In this paper, a series of fluorinated amphiphilic copolymers composed of 2-perfluorooctylethyl methacrylate (FMA) and 2-hydroxyethyl methacrylate (HEMA) monomers were prepared, and their surface properties and antifouling performance were investigated. Bovine serum albumin (BSA) and human plasma fibrinogen (HFg) were used as model proteins to study protein adsorption onto the fluorinated amphiphilic surfaces. All the fluorinated amphiphilic surfaces exhibit excellent resistant performance of protein adsorption measured by X-ray photoelectron spectroscopy (XPS). The surface compositional heterogeneities on the molecular scale play an important role in the antifouling properties. It was found that the copolymers exhibited better antifouling properties than the corresponding homopolymers did, when the percentage of hydrophilic hydroxyl groups is from 4% to 7% and the percentage of hydrophobic fluorinated moieties is from 4% to 14% on the surface. In addition, the protein molecular size scale and the pattern of microphase segregation domains on the surface strongly affect the protein adsorption behaviors. These results demonstrate the desirable protein-resistant performance from the fluorinated amphiphilic copolymers and provide deeper insight of the effect of surface compositional heterogeneity and microphase segregation on the protein adsorption behaviors.
In this paper, the relationship between the surface structures
of spin-coated fluorinated polymer films and their corresponding film-formation
solution/air interface structures was investigated. Film-forming poly(n-alkyl methacrylate) end-capped with 2-perfluorooctylethyl
methacrylate (FMA; PFMA
y
-ec-PnAMA
x
-ec-PFMA
y
) was
synthesized via a controlled/living atom-transfer radical polymerization
(ATRP) technique. The structures both at solution interface and on
the spin-coated film surface for these polymers were studied by X-ray
photoelectron spectroscopy (XPS), sum frequency spectroscopy (SFG),
and surface tension measurements. The results showed that, with increasing
polymerization degree of PnAMA, the fluorinated moieties in PFMA
y
-ec-PnAMA
x
-ec-PFMA
y
adsorbed at the solution/air interface were
gradually completely replaced by PnAMA segments, resulting in an increase
in corresponding solution surface tension until it was equal to that
of poly(n-alkyl methacrylate) solution. Additionally,
it was observed for the first time that the surface F/C ratios of
spin-coated films decreased linearly with increasing surface tension
of the corresponding film-formation polymer solution. Overall, the
results indicate that the ultimate surface composition of spin-coated
films of these fluorinated methacrylates was mainly dominated by their
corresponding film-formation solution/air interfacial structure. This
work provides a fundamental understanding of the formation of film
surface structures from fluorinated polymer solution to the resulting
solid film.
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