Cationic disulfide-functionalized worm gels

Ratcliffe, Liam P. D.; Bentley, K. J.; Wehr, Riccardo; Warren, Nicholas J.; Saunders, Brian R.; Armes, Steven P.

doi:10.1039/c7py01306j

Cited by 22 publications

(35 citation statements)

References 53 publications

(39 reference statements)

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“…Moreover, thio‐Michael addition with a quaternary amine‐based acrylate resulted in vesicles permanently bearing positive charges. Compared with the similar P(GMA‐ co ‐GlyMA)‐ b ‐PHPMA fibers, which showed a phase transition during surface protonation, no morphological transformation was observed here, probably because the change of packing parameter was not sufficient. This showcases that one should carefully consider the block copolymer design as well as the molecular structure of the reagents during surface modification of PISA nanoobjects, depending on whether the aim is to induce a morphological change or simply to introduce functionality in the initial architecture.…”

Section: Reactive Pisa Nanoobjectscontrasting

confidence: 61%

“…While the phase transition offers considerable scope for the design of new stimulus‐responsive system, crosslinking can enable tuning of this transition and, in appropriate conditions, even provide permanent nanoobject morphologies. An interesting approach to retain the phase transition character or to suppress it by crosslinking was reported through the stoichiometric control of the surface functionalization of nanofibers . Utilizing the aforementioned P(GMA‐ co ‐GlyMA) macroRAFT precursor, epoxy‐functionalized P(GMA‐ co ‐GlyMA)‐ b ‐PHPMA copolymer worm gels were prepared.…”

Section: Reactive Pisa Nanoobjectsmentioning

confidence: 99%

Section: Reactive Pisa Nanoobjectsmentioning

confidence: 99%

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Reactive and Functional Nanoobjects by Polymerization‐Induced Self‐Assembly

Lê

Keller

Delaittre

2018

Macromol. Rapid Commun.

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Polymerization‐induced self‐assembly (PISA) is becoming a standard technique for generating core–shell polymeric nanoparticles of various morphologies ranging from classic spheres to rods/fibers (“worm‐like”) and vesicles. After the initial quest for polymerization control in dispersed media, the focus of PISA research has drastically shifted, first to morphological control and now to the introduction of reactivity and functionality in order to generate useful materials. The present review is dedicated to the latter aspect. Reactivity is distinguished from functionality such as complexing, templating, and catalyzing. Approaches for either shell or core functionalization are also detailed separately.

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Section: Reactive Pisa Nanoobjectscontrasting

confidence: 61%

Section: Reactive Pisa Nanoobjectsmentioning

confidence: 99%

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Reactive and Functional Nanoobjects by Polymerization‐Induced Self‐Assembly

Lê

Keller

Delaittre

2018

Macromol. Rapid Commun.

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“…It is well‐known that the highly strained, electrophilic nature of the oxirane ring facilitates its orthogonal transformation into many useful functional groups . In the field of synthetic polymer chemistry, glycidyl methacrylate (GlyMA) is widely regarded as a highly versatile monomer: its pendent epoxy group can be readily reacted with thiols, amines, carboxylic acids, azides, and water . Recently, we reported the RAFT aqueous emulsion polymerization of glycidyl methacrylate to produce spherical diblock copolymer nanoparticles containing epoxy groups in the core‐forming block .…”

Section: Introductionmentioning

confidence: 99%

“…In contrast, we examine herein the synthesis of spherical diblock copolymer nanoparticles in which the epoxy groups are exclusively located within the stabilizer chains. In this context, Ratcliffe et al . reported the reaction of epoxy groups located within the stabilizer chains of block copolymer worms using epoxy–amine chemistry.…”

Section: Introductionmentioning

confidence: 99%

Epoxy‐Functional Sterically Stabilized Diblock Copolymer Nanoparticles via RAFT Aqueous Emulsion Polymerization: Comparison of Two Synthetic Strategies

György

Lovett

Penfold

et al. 2018

Macromol. Rapid Commun.

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Polymerization-induced self-assembly (PISA) is a powerful and versatile technique for the synthesis of a wide range of sterically stabilized diblock copolymer nano-objects. Recently, PISA has been used to prepare epoxy-functional diblock copolymer worms and spheres directly in aqueous solution by incorporating glycidyl methacrylate (GlyMA) into the core-forming hydrophobic block. Herein, the synthesis of diblock copolymer spheres via reversible addition-fragmentation chain transfer (RAFT) aqueous emulsion polymerization of benzyl methacrylate is examined, in which the epoxy groups are exclusively located within a non-ionic poly(glycerol monomethacrylate)-based stabilizer block. Two synthetic strategies are explored: i) using an epoxy-functional RAFT chain transfer agent (CTA) to place an epoxy group at the terminus of every stabilizer block and ii) incorporation of ≈1 epoxy group per stabilizer chain via copolymerization of GlyMA with glycerol monomethacrylate (GMA). The epoxy groups conferred by the GlyMA comonomer are significantly more resistant to hydrolysis than those introduced using the epoxy-functional RAFT CTA. The epoxy-functional nanoparticles are subsequently reacted with various water-soluble thiols to modify their electrophoretic behavior. Such nanoparticles are expected to offer potential applications in the context of mucoadhesion.

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Polymerization‐Induced Self‐Assembly: From Macromolecular Engineering Toward Applications

Coumes¹,

Stoffelbach²,

Rieger³

2022

Macromolecular Engineering

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Polymerization‐induced self‐assembly (PISA) is nowadays a well‐established technology that is gaining more and more attention from academics and in the industry. It relies on the extension of a solvophilic reactive chain in heterogeneous polymerization conditions. An amphiphilic block copolymer is generated and concomitantly to the growth of the solvophobic block, self‐assembly occurs. PISA was initially developed to achieve radical emulsion polymerizations in the absence of low molecular weight surfactants in order to produce surfactant‐free latexes. Shortly after, it became clear that this technology had also great potential to synthesize well‐defined amphiphilic block copolymers. Finally, researchers became more and more interested in the formed particles themselves (mainly spheres, but also worm and vesicles) and tried to functionalize them for a large variety of applications. In this article, we will start with reviewing the different PISA polymerization techniques, and highlight the possibility to use PISA as a tool to synthesize well‐defined, functional, and complex macromolecular architectures. We will then discuss the main parameters that control the particle morphology, before presenting applications of PISA‐derived particles and dispersions. The article cites more than 400 references, and presents for each polymerization technique a great number of the existing systems in tabular format.

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Cationic disulfide-functionalized worm gels

Abstract: Two types of cationic disulfide diblock copolymer worm gels are prepared by reacting cystamine with epoxy groups located within the steric stabilizer chains.

Cited by 22 publications

References 53 publications

Reactive and Functional Nanoobjects by Polymerization‐Induced Self‐Assembly

Reactive and Functional Nanoobjects by Polymerization‐Induced Self‐Assembly

Epoxy‐Functional Sterically Stabilized Diblock Copolymer Nanoparticles via RAFT Aqueous Emulsion Polymerization: Comparison of Two Synthetic Strategies

Polymerization‐Induced Self‐Assembly: From Macromolecular Engineering Toward Applications

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