TY - JOUR
T1 - Dopamine-Based Copolymer Bottlebrushes for Functional Adhesives: Synthesis, Characterization, and Applications in Surface Engineering of Antifouling Polyethylene
AU - Milatz, Roland
AU - Duvigneau, Joost
AU - Vancso, Gyula Julius
N1 - Funding Information:
This research forms part of the research program of DPI, project 823t19. The authors thank Dr. F. Radmanesh for her help with ellipsometry experiments, M.Sc. G. Kafkopoulos for the fruitful discussions, and the MESA+ Institute for Nanotechnology and the University of Twente for instrumental support.
Publisher Copyright:
© 2023 The Authors. Published by American Chemical Society
PY - 2023/7/19
Y1 - 2023/7/19
N2 - 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.
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.
KW - UT-Hybrid-D
U2 - 10.1021/acsami.3c05124
DO - 10.1021/acsami.3c05124
M3 - Article
SN - 1944-8244
VL - 15
SP - 34023
EP - 34030
JO - ACS applied materials & interfaces
JF - ACS applied materials & interfaces
IS - 28
ER -