A comparative study of different methods of

carboxylation on polyethylene terephthalate to

improve antifouling property
Balaji Ramachandran1 and Vignesh Muthuvijayan1
 1 Indian Institute of Technology Madras, Department of Biotechnology, Bhupat and Jyoti Mehta School of Biosciences,
India
Introduction: Protein adsorption on blood contacting polymers significantly increases
the rate of thrombosis and infection on biomedical devices[1]. Here, we have introduced
carboxyl groups to polyethylene terephthalate (PET) surfaces using four different
functionalization techniques. These carboxylated PET (PET-COOH) surfaces were
characterized and their protein antifouling properties were compared.

Materials and Methods: Four different methods were used to introduce carboxyl
groups on PET surfaces (Fig.1). In method 1 (M1), carboxyl groups were introduced by
two step process[2]. In method 2 (M2), initial modifications were same as M1, but
methacrylic acid grafting was done on the polymer backbone at the last step[3]. In method
3 (M3), PET was hydrolyzed using NaOH and then functional groups on the surface were
oxidized using KMnO4[4]. In method 4 (M4), oxygen plasma treatment was used to
introduce reactive peroxide groups on which acrylic acid was grafted[5],[6]. Introduction of
carboxyl group was confirmed by fourier transform infrared spectroscopy (FTIR) and
estimated using Toluidine blue O (TBO) assay. The surface properties of PET-COOH were
characterized by contact angle measurement and scanning electron microscopy (SEM).
The bulk property of PET-COOH was characterized using a universal testing machine.
Bovine serum albumin (BSA) adsorption on unmodified and modified PET surface was
compared using bicinchoninic acid (BCA) assay.
Results and Discussion: Carboxylation was confirmed by the broadening of FTIR
peaks in the region 2500-3300 cm-1 on the PET-COOH samples, due to the -OH bond
stretching of -COOH group. The amount of carboxyl group estimated by TBO assay for
control, M1, M2, M3, M4 was found to be 0.11, 0.31, 12.33, 18.40, 8.74 nmol/cm2,
respectively. M3 had maximum carboxylation compared to other methods, which is
probably due to the complete oxidation of hydroxyl groups by KMnO4 on the surface. M1
had least carboxylation which is probably due to the less reactivity of aromatic ring for
introduction of carboxyl groups. The water contact angles of PET-COOH are lower when
compared to unmodified PET (Table 1). These results support the TBO analysis that the
hydrophilicity of the modified PET increases with the carboxyl group density on the
surface. The SEM images of the modified PET showed that the methods had little or no
effect on surface topography, when compared with control (Fig.2).

The elastic modulus of PET-COOH showed no significant changes compared to

unmodified PET, suggesting these modifications have no effect on the bulk property
(Table 1). The amount of BSA adsorbed on unmodified PET, M1, M2, M3, M4 was found
to be 17.56, 16.72, 7.12, 1.87, 10.18 µg/cm2, respectively. M3, having the maximum
carboxyl density, shows effective inhibition of protein adsorption (Fig.3). This may be due
to the hydration layer formed on the modified surface, which varies depending on the
surface carboxyl density[7]. The hydrophilic surfaces forms a very tightly bound water
layer creating energy barrier to avoid protein adsorption.

Conclusion: Here, we present a study showing that selection of surface

functionalization method is significant for improving the antifouling property of PET
even though same functional group are being introduced. The modified PET by M3 was
very effective in enhancing antifouling property compared to other methods without
altering the bulk property.
We would like to thank A.N.Jeevaraj and Dr. A.Subrahmanyam, Department of Physics,
IITM for assisting with the plasma treatment; We also like to thank Department of
Biotechnology, Indian Institute of Technology Madras for facilities and fellowship
References:
[1] Banerjee, I.; Pangule, R. C.; Kane, R. S. Advanced Materials. 2011, 690–718.
[2] Yang, Z.; Belu, A. M.; Liebmann-Vinson, A.; Sugg, H.; Chilkoti, A. Langmuir 2000, 16
(19), 7482–7492.
[3] Ma, Z.; Ramakrishna, S. J. Appl. Polym. Sci. 2006, 101 (6), 3835–3841.
[4] Marchand-Brynaert, J.; Deldime, M.; Dupont, I.; Dewez, J.-L.; Schneider, Y.-J. J.
Colloid Interface Sci. 1995, 173 (1), 236–244.
[5] Junkar, I.; Vesel, A.; Cvelbar, U.; Mozetič, M.; Strnad, S. Vacuum 2009, 84 (1), 83–
85.
[6] Gupta, B.; Hilborn, J. G.; Bisson, I.; Frey, P. J. Appl. Polym. Sci. 2001, 81 (12), 2993–
3001.
[7] Chen, S.; Li, L.; Zhao, C.; Zheng, J. Polymer. 2010, 51 (23), 5283–5293.
Keywords: protein, Surface modification, Functionalization, Polymeric material

Conference: 10th World Biomaterials Congress, Montréal, Canada, 17 May - 22 May, 2016.

Presentation Type: General Session Oral

Topic: Protein interactions with biomaterials

Citation: Ramachandran B and Muthuvijayan V (2016). A comparative study of different methods of carboxylation
on polyethylene terephthalate to improve antifouling property. Front. Bioeng. Biotechnol. Conference Abstract:
10th World Biomaterials Congress. doi: 10.3389/conf.FBIOE.2016.01.00537

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Received: 27 Mar 2016; Published Online: 30 Mar 2016