Plasma initiated graft polymerization of 2-methacryloyloxyethyl
phosphorylcholine on silicone elastomer surfaces to
enhance bio(hemo)compatibility
Shuian-Yin Lin
a
, Vijaya Rohini Parasuraman
b
, Shewaye Lakew Mekuria
b
, Sydney Peng
b
,
Hsieh-Chih Tsai
b,
⁎, Ging-Ho Hsiue
c,
⁎
a
National Applied Research Laboratories, Instrument Technology Research Center, Hsinchu, Taiwan
b
Graduate Institute of Applied Science and Technology, National Taiwan University of Science and Technology, Taipei, Taiwan
c
Department of Chemical Engineering National Chung Hsing University, Taichung, Taiwan
abstract article info
Article history:
Received 23 November 2016
Revised 13 February 2017
Accepted in revised form 14 February 2017
Available online 20 February 2017
Poly-2-methacryloyloxyethyl phosphorylcholine (pMPC) was grafted from the silicone elastomer (SE) surface by
plasma-initiated polymerization to alter the surface properties. Argon plasma was used to activate the SE surface,
and the amount of peroxide produced on the surface was determined by 1,1-diphenyl-2-picryl-hydrazyl. Suc-
cessful grafting of pMPC from the SE surface was verified by attenuated total reflection-Fourier transform infrared
spectroscopy and elemental analysis. The surface morphology of cells adhered to pMPC-grafted SE also differed
from that of cells adhered to unmodified and Ar-plasma-treated SE surfaces due to the homogenous graft poly-
merization of pMPC. Biological analyses of pMPC-grafted SE revealed that, at the polymer surface, protein adsorp-
tion of bovine serum albumin was significantly reduced, and that the surface exhibited anti-coagulant activity in
human whole blood and decreased platelet adhesion. In summary, the grafting of pMPC on SE significantly en-
hanced the bio(hemo)-compatibility of SE.
© 2017 Elsevier B.V. All rights reserved.
Keywords:
2-Methacryloyloxyethyl phosphorylcholine
Silicone elastomer membrane
Plasma initiated grafted polymerization
Protein adsorption
Platelet adhesion
Human blood cells assay
Fibroblast cell adhesion
1. Introduction
Silicone elastomer (SE) is used as a soft-tissue substitute because it is
soft, stable, and bio-inert. SE is a valuable biomaterial widely used in
medical applications, but its surface properties and low wettability
cause serious problems in long-term implants [1–5]. Furthermore, the
hemocompatibility of SE is compromised after extended implantation
owing to its surface hydrophobicity [6]. Currently, several methods are
used to modify the surface of silicone polymers including corona, plas-
ma, and laser treatments. Of these, plasma-induced activation of con-
ventionally synthesized polymer surfaces using inert gas plasmas or
simple plasma UV radiation generates free radicals that enable subse-
quent grafting. Plasma treatment alone can also change the polymer
surface morphology, through controlled nanostructuring or chemical
modification by etching, cross-linking, and/or activating the polymer
substrate. Moreover, inert gas plasma treatment has played a key role
in the tuning of polymer wettability [7] and has expanded the applica-
tion spectrum of these polymers in biomedicine [8–9].
Current surface modification technologies are able to introduce ni-
trogen and phosphorous functionalities. These functionalities are attrac-
tive for biomedical applications because they are biocompatible and
enable covalent immobilization of biological molecules such as polysac-
charides [10], enzymes, and DNA [11]. On the other hand, the addition
of an inert gas (i.e. Ar) to nitrogen-based plasma can enhance radical
formation and increase the number of nitrogen and oxygen functional-
ities [12]. Ar-plasma treatment of SE increases the degree of cross-
linking, which reduces the mobility of the modified SE surface and min-
imizes hydrophobic recovery. These functionalities can be further
grafted to confer biocompatibility, anti-bacterial properties, and anti-
fouling characteristics [13]. It is desirable to endow the SE with new
functionalities for medical applications, including cell and tissue engi-
neering and drug delivery systems [14,15]. Nevertheless, many studies
have indicated that SE blood contact can lead to the formation of throm-
bi, but its use in short-term blood contact is very limited.
Phospholipid polymers with phosphorylcholine head groups, such
as poly-2-methacryloyloxyethyl phosphorylcholine (pMPC), are anti-
fouling materials suitable for biomedical use. These phospholipid poly-
mers have been used for the preparation of biocompatible polymers
that mimic the bio-membrane structure [16]. When used in implantable
micro-devices, pMPC's are hemo-compatible and inhibit the adhesion of
proteins. These zwitterionic polymers confer anti-fouling properties
Surface & Coatings Technology 315 (2017) 342–349
⁎ Corresponding author.
E-mail addresses: h.c.tsai@mail.ntust.edu.tw (H.-C. Tsai), ghhsiue@mx.nthu.edu.tw
(G.-H. Hsiue).
http://dx.doi.org/10.1016/j.surfcoat.2017.02.039
0257-8972/© 2017 Elsevier B.V. All rights reserved.
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