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From Chain Collapse to New Structures: Spectroscopic Properties of Poly(3-thiophene acetic acid) upon Binding by Alkyl Trimethylammonium Bromide Surfactants

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Institut Charles Sadron, CNRS-University of Strasbourg, 23 rue du Loess, BP 84047, 67034 Strasbourg Cedex 2, France
Cite this: Langmuir 2012, 28, 10, 4815–4828
Publication Date (Web):February 14, 2012
Copyright © 2012 American Chemical Society

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    The binding of cationic surfactants with varying alkyl chain length to a regiorandom conjugated polyanion, poly(3-thiophene acetic acid) (PTAA), is studied in an aqueous buffer by using absorption and emission spectroscopies, photon correlation spectroscopy, isothermal titration calorimetry, and cryogenic transmission electron microscopy. We study the mixed solutions as a function of composition ratio R of surfactant molecules to monomer units molar concentrations, at low polymer concentration and in a very wide composition range (10–6 < R < 102) below the critical micellar concentration. Upon surfactant binding, the molecularly dispersed chains first collapse progressively and then form new structures as the mixed aggregates get enriched in surfactant. The collapse leads to a strong decrease of the conjugation length and to a blue shift of the absorption spectra by 30 to 50 nm. The new structures are responsible for a new intense emission band at about 600 nm, red-shifted by nearly 130 nm from the initial emission maximum of the polymer (∼472 nm). As the surfactant tail becomes shorter, the blue shift of the absorption spectra and the intensity raise of the new emission are delayed to larger composition ratios while their variations become smoother functions of the surfactant concentration. These particular spectroscopic properties of PTAA seem related to its unique combination of a strongly hydrophobic backbone, a large ratio of contour length to persistence length, and an overall good aqueous solubility. Our results show that such features are well suited to design a colorimetric biosensor at small composition ratio, and a fluorescent biomarker at large composition ratio.

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    Details and figures on the following: the error made on the maximum absorption position, the influence of excitation energy on the emission characteristics, the effect of filtration on sample concentration, the evolution of the scattering intensity with composition ratio, the relative abundance of small and large objects, the analysis of the second emission band, the influence of pH on spectroscopic properties, the determination of cac values, raw ITC data, and the reproducibility of PCS results. This material is available free of charge via the Internet at

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    Cited By

    This article is cited by 13 publications.

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    10. Alexandra Arranja, André P. Schroder, Marc Schmutz, Gilles Waton, François Schosseler, Eduardo Mendes. Cytotoxicity and internalization of Pluronic micelles stabilized by core cross-linking. Journal of Controlled Release 2014, 196 , 87-95.
    11. Shin-Il Kim, Young-Jae Jin, Wang-Eun Lee, Ri Yu, Sang-Joon Park, Hyo-Jin Kim, Kyu-Ho Song, Giseop Kwak. Microporous Conjugated Polymers with Enhanced Emission in Immiscible Two-Phase System in Response to Surfactants. Advanced Materials Interfaces 2014, 1 (1) , 1300029.
    12. Rachel C. Evans. Harnessing self-assembly strategies for the rational design of conjugated polymer based materials. Journal of Materials Chemistry C 2013, 1 (27) , 4190.
    13. Rachel C. Evans, Matti Knaapila, Niamh Willis-Fox, Mario Kraft, Ann Terry, Hugh D. Burrows, Ullrich Scherf. Cationic Polythiophene–Surfactant Self-Assembly Complexes: Phase Transitions, Optical Response, and Sensing. Langmuir 2012, 28 (33) , 12348-12356.

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