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Liquid Crystalline Copolymers Containing Sulfonic and Light-Responsive Groups: From Molecular Design to Conductivity.

ABSTRACT: In the search for novel smart multifunctional liquid crystalline materials, we report the synthesis, thermal and structural characterisation, and the conductivity, of a set of new block and statistical copolymers, containing light-responsive mesogenic groups (MeOAzB), polar sulfonic acids (AMPS), and methyl(methacrylate) groups (MMA). By using a cascade of reversible addition-fragmentation chain polymerisations, RAFT, we have tailored different side-chain polymeric structures by controlling monomer composition (MeOAzB/AMPS/MMA) and configuration. We have yielded simultaneous liquid crystalline behaviour and appreciable conductivity in polymers with low concentrations of polar acid groups, by the formation of smectic phases in narrow aggregates. The light-responsiveness of the polymers, via reversible trans-to-cis photoisomerization of azobenzene groups, and the local activation of conductivity at relatively low temperatures, opens the possibility to prepare polymer electrolytes for energy conversion and storage, whose conductivity could be controlled and optimised by external stimuli, including light irradiation.

SUBMITTER: Alauddin SM

PROVIDER: S-EPMC7321325 | biostudies-literature | 2020 Jun

REPOSITORIES: biostudies-literature

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Liquid Crystalline Copolymers Containing Sulfonic and Light-Responsive Groups: From Molecular Design to Conductivity.

Alauddin Sakinah Mohd SM Aripin Nurul Fadhilah Kamalul NFK Velayutham Thamil Selvi TS Martinez-Felipe Alfonso A

Molecules (Basel, Switzerland) 20200602 11

In the search for novel smart multifunctional liquid crystalline materials, we report the synthesis, thermal and structural characterisation, and the conductivity, of a set of new block and statistical copolymers, containing light-responsive mesogenic groups (MeOAzB), polar sulfonic acids (AMPS), and methyl(methacrylate) groups (MMA). By using a cascade of reversible addition-fragmentation chain polymerisations, RAFT, we have tailored different side-chain polymeric structures by controlling mono ...[more]

PMID: 32498249

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Project description:Quantitatively understanding the self-assembly of amphiphilic macromolecules at liquid-liquid interfaces is a fundamental scientific concern due to its relevance to a broad range of applications including bottom-up nanopatterning, protein encapsulation, oil recovery, drug delivery, and other technologies. Elucidating the mechanisms that drive assembly of amphiphilic macromolecules at liquid-liquid interfaces is challenging due to the combination of hydrophobic, hydrophilic, and Coulomb interactions, which require consideration of the dielectric mismatch, solvation effects, ionic correlations, and entropic factors. Here we investigate the self-assembly of a model block copolymer with various charge fractions at the chloroform-water interface. We analyze the adsorption and conformation of poly(styrene)-block-poly(2-vinylpyridine) (PS-b-P2VP) and of the homopolymer poly(2-vinylpyridine) (P2VP) with varying charge fraction, which is controlled via a quaternization reaction and distributed randomly along the backbone. Interfacial tension measurements show that the polymer adsorption increases only marginally at low charge fractions (<5%) but increases more significantly at higher charge fractions for the copolymer, while the corresponding randomly charged P2VP homopolymer analogues display much more sensitivity to the presence of charged groups. Molecular dynamics (MD) simulations of the experimental systems reveal that the diblock copolymer (PS-b-P2VP) interfacial activity could be mediated by the formation of a rich set of complex interfacial copolymer aggregates. Circular domains to elongated stripes are observed in the simulations at the water-chloroform interface as the charge fraction increases. These structures are shown to resemble the spherical and cylindrical helicoid structures observed in bulk chloroform as the charge fraction increases. The self-assembly of charge-containing copolymers is found to be driven by the association of the charged component in the hydrophilic block, with the hydrophobic segments extending away from the hydrophilic cores into the chloroform phase.

Dataset Information

Liquid Crystalline Copolymers Containing Sulfonic and Light-Responsive Groups: From Molecular Design to Conductivity.

Publications

Liquid Crystalline Copolymers Containing Sulfonic and Light-Responsive Groups: From Molecular Design to Conductivity.

Similar Datasets

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