Applied Surface Science 300 (2014) 43–50
Contents lists available at ScienceDirect
Applied Surface Science
jou rn al h om ep age: www.elsevier.com/locate/apsusc
Polymethyl methacrylate-co-methacrylic acid coatings with
controllable concentration of surface carboxyl groups: A novel
approach in fabrication of polymeric platforms for potential
bio-diagnostic devices
Samira Hosseini
a
, Fatimah Ibrahim
a
, Ivan Djordjevic
a,∗
, Leo H. Koole
a,b
a
Center for Innovation in Medical Engineering, Department of Biomedical Engineering, Faculty of Engineering, University of Malaya, Kuala Lumpur 50603,
Malaysia
b
Department of Biomedical Engineering, Faculty of Health. Medicine & Life Science, Maastricht University, PO Box 616, NL 6200 MD Maastricht, The
Netherlands
a r t i c l e i n f o
Article history:
Received 27 November 2013
Accepted 31 January 2014
Available online 9 February 2014
Keywords:
Co-polymer
Spin-coating
Surface functional groups
Diagnostic device
a b s t r a c t
The generally accepted strategy in development of bio-diagnostic devices is to immobilize proteins on
polymeric surfaces as a part of detection process for diseases and viruses through antibody/antigen cou-
pling. In that perspective, polymer surface properties such as concentration of functional groups must be
closely controlled in order to preserve the protein activity. In order to improve the surface characteris-
tics of transparent polymethacrylate plastics that are used for diagnostic devices, we have developed an
effective fabrication procedure of polymethylmetacrylate-co-metacrylic acid (PMMA-co-MAA) coatings
with controlled number of surface carboxyl groups. The polymers were processed effectively with the
spin-coating technique and the detailed control over surface properties is here by demonstrated through
the variation of a single synthesis reaction parameter. The chemical structure of synthesized and pro-
cessed co-polymers has been investigated with nuclear magnetic resonance spectroscopy (NMR) and
matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-ToF-MS). The surface mor-
phology of polymer coatings have been analyzed with atomic force microscopy (AFM) and scanning
electron microscopy (SEM). We demonstrate that the surface morphology and the concentration of sur-
face –COOH groups (determined with UV–vis surface titration) on the processed PMMA-co-MAA coatings
can be precisely controlled by variation of initial molar ratio of reactants in the free-radical polymeriza-
tion reaction. The wettability of developed polymer surfaces also varies with macromolecular structure.
© 2014 Elsevier B.V. All rights reserved.
1. Introduction
The development of biosensors has drawn a vital role of research
interest due to the high sensitivity and selectivity in detection of
diseases and viruses. Of particular interests are polymeric mate-
rials used for surface protein immobilization. Those immobilized
surface proteins are further engaged in detection of coupling
proteins (antibody/antigen) present in diseased blood. The most
commonly applied diagnostic device, based on heterogeneous
antibody/antigen interaction, the enzyme-linked immunosorbent
assay (ELISA), still presents a “golden standard” in clinical diag-
nostic practice [1,2]. However, conventional ELISA has its own
limitations such as: tedious and labor-intensive protocol, long incu-
bation times between each step and inconsistency of the results
∗
Corresponding author. Tel.: +60 3 7967 7616; fax: +60 3 7967 4579.
E-mail address: ivan.djordjevic@um.edu.my (I. Djordjevic).
[3]. In order to overcome those serious limitations, there is a
strong need for development of advanced polymer coatings with
controllable surface properties such as surface chemistry and mor-
phology. In that perspective, a generation of functionalities such
as hydroxyl (–OH), amine (–NH
2
) and carboxyl (–COOH) groups
at the surface of polymer coatings presents the crucial step for
further immobilization of proteins and subsequent effective detec-
tion of diseases and viruses. Furthermore, the surface concentration
of those functional groups must be closely controlled in order to
avoid protein de-activation caused by either steric repulsion (over-
functionalization) or protein denaturation in close proximity of the
polymer surface (low surface concentration of functional groups)
[4].
In recent years, polymethyl methacrylate (PMMA) has shown a
great potential due to the particular properties and a wide range
of applications [5]. PMMA is a low cost polymer with chemical
inertness, low specific weight, high impact resistance and flexi-
bility. PMMA has been successfully used for the immobilization of
0169-4332/$ – see front matter © 2014 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.apsusc.2014.01.203