Influence of solvent on the RAFT-mediated polymerization of benzyl methacrylate (BzMA) and how to overcome the thermodynamic/kinetic limitation of morphology evolution during polymerization-induced self-assembly

Yang, Cheng-Lin; Zhong, Feng; Pan, Cai‐Yuan; Zhang, Wen-Jian

doi:10.1039/d2py00198e

Cited by 3 publications

(2 citation statements)

References 69 publications

(102 reference statements)

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“…Subsequently, PEO 45 -PETTC was used as a macroCTA to mediate the RAFT dispersion copolymerization of BzMA and PyAMA in an ethanol/water mixture (w/w = 80/20), and the target DP of the solvophobic block P(BzMA n - co -PyAMA (1– n ) ) x (wherein the subscript numbers are the proportions of BzMA units and PyAMA units, x represents the target DP of solvophobic block) was set as 20, 30, 40, 100, and 150, respectively. Using PEO as solvophilic block and BzMA as core forming monomer is a classic PISA formulation to produce polymer nano-objects with various morphologies, including micelles, nanowires, and vesicles; − thus, it was used in this study. In order to explore the effect of the amount of PyAMA on the fluorescence emission of the obtained nanoparticles, the feed molar ratio of PyAMA/BzMA was set as 0/100, 1/99, 2/98, 2.5/97.5, 3/97, and 3.5/96.5.…”

Section: Resultsmentioning

confidence: 99%

Smartphone-Enabled Platform for Direct Recognition of the Morphology of Copolymer Nano-Objects during Polymerization-Induced Self-Assembly

Yin

Pan

et al. 2022

ACS Appl. Polym. Mater.

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Polymerization-induced self-assembly (PISA) has been demonstrated as a robust method for the preparation of polymeric nanoparticles with various morphologies in high solid content. Developing efficient methods for the direct recognition of the morphologies of copolymer nanoparticles during PISA in a low-cost and simple manner is of practical significance. Herein, we proposed a fluorescent chroma method that enabled the direct recognition of the morphologies of copolymer nano-objects in the PISA process. Methacrylate monomer bearing pyrene fluorophore (PyAMA) with a broad emission region was first synthesized, which exhibited blue monomeric fluorescence and produced green excimer emission when stacked together in a dimer state. PyAMA was then used as a comonomer during the RAFT dispersion polymerization of benzyl methacrylate (BzMA) using 4-cyano-4-(2phenylethanesulfanyl-thiocarbonyl)sulfanylpentanoic acid (PETTC) capped poly(ethylene oxide) (PEO-PETTC) as a macromolecular chain transfer agent (macroCTA). Accompanying with the morphological transformation from micelles to nanowires to vesicles, the fluorescent color of the copolymer nanoparticles underwent the variation from blue to cyan to green due to the increased emission ratio of pyrene excimer to monomer (I excimer /I monomer ), and the direct observation of the nanostructural changes during PISA by naked eyes was realized. Furthermore, an easy-to-use smartphone program was elaborately designed to simplify the morphological recognition based on the fluorescent colors for different morphologies. This strategy provides a facile platform to monitor the morphological evolutions during PISA and realizes the preassessment of the morphologies of PISA-generated nanoparticles.

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Section: Resultsmentioning

confidence: 99%

Smartphone-Enabled Platform for Direct Recognition of the Morphology of Copolymer Nano-Objects during Polymerization-Induced Self-Assembly

Yin

Pan

et al. 2022

ACS Appl. Polym. Mater.

