Regioselective Seeded Polymerization in Block Copolymer Nanoparticles: Post‐Assembly Control of Colloidal Features

Navarro, Lucila; Thünemann, Andreas F.; Yokosawa, Tadahiro; Spiecker, Erdmann; Klinger, Daniel

doi:10.1002/anie.202208084

Cited by 11 publications

(9 citation statements)

References 89 publications

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“…[11][12][13] To produce internally structured BCP particles, [14] evaporation-induced confined assembly (EICA) has become an increasingly popular method, due to its versatility and controllability. [15][16][17][18][19][20][21] There, a BCP in DOI: 10.1002/marc.202300123 organic solvent is emulsified with an aqueous surfactant solution, before the organic solvent is allowed to evaporate. During evaporation, the BCP concentration increases, leading to microphase separation and formation of solid microparticles that show internal periodic structures deriving mainly from the composition of the BCP.…”

Section: Introductionmentioning

confidence: 99%

Effect of Surfactant Selectivity on Shape and Inner Morphology of Triblock Terpolymer Microparticles

Trömer

Zirdehi

Nikoubashman

et al. 2023

Macromol. Rapid Commun.

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The confined assembly of block copolymers (BCPs) has become a useful tool to prepare microparticles with controlled anisotropy and inner structure. While a solid understanding of the behavior of AB diblock copolymers exists, knowledge on the parameters affecting ABC triblock terpolymer assembly is much more limited. In this work, the effect of block‐selective surfactants, sodium‐4‐vinylbenzenesulfonate (VBS) and sodium dodecylsulfate (SDS), is analyzed in the evaporation‐induced confined assembly (EICA) of a polystyrene‐block‐polybutadiene‐block‐poly(methyl methacrylate) triblock terpolymer (SBM). Despite using the same terpolymer and emulsification process, SDS results in ellipsoidal microparticles with axially stacked lamellae, while VBS results in spherical microparticles with concentric lamellae or 3D spiral morphology. This change in morphology upon switching the surfactant is further substantiated by molecular simulations and enhances the understanding of terpolymer microphase separation in confinement.

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Section: Introductionmentioning

confidence: 99%

Effect of Surfactant Selectivity on Shape and Inner Morphology of Triblock Terpolymer Microparticles

Trömer

Zirdehi

Nikoubashman

et al. 2023

Macromol. Rapid Commun.

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“…23 Ellipsoidal BCP particles also become an important platform for controllable selective functionalization in the precise spatial domains to produce chemically anisotropic colloids. 10,12,24 Furthermore, the postassembly treatment for these BCP particles via shape transformation can enrich their morphological diversity and functions further. For example, the disassembly of these stacking disks will produce dissociated disks that can be functionalized selectively.…”

Section: ■ Introductionmentioning

confidence: 99%

“…The hierarchical block copolymer (BCP) nanostructures gained extensive attention recently for their great application potential. − Ellipsoidal BCP nanostructures composed of stacking lamellae are a kind of important assembled nanostructures because they are similar to the chloroplast thylakoid (granum) in structure, which plays an important role in plant photosynthesis. With the highly ordered axially stacked lamellae, they showed switchable reflecting color over the entire visible spectrum because of the photonic multilayered structure, , and they further became a Salmonella photonic sensor after antibody modification .…”

Section: Introductionmentioning

confidence: 99%

“…With the highly ordered axially stacked lamellae, they showed switchable reflecting color over the entire visible spectrum because of the photonic multilayered structure, , and they further became a Salmonella photonic sensor after antibody modification . Ellipsoidal BCP particles also become an important platform for controllable selective functionalization in the precise spatial domains to produce chemically anisotropic colloids. ,, Furthermore, the post-assembly treatment for these BCP particles via shape transformation can enrich their morphological diversity and functions further. For example, the disassembly of these stacking disks will produce dissociated disks that can be functionalized selectively. , On the other hand, the ellipsoidal particles can change to larva-like, pupa-like, swelled disk, nanocup, onion-like, and vesicle shapes via further interfacial engineering.…”

