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.