicarboxylic acid and 3-thiophene acetic acid 314-316... 

Adsorption of small redox-active molecules (e.g. ferrocene [326]) on ITO can be used to probe changes in electrochemical activity of ITO surface as a function of surface pretreatment [314]. Adsorption of ferrocene dicarboxylic add (Fc(COOH)2) and 3-thiophene acetic acid (3-TAA) onto ITO was achieved by soaking ITO in a 1 mM solution of these small molecules in pure ethanol for 10 min and then rinsing briefly with acetonitrile [314-316]. To ensure reproducibility, the adsorption of Fc(COOH)2 on pretreated ITO was repeated a minimum of three times on three separate ITO samples, for each pretreatment condition [314]. Chemisorbed small molecules on ITO will provide for better direct contact of added conducting polymer layers and/or hole transport layers (HTLs) in the devices [316],... 

Many substituted thiophenes are commercially available. Thus, the study of the effects of substituents on polythiophene is relatively straightforward in comparison with pyrrole, whose 3-monosubstituted and 3,4-substituted derivatives are not easily synthesized. Table 3 gives many substituted thiophenes that can be electrochemi-cally oxidized to produce conducting polymers. Some derivatives, such as 3-thiophene acetic acid, 3-thiophene malonic acid, 3-thiophene carboxylic acid, and 3-thiophene carboxaldehyde do not polymerize at all [205). 

CHO 11] Cho Y., Kim H., Oh M. et al., Ti02 composites for efficient poly(3-thiophene acetic acid) sensitized solar cells . Journal of The Electrochemical Society, o. 158, no. 2, pp. B106-B111, 2011. 

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