Antifouling Polymer Brushes via Oxygen-Tolerant Surface-Initiated PET-RAFT

Kuzmyn, Andriy R.; Nguyen, Ai T.; Teunissen, Lucas W.; Zuilhof, Han; Baggerman, Jacob

doi:10.1021/acs.langmuir.9b03536

Cited by 64 publications

(141 citation statements)

References 45 publications

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“…In the wide scan, only three main peaks are observed, namely, O 1s (531 eV), N 1s (388 eV), and C 1s (285 eV) in a 1.8:1:8.3 ratio. This is in reasonable agreement with the elemental composition of the poly(HMPA) structure (2:1:7) and with previously published papers on HPMA brushes, which report a ratio of 1.8:1:7.6, 48 given the possibility of atmospheric contamination…”

Section: Resultssupporting

confidence: 92%

“…Similar growth rates have been reported for this HPMA monomer using PET-RAFT on silane anchoring layers. 48 This implies that from a self-assembled polymeric PLL starting layer, the polymerization works equally well compared to well-defined silane monolayers. Figure 3 shows the XPS spectra for the polymer brushes that were grown for 80 min.…”

Section: Resultsmentioning

confidence: 99%

“… 46 , 48 Triethanolamine (TEOA) was used as a cocatalyst 46 and also acted as a sacrificing electron donor to reduce oxygen in the polymerization system. 48 The study of the polymer growth kinetics showed a linear growth for the first 40 min ( Figure 4 ), which indicates the controlled nature of this surface-initiated polymerization. The leveling off after 40 min might indicate a reduced availability of the RAFT groups by either an increased steric hindrance or chemical degradation.…”

Section: Resultsmentioning

confidence: 99%

“…This polymerization technique is oxygen-tolerant and metal-free, can be applied to polymerizations in water, 46 , 47 works with an accessible and affordable organic photocatalyst (Eosin Y), 45 , 46 and has been shown to be also applicable to surface-initiated polymerization of different monomers. 48 Especially, this final feature makes PET-RAFT very suitable for our purpose, as it works well both in solution and from a surface. Subsequently, we determined and evaluated the various properties of the thus formed coatings in detail, including ease of synthesis, scalability, reproducibility, modularity, and ease of characterization.…”

Section: Introductionmentioning

confidence: 99%

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PLL–Poly(HPMA) Bottlebrush-Based Antifouling Coatings: Three Grafting Routes

Roeven

Kuzmyn

Scheres³

et al. 2020

Langmuir

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In this work, we compare three routes to prepare antifouling coatings that consist of poly( l -lysine)–poly( N -(2-hydroxypropyl)methacrylamide) bottlebrushes. The poly( l -lysine) (PLL) backbone is self-assembled onto the surface by charged-based interactions between the lysine groups and the negatively charged silicon oxide surface, whereas the poly( N -(2-hydroxypropyl)methacrylamide) [poly(HPMA)] side chains, grown by reversible addition–fragmentation chain-transfer (RAFT) polymerization, provide antifouling properties to the surface. First, the PLL–poly(HPMA) coatings are synthesized in a bottom-up fashion through a grafting-from approach. In this route, the PLL is self-assembled onto a surface, after which a polymerization agent is immobilized, and finally HPMA is polymerized from the surface. In the second explored route, the PLL is modified in solution by a RAFT agent to create a macroinitiator. After self-assembly of this macroinitiator onto the surface, poly(HPMA) is polymerized from the surface by RAFT. In the third and last route, the whole PLL–poly(HPMA) bottlebrush is initially synthesized in solution. To this end, HPMA is polymerized from the macroinitiator in solution and the PLL–poly(HPMA) bottlebrush is then self-assembled onto the surface in just one step ( grafting-to approach). Additionally, in this third route, we also design and synthesize a bottlebrush polymer with a PLL backbone and poly(HPMA) side chains, with the latter containing 5% carboxybetaine (CB) monomers that eventually allow for additional (bio)functionalization in solution or after surface immobilization. These three routes are evaluated in terms of ease of synthesis, scalability, ease of characterization, and a preliminary investigation of their antifouling performance. All three coating procedures result in coatings that show antifouling properties in single-protein antifouling tests. This method thus presents a new, simple, versatile, and highly scalable approach for the manufacturing of PLL-based bottlebrush coatings that can be synthesized partly or completely on the surface or in solution, depending on the desired production process and/or application.

