PMID- 37392471 OWN - NLM STAT- PubMed-not-MEDLINE LR - 20230724 IS - 1944-8252 (Electronic) IS - 1944-8244 (Print) IS - 1944-8244 (Linking) VI - 15 IP - 28 DP - 2023 Jul 19 TI - Dopamine-Based Copolymer Bottlebrushes for Functional Adhesives: Synthesis, Characterization, and Applications in Surface Engineering of Antifouling Polyethylene. PG - 34023-34030 LID - 10.1021/acsami.3c05124 [doi] AB - Nonpolar materials like polyolefins are notoriously challenging substrates for surface modification. However, this challenge is not observed in nature. Barnacle shells and mussels, for example, utilize catechol-based chemistry to fasten themselves onto all kinds of materials, such as boat hulls or plastic waste. Here, a design is proposed, synthesized, and demonstrated for a class of catechol-containing copolymers (terpolymers) for surface functionalization of polyolefins. Dopamine methacrylamide (DOMA), a catechol-containing monomer, is incorporated into a polymer chain together with methyl methacrylate (MMA) and 2-(2-bromoisobutyryloxy)ethyl methacrylate (BIEM). DOMA serves as adhesion points, BIEM provides functional sites for subsequent "grafting from" reactions, and MMA provides the possibility for concentration and conformation adjustment. First, the adhesive capabilities of DOMA are demonstrated by varying its content in the copolymer. Then, terpolymers are spin-coated on model Si substrates. Subsequently, the atom transfer initiator (ATRP) initiating group is used to graft a poly(methyl methacrylate) (PMMA) layer from the copolymers, with 40% DOMA content providing a coherent PMMA film. To demonstrate functionalization on a polyolefin substrate, the copolymer is spin-coated on high-density polyethylene (HDPE) substrates. A POEGMA layer is grafted from the ATRP initiator sites on the terpolymer chain on the HDPE films to provide antifouling characteristics. Static contact angle values and Fourier transform infrared (FTIR) spectra confirm the presence of POEGMA on the HDPE substrate. Finally, the anticipated antifouling functionality of grafted POEGMA is demonstrated by observing the inhibition of nonspecific adsorption of the fluorescein-modified bovine serum albumin (BSA) protein. The poly(oligoethylene glycol methacrylate) POEGMA layers grafted on 30% DOMA-containing copolymers on HDPE show optimal antifouling performance exhibiting a 95% reduction of BSA fluorescence compared to nonfunctionalized and surface-fouled polyethylene. These results demonstrate the successful utilization of catechol-based materials for functionalizing polyolefin surfaces. FAU - Milatz, Roland AU - Milatz R AUID- ORCID: 0000-0003-1755-5590 AD - Department of Materials Science and Technology of Polymers, and Department of Sustainable Polymer Chemistry, University of Twente, Enschede 7522 NB, The Netherlands. AD - DPI, P.O. Box 902, 5600 AX Eindhoven, The Netherlands. FAU - Duvigneau, Joost AU - Duvigneau J AUID- ORCID: 0000-0002-2810-2768 AD - Department of Materials Science and Technology of Polymers, and Department of Sustainable Polymer Chemistry, University of Twente, Enschede 7522 NB, The Netherlands. FAU - Vancso, Gyula Julius AU - Vancso GJ AUID- ORCID: 0000-0003-4718-0507 AD - Department of Materials Science and Technology of Polymers, and Department of Sustainable Polymer Chemistry, University of Twente, Enschede 7522 NB, The Netherlands. LA - eng PT - Journal Article DEP - 20230701 PL - United States TA - ACS Appl Mater Interfaces JT - ACS applied materials & interfaces JID - 101504991 SB - IM PMC - PMC10360033 OTO - NOTNLM OT - antifouling OT - biomimetic adhesion OT - polydopamine OT - polyethylene grafting OT - surface functionalization COIS- The authors declare no competing financial interest. EDAT- 2023/07/01 21:09 MHDA- 2023/07/01 21:10 PMCR- 2023/07/21 CRDT- 2023/07/01 16:42 PHST- 2023/07/01 21:10 [medline] PHST- 2023/07/01 21:09 [pubmed] PHST- 2023/07/01 16:42 [entrez] PHST- 2023/07/21 00:00 [pmc-release] AID - 10.1021/acsami.3c05124 [doi] PST - ppublish SO - ACS Appl Mater Interfaces. 2023 Jul 19;15(28):34023-34030. doi: 10.1021/acsami.3c05124. Epub 2023 Jul 1.