Silica cubosomes templated by a star polymer

Cui, Congcong; Han, Lu; Che, Shunai

doi:10.1039/c8ra09130g

Cited by 12 publications

(12 citation statements)

References 31 publications

(30 reference statements)

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“…Porous particles with internal bicontinuous nanoporous networks have become important materials for potential applications such as ultrafiltration, , drug delivery, ,, catalysis, , and nanotemplating. − The direct self-assembly of BCPs can be a versatile tool to create porous nanostructures with highly ordered cubic crystalline networks. Furthermore, polymer cubosomes with high molecular weight glassy PS blocks possess better structural stability and larger lattice parameters than lipid cubosomes.…”

Section: Potential Applications Of Polymer Cubosomesmentioning

confidence: 99%

Polymer Cubosomes: Infinite Cubic Mazes and Possibilities

Kim

2020

Acc. Chem. Res.

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Conspectus Block copolymers (BCPs) have been indispensable building blocks to create a range of soft nanostructures including discrete particulates (micelles and vesicles) and periodic structures via spontaneous assembly in bulk and in solution. The size, shape, and phase of these structures can be controlled by the rational design of the molecular structure of building blocks based on the structural analogy of BCPs to lipids and small molecule surfactants. Inverse bicontinuous cubic mesophases of polymers, or polymer cubosomes when in colloidal forms, are emerging nanostructures composed of triply periodic minimal surfaces (TPMSs) of block copolymer bilayers. Created by spontaneous assembly of BCPs in solution, polymer cubosomes internalize two nonintersecting nanochannel networks arranged in a cubic crystalline order. As well-defined porous particles with highly ordered internal structures and high surface-area-to-volume ratios, polymer cubosomes can be used for chemical reactors or bioreactors, carriers capable of cargo loading and release, and scaffolds for nanotemplating. However, despite their structural similarity to lipid cubosomes and applicability, polymer cubosomes have been only sporadically observed as an outcome of serendipity until recent studies demonstrated that BCPs could form well-defined polymer cubosomes in solution. In this Account, we describe our recent progress in creating polymer cubic mesophases and their colloidal particles (polymer cubosomes) in dilute solution. BCPs with nonlinear architectures (dendritic–linear, branched–linear, and branched–branched BCPs) preferentially self-assembled to inverse mesophases in solution when the block ratio (f), defined as a molecular weight ratio of the hydrophilic block to that of the hydrophobic block, was small (<10%). The resulting lyotropic structures transformed from flat bilayers to cubic phases of primitive cubic and double diamond lattices and finally to inverted hexagonal phases as f decreased. We proposed that the architecture of a BCP plays an important role in the preferential formation of polymer cubosomes in solution. The presence of the bulky hydrophilic block limited chain stretching of the hydrophobic polymer block, which would increase the packing parameter of the BCP to greater than unity, a prerequisite for inverse mesophase formation. The structural characteristics of polymer cubosomes, such as lattice symmetries, pore sizes, and lattice parameters, could also be controlled by fine-tuning the structural parameters of BCPs. We also suggested nonsynthetic methods to precisely control the phase and internal lattice of inverse mesophases of BCPs by the coassembly of two BCPs with different block ratios (mix-and-match approach) and the modulation of the affinity of the common solvent toward the hydrophobic block of the BCP. To investigate the potential applications of polymer cubosomes, we prepared inorganic photonic crystals using a cubosome-templated synthesis. We also discussed the utilization of cubosomes as chemical reactors by...

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Section: Potential Applications Of Polymer Cubosomesmentioning

confidence: 99%

Polymer Cubosomes: Infinite Cubic Mazes and Possibilities

Kim

2020

Acc. Chem. Res.

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“…4 In the last few years, cubosomes and hexosomes prepared from amphiphilic block copolymers with larger lattice parameters (30-60 nm) have emerged as new alternatives to conventional lipid particles and have found new applications in templating, separation, catalysis and photonics. [10][11][12][13][14][15] Typically, polymer cubosomes and hexosomes are prepared via the solution self-assembly of amphiphilic block copolymers with a high degree of asymmetry between the hydrophobic and hydrophilic blocks and possessing a molecular geometry with a packing parameter (P) higher than 1. 14,16 The self-assembled structures contain negative surface-average Gaussian curvatures, leading to inverse phases.…”

Section: Introductionmentioning

confidence: 99%

Photoluminescent polymer cubosomes prepared by RAFT-mediated polymerization-induced self-assembly

et al. 2022

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“…Solution self-assembly of block copolymers (BCPs) into inverse bicontinuous cubic (IBC) mesophases is an alternative route to the creation of highly ordered 3D polymeric nanostructures. − Polymer cubosomes, colloidal particles of IBC structures composed of triply periodic minimal surfaces of BCP bilayers, have recently been attracting attention as ordered porous materials that provide unique nanospaces for the adsorption of proteins, , drug delivery, , and nanotemplating . The symmetry and dimensions of the internal lattices of polymer cubosomes are determined by the architecture, the block ratio, and the molecular weights of polymer blocks constituting the BCP. , High-molecular-weight BCPs can self-assemble to form polymer cubosomes with large lattice parameter ( a ) comparable to Nature’s length scale exhibited by biophotonic crystals .…”

Section: Introductionmentioning

confidence: 99%

Self-Assembly of Bottlebrush Block Copolymers into Triply Periodic Nanostructures in a Dilute Solution

Kim

2020

Macromolecules

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Bottlebrush block copolymers (BBCPs) exhibit a distinct brush-like topology, which extends their conformations and, consequently, limits chain−chain entanglement in bulk forms and in concentrated solutions. These characteristics make them attractive building blocks to create well-defined nanostructures with large periodicities by self-assembly. However, self-assembly of BBCPs into periodic nanostructures in a dilute solution has rarely been studied. Here, we report the solution self-assembly of amphiphilic BBCPs with poly(ethylene glycol) (PEG) and polystyrene (PS) as pendants attached to a polynorbornene backbone. Similar to the self-assembly of conventional linear block copolymers (BCPs), the BBCPs underwent a morphological transition from spherical micelles to vesicles as their brush ratio, defined by the weight fraction of hydrophilic PEG brushes compared to the weight of the block copolymer brushes (w PEG ), decreased. We found that the BBCPs self-assembled into inverse mesophases when the value of w PEG was below 7%. In particular, highly symmetric icosahedral cubosomes of BBCPs with internal double diamond lattices were formed when allowed to undergo self-assembly for an extended time period. This condition led us to find that new morphologies from self-assembly of BBCPs in a dilute solution, such as nanotubes and tubular networks, were analogous to the reticulated cylindrical micelles observed from the nonergodic assembly of linear BCPs. Our results suggested that BBCPs could serve a class of macromolecular building blocks to create complex nanostructures with unusual morphologies.

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Silica cubosomes templated by a star polymer

Abstract: Silica cubosomes were synthesized using a silica precursor and its formation mechanism was revealed.

Cited by 12 publications

References 31 publications

Polymer Cubosomes: Infinite Cubic Mazes and Possibilities

Polymer Cubosomes: Infinite Cubic Mazes and Possibilities

Photoluminescent polymer cubosomes prepared by RAFT-mediated polymerization-induced self-assembly

Self-Assembly of Bottlebrush Block Copolymers into Triply Periodic Nanostructures in a Dilute Solution

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