Surface and Particle Modification via
            <scp>RAFT</scp>
            Polymerization: An Update

Pribyl, Julia; Benicewicz, Brian C.

doi:10.1002/9783527821358.ch22

Cited by 5 publications

(4 citation statements)

References 100 publications

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“…The tethering of polymer chains to the surface of nanoparticles to form “brush particles” (aka “hairy particles”) has been shown to provide one-component hybrid materials with improved properties such as biocompatibility, enhanced thermal conductivity, or dielectric breakdown strength that depends on the architecture and composition of the brush particle system. − Recent advances in the surface-initiated controlled radical polymerization (SI-CRP) significantly expanded the control over structural parameters of surface-bound polymer ligands, such as degree of polymerization, dispersity, or grafting density. ,− This enabled the synthesis of brush particle systems with structural and dynamical properties that are tunable across the range of soft (polymer-like) to hard (particle-like) interactions. , Other advantageous features of SI-CRP include the ability to control the chain architecture via the concurrent or sequential reaction of distinct monomers, thus enabling the synthesis of random, gradient, or block copolymer brushes. − Copolymerization affords new opportunities to design the structure and properties of brush particle-based materials. Elucidation of the structure–property relations in copolymer brush particle systems with varied architecture therefore not only promises new insights into the physics of microstructured colloidal systems but also holds opportunities for the design of hybrid materials with novel functionalities.…”

Section: Introductionmentioning

confidence: 99%

Topologically Induced Heterogeneity in Gradient Copolymer Brush Particle Materials

Zhao

Wang

et al. 2022

Macromolecules

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A facile synthetic route toward silica brush particles with random and gradient copolymer grafts comprised of n-butyl acrylate (BA) and methyl methacrylate (MMA) using surface-initiated atom transfer radical polymerization (SI-ATRP) was developed. The effect of chain architecture on the structure and thermomechanical properties of copolymer-tethered brush particle films was investigated and compared to linear copolymer analogues. Random copolymer brush systems displayed a uniform and narrow glass transition, and the dependence of the glass-transition temperature followed a similar trend as for linear copolymers. In contrast, gradient brush materials featured a splitting of the glass-transition temperature with increasing MMA content along with a step-like increase of Young’s modulus and a decrease in ductility. The results were interpreted in terms of the effect of brush architecture on the microstructure of films. The results suggested a “molecularly uniform” microstructure in films of the random brush as well as linear random and linear gradient copolymer systems. In contrast, gradient brush systems featured a heterogeneous microstructure in which MMA-rich regions acted as “traps” that reduced chain mobility. The formation of compositional heterogeneity was rationalized by the “prescribed orientation” of gradient copolymer chains near the particle interface that amplified composition fluctuations and hence local segregation of repeat units. The results highlight the need for a better understanding of the role of “geometric constraints” on the physical properties of copolymer brush particle-based hybrid materials and the opportunity for multiple property enhancement by control of segment distribution in addition to the overall composition.

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Section: Introductionmentioning

confidence: 99%

Topologically Induced Heterogeneity in Gradient Copolymer Brush Particle Materials

Zhao

Wang

et al. 2022

Macromolecules

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“…In the grafting-through approach, the polymerization is not initiated at the surface, but polymerizable functional groups on the surface are quickly incorporated into the growing polymer, resulting in a tethered chain (though not always at the chain end). For many preformed proteins and biological macromolecules, grafting-to is the dominant approach while grafting-from is often used for synthetic polymers due to the degree of control and broader range of graft densities that can be obtained. , …”

