Shape-transformation of polymersomes from glassy and crosslinkable ABA triblock copolymers

Chidanguro, Tamuka; Ghimire, Elina; Simon, Yoan C.

doi:10.1039/d0tb01643h

Cited by 8 publications

(6 citation statements)

References 43 publications

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“…Recently, our group reported the shape transformation of glassy polymersomes from ABA triblock copolymers via a combination of osmotic pressure changes and crosslinking. 45 Using polymersomes assembled from PEG-block-poly(coumarin methacrylate)-stat-PS-block-PEG, we observed that, when exposed to osmotic pressure changes via dialysis, these vesicles only showed a size decrease but maintained their spherical morphology (Fig. 5(b)).…”

Section: Osmotic Pressure and Concentration Gradientsmentioning

confidence: 95%

Bent out of shape: towards non‐spherical polymersome morphologies

Chidanguro

Simon

2021

Polymer International

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Polymersomes have gained a lot of attention in recent years. Their compartmentalized, hollow nature, stability and ability to transport both hydrophilic and hydrophobic cargo has made them attractive for increasingly complex applications in various fields of biomedicine, catalysis and diagnostics. Progress in these fields would therefore benefit from improvements in polymersome functionality. Recently, morphological control of polymersomes, namely the fabrication of various non-spherical morphologies, has emerged as a means to enhance the usefulness of the polymersomes. In the present review, we highlight the most topical trends in this field and how these developments and the newly acquired knowledge about their nature can be leveraged towards applications.

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Section: Osmotic Pressure and Concentration Gradientsmentioning

confidence: 95%

Bent out of shape: towards non‐spherical polymersome morphologies

Chidanguro

Simon

2021

Polymer International

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“…Advances in precise block copolymer synthesis (i.e., molecular weight control, end-group fidelity, monomer selection) have led to tailorable interfacial curvature and block copolymer asymmetry that generate predictable morphologies and nanostructure organization. 13 For a given amphiphilic block copolymer system, adjustments in block volume fraction and nature (i.e., glassy 14,15 vs. soft) can generate a plethora of morphologies in dilute aqueous environments-including spherical or cylindrical micelles, 16,17 network phase and bilayers/vesicles. 18 The introduction of stimuli-responsive motifs to these self-assembled systems, such as photoresponsive functional groups (i.e., azobenzene, 19,20 o-nitrobenzene, 21 ) temperature-responsive blocks (i.e., poly(N-isopropylacrylamides), 22,23 or even so-called rigid-flexible blocks, 24 grant access to incredibly versatile and responsive nanoobjects.…”

Section: Introductionmentioning

confidence: 99%

Self‐assembly and degradation of photolabile diblock bottlebrushes

Liu,

Dugas,

Dishner

et al. 2024

Journal of Polymer Science

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Aqueous self‐assembly of amphiphilic block copolymers form diverse nanostructured morphologies depending on block volume fraction and solvophilicity. Stimuli‐responsive motifs have been combined with self‐assembled micelles to afford spatiotemporal, on‐demand encapsulation and payload release. However, the role of modular polymer architecture (i.e., bottlebrushes) in stimuli‐responsive aqueous self‐assembly is not fully understood. The synthesis, aqueous self‐assembly, and photoirradiation of photolabile, amphiphilic bottlebrush block copolymers is presented herein. Specifically, the efficient photoscission of o‐nitrobenzene motifs at the junction of a poly(norbornene o‐nitrobenzene polystyrene)‐block‐poly(norbornene polyethylene glycol) diblock bottlebrush side chain and backbone cleaved away hydrophobic polystyrene side chains and artificially increased the volume fraction of poly(ethylene glycol) (fPEG). In doing so, self‐assembled micelles readily degrade to micelle‐to‐micelle and micelle‐to‐aggregate structures after photoirradiation. Finally, this bottlebrush micelle system is used to demonstrate the efficient encapsulation and stimuli‐responsive release of Nile Red that is monitored by fluorescence spectroscopy and dynamic light scattering. The contribution of this work expands the utility of amphiphilic bottlebrush systems as highly efficient and responsive, hierarchically assembled nanomaterials.

