Mechanism and application of surface-initiated ATRP in the presence of a Zn<sup>0</sup> plate

Albers, Rebecca Faggion; Yan, Wenqing; Romio, Matteo; Leite, E. R.; Spencer, Nicholas D.; Matyjaszewski, Krzysztof; Benetti, Edmondo M.

doi:10.1039/d0py01233e

Cited by 27 publications

(22 citation statements)

References 27 publications

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“…This method opens up exciting possibilities to perform surface modifications on the substrates of cell cultures without affecting their viability. Recently, we extended this technique to Zn(0) plates . Oxygen-tolerant SI-Zn(0)-ATRP allowed the rapid grafting of thick brush films from flat inorganic supports and cotton fabrics.…”

Section: Atrp Mediated By Zero-valent Metalsmentioning

confidence: 99%

Making ATRP More Practical: Oxygen Tolerance

et al. 2021

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Conspectus Atom-transfer radical polymerization (ATRP) is a well-known technique for the controlled polymerization of vinyl monomers under mild conditions. However, as with any other radical polymerization, ATRP typically requires rigorous oxygen exclusion, making it time-consuming and challenging to use by nonexperts. In this Account, we discuss various approaches to achieving oxygen tolerance in ATRP, presenting the overall progress in the field. Copper-mediated ATRP, which we first discovered in the late 1990s, uses a CuI/L activator that reversibly reacts with the dormant C(sp3)–X polymer chain end, forming a X–CuII/L deactivator and a propagating radical. Oxygen interferes with activation and chain propagation by quenching the radicals and oxidizing the activator. At ATRP equilibrium, the activator is present at a much higher concentration than the propagating radicals. Thus, oxidation of the activator is the dominant inhibition pathway. In conventional ATRP, this reaction is irreversible, so oxygen must be strictly excluded to achieve good results. Over the last two decades, our group has developed several ATRP techniques based on the concept of regenerating the activator. When the oxidized activator is continuously converted back to its active reduced form, then the catalytic system itself can act as an oxygen scavenger. Regeneration can be accomplished by reducing agents and photo-, electro-, and mechanochemical stimuli. This family of methods offers a degree of oxygen tolerance, but most of them can tolerate only a limited amount of oxygen and do not allow polymerization in an open vessel. More recently, we discovered that enzymes can be used in auxiliary catalytic systems that directly deoxygenate the reaction medium and protect the polymerization process. We developed a method that uses glucose oxidase (GOx), glucose, and sodium pyruvate to very effectively scavenge oxygen and enable open-vessel ATRP. By adding a second enzyme, horseradish peroxidase (HPR), we managed to extend the role of the auxiliary enzymatic system to generating carbon-based radicals and changed ATRP from an oxygen-sensitive to an oxygen-fueled reaction. While performing control experiments for the enzymatic methods, we noticed that using sodium pyruvate under UV irradiation triggers polymerization without the presence of GOx. This serendipitous discovery allowed us to develop the first oxygen-proof, small-molecule-based, photoinduced ATRP system. It has oxygen tolerance similar to that of the enzymatic methods, exhibits superior compatibility with both aqueous media and organic solvents, and avoids problems associated with purifying polymers from enzymes. The system was able to rapidly polymerize N-isopropylacrylamide, a challenging monomer, with a high degree of control. These contributions have substantially simplified the use of ATRP, making it more practical and accessible to everyone.

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Section: Atrp Mediated By Zero-valent Metalsmentioning

confidence: 99%

Making ATRP More Practical: Oxygen Tolerance

et al. 2021

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“…Despite these challenges, research on antibacterial coatings will continue to advance at a rapid pace spurred by new developments in polymer science and fabrication technology. The development of oxygen-tolerant controlled/living radical polymerization methods , will enable well-controlled antibacterial polymer brushes to be grown on surfaces of different substrates without the need for specialized equipment or lengthy degassing procedures. Electrophoretic deposition has been shown to be a simple and versatile technique that yields a uniform and stable coating with a tunable thickness at room temperature and is rapid and cost-effective compared to solvent casting, LbL deposition, and plasma-based coating. − This method has been used to incorporate antibacterial agents such as antibiotics and Ag NPs in different hydrogels and to deposit CH/gelatin composite coating loaded with antibiotics on 3D-printed Ti implants .…”

Section: Concluding Remarks and Perspectivementioning

confidence: 99%

Polymer-Based Coatings with Integrated Antifouling and Bactericidal Properties for Targeted Biomedical Applications

Mitra

Kang

Neoh

2021

ACS Appl. Polym. Mater.

