Poly(vinylpyridine)-containing block copolymers for smart, multicompartment particles

Lee, Dahye; Kim, Jin-Woo; Ku, Kang Hee; Li, Sheng; Shin, Jae Man; Kim, Bumjoon J.

doi:10.1039/d2py00150k

Cited by 22 publications

(22 citation statements)

References 185 publications

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“…One promising approach to tune the interfacial and structural properties of BCP-containing emulsions is the incorporation of organic/inorganic additives that interact with one of the BCP blocks. − In particular, BCPs containing pyridinyl-based monomer units have been widely used to integrate organic/inorganic guest materials via non-covalent bindings including ionic interactions and hydrogen bonding. − For example, hydrolysis of Fe(III) ions co-assembled with polystyrene- block -poly(4-vinylpyridine) (PS- b -P4VP) induced the protonation of P4VP units, which triggered the splitting of emulsion droplets into nanosized micelles . In addition, alkyl halide additives have been reported to induce an interesting shape transition of ellipsoidal polystyrene- block -poly(2-vinylpyridine) (PS- b -P2VP) BCP particles into larva and disassembled spheres .…”

Section: Introductionmentioning

confidence: 99%

Investigating Structural Effects of Quaternizing Additives on Shape Transitions of Block Copolymer Particles

et al. 2022

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Co-assembly of block copolymers (BCPs) and organic/inorganic additives affords the design of various hierarchical nanostructures. In this work, we investigate the shape-changing capabilities of poly(styrene-block-2-vinylpyridine) (PS-b-P2VP) BCP particles upon quaternization with a series of bromoalkyl benzene additives with different alkyl spacer lengths. The bromoalkyl benzene additives exhibit different hydrolyzing and quaternizing behaviors depending on their chemical structures. When benzyl bromide (BB) is used, the PS-b-P2VP BCP particles exhibit dramatic shape transitions from ellipsoids to ellipsoids with swelled discs, swelled buds, and vesicles. These morphological transitions are attributed to the synergistic quaternization and protonation of the P2VP chains via the hydrolysis of BB in aqueous media. Upon increasing the molar ratio of BB to 2VP units, the pH of the surrounding aqueous solutions significantly decreases, and the protonated P2VP domains are swelled by the surrounding water, which eventually results in interfacial instability of the emulsion interface. When the additives contain longer alkyl spacers (e.g., ethyl, butyl, and hexyl), the additives lead to a narrower range of quaternization-dependent particle morphologies due to the absence of the hydrolysis of the additives. However, a broader spectrum of particle shapes is observed for additives with longer alkyl chains, due to their stronger quaternizing capabilities. We carefully investigate the structural effect of the quaternizing additives on the change of pH, degree of quaternization, and interfacial tension to elucidate the mechanism of the additive-driven particle morphology transitions.

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Section: Introductionmentioning

confidence: 99%

Investigating Structural Effects of Quaternizing Additives on Shape Transitions of Block Copolymer Particles

et al. 2022

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“…Block copolymers (BCPs) made up of distinct different segments linked by covalent bonds can spontaneously self-assemble into various nanosized micelles or particles, which have great potential in catalysis, devices, diagnostics, and drug delivery. − Recently, it has been reported that BCPs can assemble into some unique nanostructured particles when they are confined within organic emulsion droplets. With the gradual evaporation of emulsion solvent, BCPs are aggregated together and phase separated, thus forming well-ordered polymeric nanoparticles. − This strategy is called emulsion solvent evaporation-induced self-assembly or confined self-assembly within emulsion droplets. Compared to the self-assembly of BCPs in solution or the bulk state, there is a template effect and structural frustration imposed by the spherically confined geometry as the self-assembly of BCPs occurs inside the emulsion droplet.…”

Section: Introductionmentioning

confidence: 99%

Confined Self-Assembly of Block Copolymers within Emulsion Droplets: A Perspective

Peng

Chang

et al. 2022

J. Phys. Chem. B

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When the self-assembly of block copolymers (BCPs) occurs within organic emulsion droplets in the aqueous phase, the strong structural frustration of BCP chains causes the formation of a series of well-regulated BCP particles that cannot be obtained from the self-assembly of BCPs in the bulk state or solution. In this Perspective, we review the recent progress of the self-assembly of BCPs confined in emulsion droplets. The governing factors of the structure and morphology of the as-prepared BCP particles are summarized. In addition, the applications of the as-prepared BCP particles in photonic crystals and drug release are discussed. Finally, we also give a forward-looking perspective on future challenges in this field.

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“…Besides generating BCP particles with different shapes or structures during the self-assembly process, it is more attractive to fabricate the shape-switchable BCP particles that can change their morphology and internal structure triggered by external stimuli. Stimuli-responsive surfactants have been introduced into the emulsion confined self-assembly of BCPs to regulate the internal structure and the morphologies of the resulting BCP particles via external stimuli. ,− For instance, Kim and co-workers developed pH-responsive shape-switchable particles by introducing pH-responsive surfactants into the self-assembly of polystyrene- b -poly(4-vinylpyridine) (PS- b -P4VP) within the emulsions, which exhibited the shape reversibility over continuous cycles of pH variations . In our previous work, we employed a light-active surfactant to realize reversibly light-responsive morphological transformation between onion-shaped particles with a PS outermost layer and the inverse onion-like particles with a P4VP outermost layer .…”

Section: Introductionmentioning

confidence: 99%

Temperature-Driven Reversible Shape Transformation of Polymeric Nanoparticles from Emulsion Confined Coassembly of Block Copolymers and Poly(N-isopropylacrylamide)

Wang

Chang

et al. 2022

Macromolecules

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Shape-tunable particles in response to external stimuli have gained unprecedented opportunities for their great and remarkable potential in catalysts, sensors, and clinical systems. Especially, temperature-responsive particles are highly worthwhile due to their simplicity for manipulation. Herein, we incorporated thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) into the self-assembly of block copolymers (BCPs) within confined emulsion droplets, which generated novel temperature-triggered shapeswitchable particles. At a temperature higher than the lower critical solution temperature (LCST) of PNIPAM, raspberry-like particles are formed initially. Interestingly, the raspberry-like particles can automatically transform into onion-shaped particles as the temperature is lower than the LCST of PNIPAM. This shape transformation is attributed to the temperature-mediated hydrophobic−hydrophilic transition of the anchored PNIPAM in BCP domains. This successful immobilization of PNIPAM within BCP domains is ascribed to the hydrogen bonds between them. Afterward, the onion-shaped BCP particles turn into raspberry-like particles again when the temperature is switched back to higher than the LCST of PNIPAM. More importantly, the change in BCP particle shape is reversible and can be repeated over many cycles upon adjusting the ambient temperature. In addition, the temperature-driven shape-switching BCP particles can be utilized to regulate temperature-triggered drug release, demonstrating their promising applications in clinical and biomedical systems.

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Poly(vinylpyridine)-containing block copolymers for smart, multicompartment particles

Abstract: Multicompartment particles generated by the self-assembly of block copolymers (BCPs) have received considerable attention due to their unique morphologies and functionalities. A class of important building blocks for multicomponent particles...

Cited by 22 publications

References 185 publications

Investigating Structural Effects of Quaternizing Additives on Shape Transitions of Block Copolymer Particles

Investigating Structural Effects of Quaternizing Additives on Shape Transitions of Block Copolymer Particles

Confined Self-Assembly of Block Copolymers within Emulsion Droplets: A Perspective

Temperature-Driven Reversible Shape Transformation of Polymeric Nanoparticles from Emulsion Confined Coassembly of Block Copolymers and Poly(N-isopropylacrylamide)

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