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“…In the initial phase spanning from 1999 to 2009, shape transformation of polymer vesicles was successfully induced without the use of biological shape-modulating factors, for instance, transformation from a tubule to a vesicle by osmotic pressure, tubule generation by optical tweezers, and destruction of a vesicle by light irradiation (Table ). ,− The subsequent phase starting in 2010 witnessed the emergence of controlled shape transformation and the identification of different deformation pathways (Figure b). − Spherical vesicles have been transformed into a variety of nonspherical shapes including a disc, stomatocyte (sto), nest, sto-in-sto, tubule, disc with tubular arms, tubule with sto, etc. Although more and more shapes have been accessed, shape transformation of polymer vesicles still lies in the trial-and-error stage.…”

Section: Introductionmentioning

confidence: 99%

Shape Transformation of Polymer Vesicles

Li,

Zhang,

Sun

et al. 2024

Acc. Mater. Res.

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Metrics & MoreArticle Recommendations CONSPECTUS: Life activities, such as respiration, are accomplished through the continuous shape modulation of cells, tissues, and organs.Developing smart materials with shape-morphing capability is a pivotal step toward life-like systems and emerging technologies of wearable electronics, soft robotics, and biomimetic actuators. Drawing inspiration from cells, smart vesicular systems have been assembled to mimic the biological shape modulation. This would enable the understanding of cellular shape adaptation and guide the design of smart materials with shape-morphing capability. Polymer vesicles assembled by amphiphilic molecules are an example of remarkable vesicular systems. The chemical versatility, physical stability, and surface functionality promise their application in nanomedicine, nanoreactor, and biomimetic systems. However, it is difficult to drive polymer vesicles away from equilibrium to induce shape transformation due to the unfavorable energy landscapes caused by the low mobility of polymer chains and low permeability of the vesicular membrane. Extensive studies in the past decades have developed various methods including dialysis, chemical addition, temperature variation, polymerization, gas exchange, etc., to drive shape transformation. Polymer vesicles can now be engineered into a variety of nonspherical shapes. Despite the brilliant progress, most of the current studies regarding the shape transformation of polymer vesicles still lie in the trial-and-error stage. It is a grand challenge to predict and program the shape transformations of polymer vesicles. An in-depth understanding of the deformation pathway of polymer vesicles would facilitate the transition from the trial-and-error stage to the computing stage. In this Account, we introduce recent progress in the shape transformation of polymer vesicles. To provide an insightful analysis, the shape transformation of polymer vesicles is divided into basic and coupled deformation. First, we discuss the basic deformation of polymer vesicles with a focus on two deformation pathways: the oblate pathway and the prolate pathway. Strategies used to trigger different deformation pathways are introduced. Second, we discuss the origin of the selectivity of two deformation pathways and the strategies used to control the selectivity. Third, we discuss the coupled deformation of polymer vesicles with a focus on the switch and coupling of two basic deformation pathways. Last, we analyze the challenges and opportunities in the shape transformation of polymer vesicles. We envision that a systematic understanding of the deformation pathway would push the shape transformation of polymer vesicles from the trial-and-error stage to the computing stage. This would enable the prediction of deformation behaviors of nanoparticles in complex environments, like blood and interstitial tissue, and access to advanced architecture desirable for man-made applications.

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Shape-transformation of polymersomes from glassy and crosslinkable ABA triblock copolymers

Abstract: We used osmotic pressure changes to induce shape transformation in glassy polymersomes from crosslinkable ABA triblock copolymers. We observed that both the speed of osmotic pressure changes and order of crosslinking affect shape change behavior.

Cited by 8 publications

References 43 publications

Bent out of shape: towards non‐spherical polymersome morphologies

Bent out of shape: towards non‐spherical polymersome morphologies

Self‐assembly and degradation of photolabile diblock bottlebrushes

Shape Transformation of Polymer Vesicles

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