Section: Penetration Of Biofilms: the Major Barrier Of In Situ Infect...mentioning

confidence: 99%

Nanotargeting of Resistant Infections with a Special Emphasis on the Biofilm Landscape

et al. 2021

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Bacterial resistance to antimicrobial compounds is a growing concern in medical and public health circles. Overcoming the adaptable and duplicative resistance mechanisms of bacteria requires chemistry-based approaches. Engineered nanoparticles (NPs) now offer unique advantages toward this effort. However, most in situ infections (in humans) occur as attached biofilms enveloped in a protective surrounding matrix of extracellular polymers, where survival of microbial cells is enhanced. This presents special considerations in the design and deployment of antimicrobials. Here, we review recent efforts to combat resistant bacterial strains using NPs and, then, explore how NP surfaces may be specifically engineered to enhance the potency and delivery of antimicrobial compounds. Special NP-engineering challenges in the design of NPs must be overcome to penetrate the inherent protective barriers of the biofilm and to successfully deliver antimicrobials to bacterial cells. Future challenges are discussed in the development of new antibiotics and their mechanisms of action and targeted delivery via NPs.

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“…Nanoparticle brushes represent a class of hybrid materials that combine functional polymers with inorganic/organic nanostructured compounds. − Over the decades, with the advancements in nanoparticle surface modification strategies − and various surface-initiated polymerization methods, − polymer nanohybrids with tailored architectures have gathered significant attention . One key advantage is that the nanoparticles (NPs) can retain their inherent properties while polymer grafts afford improved stability and processability of nanoparticle-based materials. − Furthermore, the connectivity and interactions between polymer and particle components can generate synergistic effects and result in novel properties that render polymer-modified nanoparticles (also brush particles) interesting for applications such as lubricants, lithography, battery electrodes, and gas separation. − …”

Section: Introductionmentioning

confidence: 99%

“…Nanoparticle brushes represent a class of hybrid materials that combine functional polymers with inorganic/organic nanostructured compounds. 1 − 5 Over the decades, with the advancements in nanoparticle surface modification strategies 6 − 9 and various surface-initiated polymerization methods, 10 − 14 polymer nanohybrids with tailored architectures have gathered significant attention. 15 One key advantage is that the nanoparticles (NPs) can retain their inherent properties while polymer grafts afford improved stability and processability of nanoparticle-based materials.…”

Section: Introductionmentioning

confidence: 99%

Composition-Orientation Induced Mechanical Synergy in Nanoparticle Brushes with Grafted Gradient Copolymers

Yin,

Zhao,

Jeong

et al. 2023

Macromolecules

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Gradient poly(methyl methacrylate/ n -butyl acrylate) copolymers, P(MMA/BA), with various compositional ratios, were grafted from surface-modified silica nanoparticles (SiO 2 - g -PMMA- grad -PBA) via complete conversion surface-initiated activator regenerated by electron transfer (SI-ARGET) atom transfer radical polymerization (ATRP). Miniemulsion as the reaction medium effectively confined the interparticle brush coupling within micellar compartments, preventing macroscopic gelation and enabling complete conversion. Isolation of dispersed and gelled fractions revealed dispersed particle brushes to feature a higher Young’s modulus, toughness, and ultimate strain compared with those of the “gel” counterparts. Upon purification, brush nanoparticles from the dispersed phase formed uniform microstructures. Uniaxial tension testing revealed a “mechanical synergy” for copolymers with MMA/BA = 3:2 molar ratio to concurrently exhibit higher toughness and stiffness. When compared with linear analogues of similar composition, the brush nanoparticles with gradient copolymers had better mechanical properties, attributed to the synergistic effects of the combination of composition and propagation orientation, highlighting the significance of architectural design for tethered brush layers of such hybrid materials.

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Surface and Particle Modification via RAFT Polymerization: An Update

Cited by 5 publications

References 100 publications

Topologically Induced Heterogeneity in Gradient Copolymer Brush Particle Materials

Topologically Induced Heterogeneity in Gradient Copolymer Brush Particle Materials

Nanotargeting of Resistant Infections with a Special Emphasis on the Biofilm Landscape

Composition-Orientation Induced Mechanical Synergy in Nanoparticle Brushes with Grafted Gradient Copolymers

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