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“…Such nanoparticles exhibit promising applications in drug delivery and emulsions. , For example, MSPNs present high interfacial activities in that their different shells can extend themselves to different phases at the liquid/liquid interfaces in light of their respective phase preferences, behaving as Janus nanoparticles. − Self-assembly of amphiphilic ABC triblock copolymers or coassembly of AB/BC diblock copolymers in a selective solvent is a robust method to prepare MSPNs with tunable morphologies, in which A and C are shell-forming blocks and B is a core-forming block. ,, However, solution-based self-assembly of amphiphilic block copolymers inevitably suffers from low preparation efficiency, because of a very low polymer concentration. Polymerization-induced self-assembly (PISA), which has attracted considerable interest in recent years, − is an efficient strategy for the preparation of copolymer nanoparticles with varied morphologies including spheres, worms, vesicles, etc. Essentially, a soluble block is chain extended by a soluble monomer to form an insoluble second block in a suitable solvent, driving as-formed amphiphilic diblock copolymers in situ self-assembly during the chain growth .…”

Section: Introductionmentioning

confidence: 99%

Formation of n-Hexane-in-DMF Nonaqueous Pickering Emulsions: ABC Triblock Worms versus AB Diblock Worms

Sun

Zhou

et al. 2022

Langmuir

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Nonaqueous Pickering emulsions exhibit promising applications in many industrial areas but have been relatively less studied in the past. In this study, n-hexane-in-DMF nonaqueous Pickering emulsions stabilized by core cross-linked copolymer worms with mixed shells are demonstrated for the first time. Core cross-linked copolymer worms with mixed shells were prepared by seeded reversible addition–fragmentation chain transfer (RAFT) quasi-solution polymerization. Specifically, polystyrene-poly(4-vinylpyridine) (PS-P4VP) diblock copolymer worms were first prepared via RAFT-mediated dispersion polymerization in toluene under the given conditions using PS as both the macro-CTA and the stabilizer block. After the chemical cross-linking of P4VP cores, PS-P4VP diblock copolymer worms were chain-extended with LMA in DMF/toluene (1:9, weight ratio) mixed solvents, producing core cross-linked PS-P4VP-PLMA worms with PS/PLMA mixed shells. The as-prepared core cross-linked PS-P4VP-PLMA worms with mixed PS/PLMA shells were further utilized as Pickering emulsifiers for the generation of nonaqueous n-hexane-in-DMF Pickering emulsions. The emulsifying performances of mixed-shell copolymer worms were compared with those of their spherical and linear analogues with entirely identical chemical compositions as well as PS-P4VP diblock copolymer worm precursors, respectively.

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Polymerization‐induced self‐assembly for drug delivery: A critical appraisal

Hochreiner,

van Ravensteijn

2023

Journal of Polymer Science

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Polymerization‐induced self‐assembly (PISA) with (in situ) encapsulation of (therapeutic) cargo has proven to be an efficient preparation method for loaded polymeric micelles and polymersomes, thereby presenting significant opportunities in the field of drug delivery. However, despite extensive research efforts, no significant advances toward systematic in vivo studies or clinical applications have been achieved to date. In this Review, we outline the current state‐of‐the‐art of cargo encapsulation via PISA with a specific focus on developments achieved in the past 5 years. Considering the general requirements for functional drug delivery systems, we identify the major hurdles that still need to be overcome in order to push PISA‐derived systems from a promising academic exercise to viable candidates for clinical translation.

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Influence of solvent on the RAFT-mediated polymerization of benzyl methacrylate (BzMA) and how to overcome the thermodynamic/kinetic limitation of morphology evolution during polymerization-induced self-assembly

Abstract: Polymerization-induced self-assembly (PISA) has been demonstrated to be a powerful strategy to produce polymeric nano-objects of various morphologies. Dependent on the solubility of monomers, PISA is usually classified into two...

Cited by 3 publications

References 69 publications

Smartphone-Enabled Platform for Direct Recognition of the Morphology of Copolymer Nano-Objects during Polymerization-Induced Self-Assembly

Smartphone-Enabled Platform for Direct Recognition of the Morphology of Copolymer Nano-Objects during Polymerization-Induced Self-Assembly

Formation of n-Hexane-in-DMF Nonaqueous Pickering Emulsions: ABC Triblock Worms versus AB Diblock Worms

Polymerization‐induced self‐assembly for drug delivery: A critical appraisal

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