Synthesis of Thermoresponsive Diblock Copolymer Nano-Objects via RAFT Aqueous Emulsion Polymerization of Hydroxybutyl Methacrylate

Hunter, Saul J.; Penfold, Nicholas J. W.; Jones, Elizabeth R.; Zinn, Thomas; Mykhaylyk, Oleksandr O.; Armes, Steven P.

doi:10.1021/acs.macromol.2c00379

Cited by 11 publications

(10 citation statements)

References 128 publications

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“…[3,19,[20][21][22][23][24][25][26][27]28,29] The latter formulations are often associated with kineticallytrapped spherical morphologies even when targeting highly asymmetric diblock copolymer compositions, [30][31][32][33] although access to either worms or vesicles can be achieved for certain formulations. [12,[34][35][36][37] Two of the most common hydrophilic steric stabilizers used in the aqueous PISA literature are poly(ethylene glycol) (PEG) [38,39] and poly(glycerol monomethacrylate) (PGMA). [12,34,[40][41][42][43][44][45][46][47] Recently, we reported a new hybrid water-soluble polymer that combined the structural feature associated with PEG and PGMA (see Scheme S1, Supporting Information).…”

Section: Introductionmentioning

confidence: 99%

Histidine‐Functionalized Diblock Copolymer Nanoparticles Exhibit Enhanced Adsorption onto Planar Stainless Steel

Brotherton

Josland

György

et al. 2023

Macromol. Rapid Commun.

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RAFT aqueous emulsion polymerization of isopropylideneglycerol monomethacrylate (IPGMA) is used to prepare a series of PGEO5MA 46 -PIPGMA y nanoparticles, where PGEO5MA is a hydrophilic methacrylic steric stabilizer block bearing pendent cis-diol groups. TEM studies confirm a spherical morphology while dynamic light scattering (DLS) analysis indicated that the z-average particle diameter can be adjusted by varying the target degree of polymerization for the core-forming PIPGMA block. Periodate oxidation is used to convert the cis-diol groups on PGEO5MA 46 -PIPGMA 500 and PGEO5MA 46 -PIPGMA 1000 nanoparticles into the analogous aldehyde-functionalized nanoparticles, which are then reacted with histidine via reductive amination. In each case, the extent of functionalization is more than 99% as determined by 1 H NMR spectroscopy. Aqueous electrophoresis studies indicate that such derivatization converts initially neutral nanoparticles into zwitterionic nanoparticles with an isoelectric point at pH 7. DLS studies confirmed that such histidine-derivatized nanoparticles remain colloidally stable over a wide pH range. A quartz crystal microbalance is employed at 25°C to assess the adsorption of both the cis-diol-and histidine-functionalized nanoparticles onto planar stainless steel at pH 6. The histidine-bearing nanoparticles adsorb much more strongly than their cis-diol counterparts. For the highest adsorbed amount of 70.5 mg m -2 ,SEM indicates a fractional surface coverage of 0.23 for the adsorbed nanoparticles.

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Section: Introductionmentioning

confidence: 99%

Histidine‐Functionalized Diblock Copolymer Nanoparticles Exhibit Enhanced Adsorption onto Planar Stainless Steel

Brotherton

Josland

György

et al. 2023

Macromol. Rapid Commun.

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“…Among these, thermo-responsive polymers that are able to sharply change their solubility in the solvent following temperature modifications are particularly appealing because of the ease of application of thermal stimuli. Indeed, thermo-responsive polymers have attracted considerable attention for controlled drug delivery and tissue engineering. , At the same time, only few studies investigate thermo-responsive polymers synthesized in non-polar media, mainly discussing the influence of the thermo-responsive segment length on the phase separation. ,,− …”

