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Modular and Substrate-Independent Grafting-To Procedure for Functional Polymer Coatings.

ABSTRACT: The ability to tailor polymer brush coatings to the last nanometer has arguably placed them among the most powerful surface modification techniques currently available. Generally, the synthesis procedures for polymer brushes are designed for a specific surface type and monomer functionality and cannot be easily employed otherwise. Herein, we describe a modular and straightforward two-step grafting-to approach that allows introduction of polymer brushes of a desired functionality onto a large range of chemically different substrates. To illustrate the modularity of the procedure, gold, silicon oxide (SiO₂), and polyester-coated glass substrates were modified with five different block copolymers. In short, the substrates were first modified with a universally applicable poly(dopamine) primer layer. Subsequently, a grafting-to reaction was performed on the poly(dopamine) films using five distinct block copolymers, all of which contained a short poly(glycidyl methacrylate) segment and longer segment of varying chemical functionality. Ellipsometry, X-ray photoelectron spectroscopy, and static water contact angle measurements confirmed successful grafting of all five block copolymers to the poly(dopamine)-modified gold, SiO₂, and polyester-coated glass substrates. In addition, our method was used to provide direct access to binary brush coatings, by simultaneous grafting of two different polymer materials. The ability to synthesize binary brush coatings further adds to the versatility of our approach and paves the way toward production of novel multifunctional and responsive polymer coatings.

SUBMITTER: Teunissen LW

PROVIDER: S-EPMC10249404 | biostudies-literature | 2023 Jun

REPOSITORIES: biostudies-literature

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Modular and Substrate-Independent Grafting-To Procedure for Functional Polymer Coatings.

Teunissen Lucas W LW Smulders Maarten M J MMJ Zuilhof Han H

Langmuir : the ACS journal of surfaces and colloids 20230522 22

The ability to tailor polymer brush coatings to the last nanometer has arguably placed them among the most powerful surface modification techniques currently available. Generally, the synthesis procedures for polymer brushes are designed for a specific surface type and monomer functionality and cannot be easily employed otherwise. Herein, we describe a modular and straightforward two-step grafting-to approach that allows introduction of polymer brushes of a desired functionality onto a large ran ...[more]

PMID: 37216307

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Project description: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.

Dataset Information

Modular and Substrate-Independent Grafting-To Procedure for Functional Polymer Coatings.

Publications

Modular and Substrate-Independent Grafting-To Procedure for Functional Polymer Coatings.

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