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Cubosomes from hierarchical self-assembly of poly(ionic liquid) block copolymers.

ABSTRACT: Cubosomes are micro- and nanoparticles with a bicontinuous cubic two-phase structure, reported for the self-assembly of low molecular weight surfactants, for example, lipids, but rarely formed by polymers. These objects are characterized by a maximum continuous interface and high interface to volume ratio, which makes them promising candidates for efficient adsorbents and host-guest applications. Here we demonstrate self-assembly to nanoscale cuboidal particles with a bicontinuous cubic structure by amphiphilic poly(ionic liquid) diblock copolymers, poly(acrylic acid)-block-poly(4-vinylbenzyl)-3-butyl imidazolium bis(trifluoromethylsulfonyl)imide, in a mixture of tetrahydrofuran and water under optimized conditions. Structure determining parameters include polymer composition and concentration, temperature, and the variation of the solvent mixture. The formation of the cubosomes can be explained by the hierarchical interactions of the constituent components. The lattice structure of the block copolymers can be transferred to the shape of the particle as it is common for atomic and molecular faceted crystals.

SUBMITTER: He H

PROVIDER: S-EPMC5241804 | biostudies-other | 2017 Jan

REPOSITORIES: biostudies-other

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Cubosomes from hierarchical self-assembly of poly(ionic liquid) block copolymers.

He Hongkun H Rahimi Khosrow K Zhong Mingjiang M Mourran Ahmed A Luebke David R DR Nulwala Hunaid B HB Möller Martin M Matyjaszewski Krzysztof K

Nature communications 20170116

Cubosomes are micro- and nanoparticles with a bicontinuous cubic two-phase structure, reported for the self-assembly of low molecular weight surfactants, for example, lipids, but rarely formed by polymers. These objects are characterized by a maximum continuous interface and high interface to volume ratio, which makes them promising candidates for efficient adsorbents and host-guest applications. Here we demonstrate self-assembly to nanoscale cuboidal particles with a bicontinuous cubic structur ...[more]

PMID: 28091605

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Project description:Cu(0)-mediated atom transfer radical polymerization was used to synthesize a poly(ionic liquid), poly[4-vinylbenzyl-3-butylimidazolium bis(trifluoromethylsulfonyl)imide] (PVBBImTf2N), a stimuli-responsive polyelectrolyte, poly[2-(dimethylamino)ethyl methacrylate] (PDMAEMA), and a novel block copolymer formed from these two polymers. The synthesis of the block copolymer, poly[2-(dimethylamino) ethyl methacrylate]-block-[poly(4-vinylbenzyl-3-butylimidazolium bis(trifluoromethylsulfonyl)imide] (PDMAEMA-b-PVBBImTf2N), was examined to evaluate the control of "livingness" polymerization, as indicated by molecular weight, characterizations of degree of polymerization, and 1HNMR spectroscopy. 2D DOSY NMR measurements revealed the successful formation of block copolymer and the connection between the two polymer blocks. PDMAEMA-b-PVBBImTf2N was further characterized for supramolecular interactions in both the bulk and solution states through FTIR and 1H NMR spectroscopies. While the block copolymer demonstrated similar intermolecular behavior to the PIL homopolymer in the bulk state as indicated by FTIR, hydrogen bonding and counterion interactions in solution were observed in polar organic solvent through 1H NMR measurements. The DLS characterization revealed that the PDMAEMA-b-PVBBImTf2N block copolymer forms a network-like aggregated structure due to a combination of hydrogen bonding between the PDMAEMA and PIL group and electrostatic repulsive interactions between PIL blocks. This structure was found to collapse upon the addition of KNO3 while still maintaining hydrogen bonding interactions. AFM-IR analysis demonstrated varied morphologies, with spherical PDMAEMA in PVBBImTf2N matrix morphology exhibited in the region approaching the film center. AFM-IR further revealed signals from silica nano-contaminates, which selectively interacted with the PDMAEMA spheres, demonstrating the potential for the PDMAEMA-b-PVBBImTf2N PIL block copolymer in polymer-inorganic nanoparticle composite applications.

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

Cubosomes from hierarchical self-assembly of poly(ionic liquid) block copolymers.

Publications

Cubosomes from hierarchical self-assembly of poly(ionic liquid) block copolymers.

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