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Section: Resultssupporting

confidence: 92%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

PLL–Poly(HPMA) Bottlebrush-Based Antifouling Coatings: Three Grafting Routes

Roeven

Kuzmyn

Scheres³

et al. 2020

Langmuir

Self Cite

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“…Beyond RAFT- and ATRP-related processes, photo-polymerizations have recently been developed to tolerate atmospheric levels of oxygen. The polymerizations are metal-free, which in terms of environmental and health considerations is an attractive trait [ 19 , 20 ]. However, being the most popular and matured polymer brush synthesis method, we herein put our focus on ATRP-related processes and their upscaling.…”

Section: Introductionmentioning

confidence: 99%

Polymer Brush Coating and Adhesion Technology at Scale

Buhl

Agergaard

Lillethorup³

et al. 2020

Polymers

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Creating strong joints between dissimilar materials for high-performance hybrid products places high demands on modern adhesives. Traditionally, adhesion relies on the compatibility between surfaces, often requiring the use of primers and thick bonding layers to achieve stable joints. The coatings of polymer brushes enable the compatibilization of material surfaces through precise control over surface chemistry, facilitating strong adhesion through a nanometer-thin layer. Here, we give a detailed account of our research on adhesion promoted by polymer brushes along with examples from industrial applications. We discuss two fundamentally different adhesive mechanisms of polymer brushes, namely (1) physical bonding via entanglement and (2) chemical bonding. The former mechanism is demonstrated by e.g., the strong bonding between poly(methyl methacrylate) (PMMA) brush coated stainless steel and bulk PMMA, while the latter is shown by e.g., the improved adhesion between silicone and titanium substrates, functionalized by a hydrosilane-modified poly(hydroxyethyl methacrylate) (PHEMA) brush. This review establishes that the clever design of polymer brushes can facilitate strong bonding between metals and various polymer materials or compatibilize fillers or nanoparticles with otherwise incompatible polymeric matrices. To realize the full potential of polymer brush functionalized materials, we discuss the progress in the synthesis of polymer brushes under ambient and scalable industrial conditions, and present recent developments in atom transfer radical polymerization for the large-scale production of brush-modified materials.

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Creating Anti‐Biofouling Surfaces by Degradable Main‐chain Polyphosphoester Polymer Brushes

Pérez,

Resendiz‐Lara,

Matsushita

et al. 2024

Adv Funct Materials

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The implementation of polymer brush coatings has proven crucial in biomedical and biotechnological applications for controlling biological interactions. Despite the extensive research and use of synthetic polymer coatings, concerns regarding their long‐term non‐biodegradability have arisen. This issue is significant as non‐degradable polymers can lead to complications such as inflammatory responses and bioaccumulation, highlighting the need for polymers that degrade in a controlled manner. To address this, polyphosphonate brushes are synthesized as anti‐biofouling coatings on silicon surfaces via controlled surface‐initiated organocatalytic ring‐opening polymerization (SI‐ROP) of cyclic phospholanes. 2‐Ethyl‐2‐oxo‐1,3,2‐dioxaphospholane and 2‐hexyl‐2‐oxo‐1,3,2‐dioxaphospholane are chosen as the monomers to prepare hydrophilic and hydrophobic brushes with thicknesses up to 55 nm, with a proven degradability in aqueous media. In addition, protein adsorption, bacterial adhesion, and biofilm formation are investigated as a function of the polyphosphonate side chain. Compared to non‐coated surfaces and polyester brushes, hydrophilic poly(2‐ethyl‐2‐oxo‐1,3,2‐dioxaphospholane) brushes have an enhanced resistance toward fouling of albumin, fibrinogen, and diluted human serum proteins, as well as toward Escherichia coli and Staphylococcus aureus bacteria. The stability and anti‐biofouling performance of hydrophilic polyphosphonate brushes position them as an attractive option as degradable materials for anti‐biofouling matrices on medical devices and/or lubricious coatings for artificial implant technologies.

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Antifouling Polymer Brushes via Oxygen-Tolerant Surface-Initiated PET-RAFT

Cited by 64 publications

References 45 publications

PLL–Poly(HPMA) Bottlebrush-Based Antifouling Coatings: Three Grafting Routes

PLL–Poly(HPMA) Bottlebrush-Based Antifouling Coatings: Three Grafting Routes

Polymer Brush Coating and Adhesion Technology at Scale

Creating Anti‐Biofouling Surfaces by Degradable Main‐chain Polyphosphoester Polymer Brushes

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