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Controlling Self-Assembly with Light and Temperature

Cite this: Langmuir 2020, 36, 1, 223–231
Publication Date (Web):December 10, 2019
https://doi.org/10.1021/acs.langmuir.9b03040
Copyright © 2019 American Chemical Society

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    Abstract

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    Complexes between the anionic polyelectrolyte sodium polyacrylate (PA) and an oppositely charged divalent azobenzene dye are prepared in aqueous solution. Depending on the ratio between dye and polyelectrolyte stable aggregates with a well-defined spherical shape are observed. Upon exposure of these complexes to UV light, the trans → cis transition of the azobenzene is excited resulting in a better solubility of the dye and a dissolution of the complexes. The PA chains reassemble into well-defined aggregates when the dye is allowed to relax back into the trans isomer. Varying the temperature during this reformation step has a direct influence on the final size of the aggregates rendering temperature in an efficient way to easily change the size of the self-assemblies. Application of time-resolved small-angle neutron scattering (SANS) to study the structure formation reveals that the cis → trans isomerization is the rate-limiting step followed by a nucleation and growth process.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.langmuir.9b03040.

    • Additional data on the synthesis of the polymer and diAzoEt, determination of the activation energy of the cis → trans isomerization, scattering length density and molecular volumes of diAzoEt and PA, form factor models and the aggregation kinetics at 58 and 66 °C (PDF)

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    Cited By

    This article is cited by 11 publications.

    1. Ryou Kubota, Taro Hiroi, Yuriki Ikuta, Yuchong Liu, Itaru Hamachi. Visualizing Formation and Dynamics of a Three-Dimensional Sponge-like Network of a Coacervate in Real Time. Journal of the American Chemical Society 2023, 145 (33) , 18316-18328. https://doi.org/10.1021/jacs.3c03793
    2. Mikhail Kim, Coral Hillel, Kayrel Edwards, Tristan H. Borchers, Ozzy Mermut, William J. Pietro, Christopher J. Barrett. Azo dye polyelectrolyte multilayer films reversibly re-soluble with visible light. Frontiers in Materials 2024, 11 https://doi.org/10.3389/fmats.2024.1334863
    3. Alexander Zika, Mohit Agarwal, Wiebke Zika, Dirk M. Guldi, Ralf Schweins, Franziska Gröhn. Photoacid-macroion assemblies: how photo-excitation switches the size of nano-objects. Nanoscale 2024, 16 (2) , 923-940. https://doi.org/10.1039/D3NR04570F
    4. Muhammad Younis, Sadia Ahmad, Atia Atiq, Muhammad Amjad Farooq, Mu‐Hua Huang, Manzar Abbas. Recent Progress in Azobenzene‐Based Supramolecular Materials and Applications. The Chemical Record 2023, 23 (11) https://doi.org/10.1002/tcr.202300126
    5. Wenke Müller, Ralf Schweins, Bernd Nöcker, Joachim Kohlbrecher, Glen J Smales, Klaus Huber. Comparative study of the co-assembly behaviour of 3-chloro-4-hydroxy-phenylazo dyes with DTAB. Soft Matter 2023, 19 (24) , 4588-4598. https://doi.org/10.1039/D3SM00501A
    6. Anja Krieger, Alexander Zika, Franziska Gröhn. Functional Nano-Objects by Electrostatic Self-Assembly: Structure, Switching, and Photocatalysis. Frontiers in Chemistry 2022, 9 https://doi.org/10.3389/fchem.2021.779360
    7. Alexander Zika, Anja Krieger, Franziska Gröhn. Nano-Objects by Spontaneous Electrostatic Self-Assembly in Aqueous Solution. 2022, 119-167. https://doi.org/10.1007/978-3-031-00657-9_5
    8. Pasquale Porcu, Aldo S. Estrada-Montaño, Mireille Vonlanthen, Fabián Cuétara-Guadarrama, Israel González-Méndez, Kendra Sorroza-Martínez, Gerardo Zaragoza-Galán, Ernesto Rivera. Azobenzene dyads containing fullerene, porphyrin and pyrene chromophores: Molecular design and optical properties. Dyes and Pigments 2022, 197 , 109858. https://doi.org/10.1016/j.dyepig.2021.109858
    9. Mario Samperi, Bilel Bdiri, Charlotte D. Sleet, Robert Markus, Ajith R. Mallia, Lluïsa Pérez-García, David B. Amabilino. Light-controlled micron-scale molecular motion. Nature Chemistry 2021, 13 (12) , 1200-1206. https://doi.org/10.1038/s41557-021-00791-2
    10. Alexander Zika, Franziska Gröhn. Multiswitchable photoacid–hydroxyflavylium–polyelectrolyte nano-assemblies. Beilstein Journal of Organic Chemistry 2021, 17 , 166-185. https://doi.org/10.3762/bjoc.17.17
    11. Cedric J. Gommes, Raphael Chattot, Jakub Drnec. Stochastic models of dense or hollow nanoparticles and their scattering properties. Journal of Applied Crystallography 2020, 53 (3) , 811-823. https://doi.org/10.1107/S1600576720005464

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