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One of the most detrimental consequences of surface colonization by bacteria is healthcare-associated infections (HAIs), which contribute to increased patient mortality and morbidity. Medical devices inserted into the body provide a route for bacterial migration and conducive surfaces for their attachment and proliferation. Antibacterial coatings can potentially minimize bacterial colonization and consequently reduce the occurrence of HAIs. Antibacterial coatings function by either inhibiting the attachment of bacteria (antifouling coatings) or killing bacteria attached to the surface and/or in the vicinity (bactericidal coatings). On an antifouling coating, any bacterium that manages to attach will proliferate, while on bactericidal coatings, the accumulation of dead bacteria and debris provides opportunities for other bacteria to colonize the surface. As such, the integration of antifouling and bactericidal functionalities in a single coating combines the advantages of each, increasing the probability that bacterial colonization can be successfully inhibited. This Review highlights recent developments in dual-functional polymer-based antibacterial coatings for specific biomedical applications. General strategies for endowing surfaces with either antifouling or bactericidal polymeric coatings are first discussed, followed by more detailed descriptions of coatings with integrated antifouling and bactericidal functionalities that target the important biomedical applications: blood-contacting devices, orthopedic implants, wound dressings, ocular devices, urinary catheters, endotracheal tubes, and hospital textiles. The importance of tailoring the coatings to meet the specific constraints and requirements of the intended application beyond the antibacterial functionality is emphasized, and finally, the potential challenges in translating such coatings to clinical application are highlighted.

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“…Advances in surface-initiated reversible deactivation radical polymerization (SI-RDRP) processes, such as surface-initiated atom transfer radical polymerization (SI-ATRP − ) and surface-initiated reversible addition-fragmentation chain transfer polymerization (SI-RAFT − ), have made it possible to modify the physicochemical properties of substrates. Depending on the chemical composition and architecture of the tethered polymer chains, the modified surfaces are utilized in applications such as sample purification; − biosensing; ,, antifouling coatings, ,, cell culture platform development, , adhesion and controlled cell shedding, , drug and gene delivery; catalysis and control of enzyme activity; − and capacitors, batteries, and fuel cells. − Many studies have therefore tuned macroscopic properties such as adhesion, lubrication, friction, and (bio)compatibility, , but still, challenges are (i) to fully characterize surface-initiated polymerization (SIP) at the molecular level and (ii) to understand macromolecular variations compared to conventional solution/bulk synthesis routes.…”

Section: Introductionmentioning

confidence: 99%

Conformational Variations for Surface-Initiated Reversible Deactivation Radical Polymerization: From Flat to Curved Nanoparticle Surfaces

Hernandez¹,

Steenberge²,

Sobieski

et al. 2021

Macromolecules

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Although progress in surface-initiated reversible deactivation radical polymerization (SI-RDRP) has already enabled the production of increasingly novel and advanced polymer structures on solid surfaces, fundamental kinetic questions remain regarding the impact of reaction conditions on the molecular properties of synthesized tethered chains. In the current work, we put forward a matrix-based kinetic Monte Carlo (kMC) model, which is based on an implicit SI-RDRP reaction scheme and continuous three-dimensional (3D) representations, capable of following the temporal evolution of the molecular properties of individual free and surface-tethered polymer chains. This is uniquely possible for variable surface curvature (nanoparticle radii from 4.5 to 32 nm; 353 K; monomer: methyl methacrylate), also including the comparison with the limiting case of a flat surface and addressing various (average) RDRP initiator surface coverages. For the tethered chains, we emphasize the prediction of the variation of the molecular height, monomer occupancy, and radius of gyration and also focus on the simulation of the chain length distribution (CLD) to enable a comparison with solution RDRP results. It is shown that confinement effects on the surface lead to the formation of heterogeneous polymer layers with a marked bimodality in the number CLD. This bimodality is, however, wiped out in experimental analysis based on log-molar mass distributions. It is also shown that an increase in the size of the spherical particles and, hence, a decrease in their curvature results in a deterioration of the control over molecular properties, leading to behavior more similar to that of flat surfaces. Average molecular heights and monomer occupancies can vary with a factor of 2. The impact of the targeted chain length is shown to be of lower importance.

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Mechanism and application of surface-initiated ATRP in the presence of a Zn⁰ plate

Abstract: Surface-initiated Zn0-mediated atom transfer radical polymerization (SI-Zn0-ATRP) enables the rapid synthesis of chemically diverse polymer brushes from both planar inorganic supports, and fabrics made of natural fibers. This process enables...

Cited by 27 publications

References 27 publications

Making ATRP More Practical: Oxygen Tolerance

Making ATRP More Practical: Oxygen Tolerance

Polymer-Based Coatings with Integrated Antifouling and Bactericidal Properties for Targeted Biomedical Applications

Conformational Variations for Surface-Initiated Reversible Deactivation Radical Polymerization: From Flat to Curved Nanoparticle Surfaces

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Mechanism and application of surface-initiated ATRP in the presence of a Zn0 plate

Abstract: Surface-initiated Zn0-mediated atom transfer radical polymerization (SI-Zn0-ATRP) enables the rapid synthesis of chemically diverse polymer brushes from both planar inorganic supports, and fabrics made of natural fibers. This process enables...

Cited by 27 publications

References 27 publications

Making ATRP More Practical: Oxygen Tolerance

Making ATRP More Practical: Oxygen Tolerance

Polymer-Based Coatings with Integrated Antifouling and Bactericidal Properties for Targeted Biomedical Applications

Conformational Variations for Surface-Initiated Reversible Deactivation Radical Polymerization: From Flat to Curved Nanoparticle Surfaces

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Product

Resources

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Mechanism and application of surface-initiated ATRP in the presence of a Zn⁰ plate