Journal of colloid and interface science · 2024
Photo-responsive supramolecular polymer bottle-brushes: The key role of the solvent on self-assembly and responsiveness.
СтатьяНазвание и аннотация: Перевод в очереди
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Harvey Luke, Schweins Ralf, Morfin Isabelle, Chahine Gilbert, Brotons Guillaume, Bouteiller Laurent, Nicol Erwan, Colombani Olivier
Аннотация
HYPOTHESIS: Supramolecular polymer bottlebrushes (SPBs) consist in the 1D self-assembly of building blocks composed of a self-assembling core with pendant polymer arms. Kinetic hurdles often hinder their stimuli-responsiveness in solution. Changing the nature of the solvent should alleviate these hurdles by modulating the self-association strength, leading to stimuli-responsive SPBs.
EXPERIMENTS: The SPBs were formed, in various solvents, by hydrogen bond-driven self-assembly of an azobenzene-bisurea decorated with poly(ethylene oxide) polymer arms. The photo-isomerization of the azobenzene unit was studied by UV/visible spectroscopy and proton NMR spectroscopy, whereas the consequences on supramolecular self-assembly were studied by small angle neutron and X-ray scattering.
FINDINGS: In water, the assembly was previously shown to be driven by both hydrogen-bonds and strong hydrophobic effects, the latter rendering the system kinetically frozen and the disassembly irreversible. Here we show that in organic solvents such as toluene or chloroform, reversible light-responsive dissociation is achieved. Solvophobic effects in these solvents are expected to be much weaker than in water, which probably allows reversibility of the light-response in the former solvents. The key role of the solvent on the reversibility of the process opens up new perspectives for the design of stimuli-responsive SPBs and their applications in various fields.
EXPERIMENTS: The SPBs were formed, in various solvents, by hydrogen bond-driven self-assembly of an azobenzene-bisurea decorated with poly(ethylene oxide) polymer arms. The photo-isomerization of the azobenzene unit was studied by UV/visible spectroscopy and proton NMR spectroscopy, whereas the consequences on supramolecular self-assembly were studied by small angle neutron and X-ray scattering.
FINDINGS: In water, the assembly was previously shown to be driven by both hydrogen-bonds and strong hydrophobic effects, the latter rendering the system kinetically frozen and the disassembly irreversible. Here we show that in organic solvents such as toluene or chloroform, reversible light-responsive dissociation is achieved. Solvophobic effects in these solvents are expected to be much weaker than in water, which probably allows reversibility of the light-response in the former solvents. The key role of the solvent on the reversibility of the process opens up new perspectives for the design of stimuli-responsive SPBs and their applications in various fields.