Virus-like particles composed of sphere-forming polystyrene-block-poly(t-butyl acrylate) (PS-b-PtBA) and control of surface morphology by homopolymer blending

Hirai, Yasuaki; Wakiya, Takeshi; Yabu, Hiroshi

doi:10.1039/c7py00013h

Cited by 25 publications

(21 citation statements)

References 48 publications

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“…For example, Robb et al described the use of self‐assembled nanoparticles from post‐modified poly(allyl glycidyl ether)‐ b ‐polylactide as modular delivery vehicles . Very recently, Hirai et al reported the preparation of virus‐like particles using an asymmetric polystyrene‐ b ‐poly( t ‐butyl acrylate) BCP and Schmidt et al that of reactive ellipsoidal striped nanoparticles from polystyrene‐ b ‐poly(2‐vinylpyridine) BCP blended with analogue functional homopolymers …”

Section: Introductionmentioning

confidence: 99%

Surface‐Reactive Patchy Nanoparticles and Nanodiscs Prepared by Tandem Nanoprecipitation and Internal Phase Separation

Varadharajan

Turgut

Lahann

et al. 2018

Adv Funct Materials

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Nanoparticles with structural or chemical anisotropy are promising materials in domains as diverse as cellular delivery, photonic materials, or interfacial engineering. The surface chemistry may play a major role in some of these contexts. Introducing reactivity into such polymeric nanomaterials is thus of great potential, yet is still a concept in its infancy. In the current contribution, a simple nanoprecipitation technique leads to nanoparticles with diameters as low as 150 nm and well-defined reactive surface patches of less than 30 nm in width, as well as surface-reactive flat, disc-like nanoparticles with corresponding dimensions, via an additional crosslinking/delamination sequence. To this aim, chemically doped block copolymers (BCPs) are employed. Control over morphology is attained by tuning preparation conditions, such as polymer concentration, solvent mixture composition, and blending with non-functional BCP. Surface reactivity is demonstrated using a modular ligation method for the site-selective immobilization of thiol molecules. The current approach constitutes a straightforward methodology requiring minimal engineering to produce nanoparticles with confined surface reactivity and/or shape anisotropy.

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Section: Introductionmentioning

confidence: 99%

Surface‐Reactive Patchy Nanoparticles and Nanodiscs Prepared by Tandem Nanoprecipitation and Internal Phase Separation

Varadharajan

Turgut

Lahann

et al. 2018

Adv Funct Materials

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“…As an example, the morphologies formed inside microspheres will transition between spherical, cylindrical, and lamellar with increases in the proportion of one polymer block . Figure a shows a poly(styrene ‐block‐ tert‐butyl acrylate) (PS‐ b ‐PtBA) microsphere obtained by the SORP technique that exhibits a dot‐like morphology . At a copolymerization ratio of almost 0.5, the morphologies of the block copolymers changed from spherical to cylindrical and then to lamellar.…”

Section: Controlling the Structures Of Phase Separated Polymer Microsmentioning

confidence: 99%

“…Block copolymer microspheres composed of a) PS‐ b ‐PtBA spheres (Reproduced with permission . Copyright 2017, Royal Society of Chemistry), and b) PS‐ b ‐PI cylinders and c) lamellae (Reproduced with permission .…”

Section: Controlling the Structures Of Phase Separated Polymer Microsmentioning

confidence: 99%

Fabrication of Nanostructured Composite Microspheres Based on the Self‐Assembly of Polymers and Functional Nanomaterials