Section: Introductionmentioning

confidence: 99%

Role of the Polymer Microstructure in Controlling Colloidal and Thermo-Responsive Properties of Nano-Objects Prepared Via RAFT Polymerization in a Non-polar Medium

et al. 2023

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After having demonstrated their potential in biomedical applications, thermo-responsive block copolymers that are able to self-assemble into nano-objects in response to temperature modifications are becoming more and more appealing in other sectors, such as the oil and gas and lubricant fields. Reversible addition−fragmentation chain transfer (RAFT) polymerization-induced self-assembly has been demonstrated as a valuable strategy for producing nano-objects from modular block copolymers in non-polar media, required for the mentioned applications. Although the influence of the nature and size of the thermo-responsive block of these copolymers on the properties of the nano-objects is extensively studied in the literature, the role of the solvophilic block is often neglected. In this work, we elucidate the role of the main microstructural parameters, including those of the solvophilic portion, of block copolymers produced by RAFT polymerization in the hydrocarbon blend decane/toluene 50:50 v/v on the thermo-responsive behavior and colloidal properties of the resulting nano-objects. Two long-aliphatic chain monomers were employed for the synthesis of four macromolecular chain transfer agents (macroCTAs), with increasing solvophilicity according to the number of units (n) or length of the alkyl side chain (q). Subsequently, the macroCTAs were chain-extended with different repeating units of di(ethylene glycol) methyl ether methacrylate (p), leading to copolymers that are able to self-assemble below a critical temperature. We show that this cloud point can be tuned by acting on n, p, and q. On the other hand, the colloidal stability, expressed in terms of area of the particle covered by each solvophilic segment, is only a function of n and q, which provides a way for controlling the size distribution of the nano-objects and to decouple it from the cloud point.

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“…Various thermosensitive hydrogels have been developed over the past few decades, − among which, the PEG/polyester thermogel is one of the most promising biomedical materials. − Degradation is, as a significant character of this kind of materials, particularly useful for regenerative biomaterials and drug delivery vehicles, yet has been regarded as a “destroy” factor for many years. The present study highlights that degradation could be utilized as a “construction” factor to influence materials in a dynamic manner.…”

Section: Discussionmentioning

confidence: 99%

Degradation-Influenced/Induced Self-Assembly of Copolymers with the Combinatory Effects of Changed Molecular Weight and Dispersity

Wei

Cui

et al. 2023

Macromolecules

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Biodegradable polymers constitute an important class of new materials, in particular biomedical materials. While degradation has been studied extensively as a "destroy" factor of a material for many years, it is less investigated when treated as a "construction" factor to influence a material in a dynamic manner. Herein, we examined a hydrolyzable amphiphilic block copolymer and found significant reorganization of the condensed state of copolymers during degradation in water. The reorganization occurs, depending upon polymer composition and experimental condition, both mesoscopically and macroscopically, which we term as "degradation-influenced/induced self-assembly (DISA)". To this end, we developed dynamic Monte Carlo simulations by introduction of hydrolysis probability while keeping the chain microrelaxation modes. A series of dynamic Monte Carlo simulations of amphiphilic triblock copolymers was carried out in a selective solvent, and three types of DISA were revealed: micelle 1 to micelle 2, sol−gel 1 to sol−gel 2, and precipitate to sol−gel−precipitate. Subsequently, amphiphilic block copolymers poly(D,L-lactide)-bpoly(ethylene glycol)-b-poly(D,L-lactide) (PLA-PEG-PLA) were synthesized, and all of the three DISA types were confirmed in experiments of the aqueous systems of three copolymers of different block lengths. We found that the DISA was regulated by both the decrease of molecular weight (MW) and the increase of dispersity. Here the term "dispersity" emphasizes not only the conventional molecular weight distribution (MWD) of all species but also the more diversified components after degradation, which include blends of copolymers and the degradation-generated homopolymers and oligomers. We also employed fluorescence resonance energy transfer to confirm the percolated network of semibald micelles underlying the temperature-induced physical hydrogel in such systems. The present study illustrates that degradation can act as a new strategy to influence the hierarchical selfassembly of amphiphilic block copolymer chains.

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Synthesis of Thermoresponsive Diblock Copolymer Nano-Objects via RAFT Aqueous Emulsion Polymerization of Hydroxybutyl Methacrylate

Cited by 11 publications

References 128 publications

Histidine‐Functionalized Diblock Copolymer Nanoparticles Exhibit Enhanced Adsorption onto Planar Stainless Steel

Histidine‐Functionalized Diblock Copolymer Nanoparticles Exhibit Enhanced Adsorption onto Planar Stainless Steel

Role of the Polymer Microstructure in Controlling Colloidal and Thermo-Responsive Properties of Nano-Objects Prepared Via RAFT Polymerization in a Non-polar Medium

Degradation-Influenced/Induced Self-Assembly of Copolymers with the Combinatory Effects of Changed Molecular Weight and Dispersity

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