Section: Introductionmentioning

confidence: 99%

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Interfacial Engineering of Block Copolymer Nanostructures: Morphology and Solvent Stability

Zhang

et al. 2023

Langmuir

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Interfacial engineering is a critical pathway for modulating the self-assembled nanostructures of block copolymers (BCPs) during solvent exchange. Herein, we demonstrated the generation of different stacked lamellae of polystyrene-block-poly(2-vinyl pyridine) (PS-b-P2VP) nanostructures during solvent exchange by using phosphotungstic acid (PTA) or PTA/NaCl aqueous solution as the nonsolvent. The participation of PTA in the confined microphase separation of PS-b-P2VP in droplets increases the volume fraction of P2VP and decreases the tension at the oil/water interface. Moreover, the addition of NaCl to the PTA solution can further increase the surface coverage of P2VP/PTA on droplets. All factors impact the morphology of assembled BCP nanostructures. In the presence of PTA, ellipsoidal particles composed of alternatively stacked lamellae of PS and P2VP were formed (named BP), whereas, in the coexistence of PTA and NaCl, they changed to stacked disks with PS-core–P2VP-shell (called BPN). The different structures of assembled particles induce their different stabilities in solvents and different dissociation conditions as well. The dissociation of BP particles was easy because PS chains were only entangled together which can be swollen in toluene or chloroform. However, the dissociation of BPN was hard, requiring an organic base in hot ethanol. The structural difference in BP and BPN particles further extended to their dissociated disks, which makes the cargo (like R6G) loaded on these disks to show a different stability in acetone. This study demonstrated that a subtle structural change can greatly affect their properties.

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“…[16][17][18][19][20] As mentioned above, once the particles have been obtained, solvent vapor annealing (SVA) and surfactant are commonly used to regulate both the apparent shape and inner structure of these particles. [21][22][23][24][25] In more details, the suspension is first put into a close chamber containing organic solvent vapor. The solvent dissolves, penetrates into the BCP-rich region and swells the particles.…”

Section: Introductionmentioning

confidence: 99%

The Process‐Directed Self‐Assembly of Block Copolymer Particles

Zhu

Huang

Zhang

et al. 2023

Macromol. Rapid Commun.

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The kinetic paths of structural evolution and formation of block copolymer (BCP) particles are explored using dynamic self‐consistent field theory (DSCFT). It is shown that the process‐directed self‐assembly of BCP immersed in a poor solvent leads to the formation of striped ellipsoids, onion‐like particles and double‐spiral lamellar particles. The theory predicts a reversible path of shape transition between onion‐like particles and striped ellipsoidal ones by regulating the temperature (related to the Flory–Huggins parameter between the two components of BCP, χAB) and the selectivity of solvent toward one of the two BCP components. Furthermore, a kinetic path of shape transition from onion‐like particles to double‐spiral lamellar particles, and then back to onion‐like particles is demonstrated. By investigating the inner‐structural evolution of a BCP particle, it is identified that changing the intermediate bi‐continuous structure into a layered one is crucial for the formation of striped ellipsoidal particles. Another interesting finding is that the formation of onion‐like particles is characterized by a two‐stage microphase separation. The first is induced by the solvent preference, and the second is controlled by the thermodynamics. The findings lead to an effective way of tailoring nanostructure of BCP particles for various industrial applications.

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Regioselective Seeded Polymerization in Block Copolymer Nanoparticles: Post‐Assembly Control of Colloidal Features

Cited by 11 publications

References 89 publications

Effect of Surfactant Selectivity on Shape and Inner Morphology of Triblock Terpolymer Microparticles

Effect of Surfactant Selectivity on Shape and Inner Morphology of Triblock Terpolymer Microparticles

Interfacial Engineering of Block Copolymer Nanostructures: Morphology and Solvent Stability

The Process‐Directed Self‐Assembly of Block Copolymer Particles

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