Yabu

2019

Part & Part Syst Charact

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Achieving the specific properties required for the applications discussed above necessitates control over the morphologies of the polymer particles as well as the precise alignment of functional nanoparticles at particle interiors and surfaces. Studies using seed polymerization and related so-called second generation particle preparation techniques have succeeded in preparing polymer microspheres having anisotropic morphologies. [10] These techniques for the synthesis of nonspherical polymer microparticles are both powerful and practical, although the particle shape has been found to be greatly affected by the preparation conditions employed. These conditions involve numerous parameters, and so controlling the particle morphology remains challenging. In addition to first and second generation particle preparation technologies employing emulsion polymerization, recent studies have demonstrated the fabrication of nanostructured microspheres based on the phase separation of polymers. [11,12] These methods can be considered as the third generation of progress in this field and allow the tuning of particle morphologies in association with phase separation theories developed during prior work with bulk polymer blends, alloys, and composites. The alignment of nanoparticles in phase separated polymer microspheres could lead to nanostructured particles with many practical applications. Figure 1 presents some of the many methods developed for the synthesis of polymer microspheres. This diagram indicates representative existing approaches used to obtain controlled particle sizes, as well as specific phases in the interior and at the surfaces of such microspheres, and can be divided into two main categories; top-down and bottom-up. These two types of procedures differ with regard to the process used to form internal and surface structures. The polymerization or crosslinking of uniformly sized oil/water (O/W) or water/oil (W/O) emulsion droplets formed by microfluidic devices is a well-known topdown fabrication technique used to produce structured polymer microspheres with sizes on the scale of tens of micrometers. [13] Taking advantage of the laminar flow inside narrow capillaries, multiple phases can be formed in the interiors of the emulsion droplets, resulting in the formation of multiphase polymer microspheres. [14] In contrast, in the case of bottom-up approaches, the phase separation of polymers is used to create internal and surface nanostructures. The latter methods have received considerable attention because they permit size control on a variety of size scales as well as morphological tuning. [15] This Review examines recent developments in the morphological control of polymer microspheres fabricated via the phase separation of polymers as well as the alignment of functional nanoparticles inside microspheres prepared by so-called bottom-up synthesis techniques. Several methods for adjusting the internal and surface morphologies of polymer microspheres based on the phase separation of polymer blends and block copoly...

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“…[12][13][14][15][16][17][18] Hydrophobic homopolymers (HPs) have been found to be efficient morphology modifiers for BCP aggregates. [19][20][21][22][23][24][25][26][27] In most of the reported BCP/HP self-assembly systems, the molecular weight of the hydrophobic core-forming HPs is lower than or…”

Section: Introductionmentioning

confidence: 99%

“…A variety of strategies such as introducing a second component, controlling copolymer composition, and altering self‐assembly condition have been applied to tune the morphology of BCP aggregates . Hydrophobic homopolymers (HPs) have been found to be efficient morphology modifiers for BCP aggregates . In most of the reported BCP/HP self‐assembly systems, the molecular weight of the hydrophobic core‐forming HPs is lower than or close to that of the core‐forming blocks in BCPs.…”

Section: Introductionmentioning

confidence: 99%

Role of High‐Molecular‐Weight Homopolymers on Block Copolymer Self‐Assembly: From Morphology Modifier to Template

Zhang

Cai

et al. 2018

Macro Chemistry & Physics

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For block copolymer (BCP)/homopolymer self‐assembly systems, the molecular weight of homopolymers is usually lower than that of BCPs. Herein, the cooperative self‐assembly of polystyrene‐b‐poly(ethylene glycol) (PS‐b‐PEG) BCPs with high‐molecular‐weight polystyrene (PS) homopolymers is reported. The molecular weight of PS homopolymers is 3–63 times that of the PS blocks. Typically, a spherical micelle–vesicle–large sphere morphology transition is observed by increasing the weight fraction of PS homopolymers in the polymer mixtures (f HP). Dynamic process studies reveal that with adding water to the solution of polymer mixtures in organic solvent, the homopolymers first collapse into globules, and their size increases with f HP and the molecular weight. Then these PS globules cooperatively self‐assemble with the PS‐b‐PEG BCPs. Depending on their size, these PS globules play different roles in the self‐assembly process. Small PS globules act as morphology modifiers inducing the micelle–vesicle transition, while large PS globules serve as self‐assembly templates for PS‐b‐PEG resulting in large spheres.

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Virus-like particles composed of sphere-forming polystyrene-block-poly(t-butyl acrylate) (PS-b-PtBA) and control of surface morphology by homopolymer blending

Abstract: Submicron-sized virus-like particles comprising asymmetric PS-b-PtBA diblock copolymer particles having dot patterns on their surface were successfully prepared by a simple solvent evaporation process.

Cited by 25 publications

References 48 publications

Surface‐Reactive Patchy Nanoparticles and Nanodiscs Prepared by Tandem Nanoprecipitation and Internal Phase Separation

Surface‐Reactive Patchy Nanoparticles and Nanodiscs Prepared by Tandem Nanoprecipitation and Internal Phase Separation

Fabrication of Nanostructured Composite Microspheres Based on the Self‐Assembly of Polymers and Functional Nanomaterials

Role of High‐Molecular‐Weight Homopolymers on Block Copolymer Self‐Assembly: From Morphology Modifier to Template

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