Radiation Physics and Chemistry 55 (1999) 685±689

www.elsevier.com/locate/radphyschem

Laser surface modi®cation of polymers to improve

biocompatibility: HEMA grafted PDMS, in vitro
assayÐIII
M.T. Khorasani a, H. Mirzadeh a,*, P.G. Sammes b
a
Iran Polymer Institute, P.O. Box 14965/159, Tehran, Iran
b
Department of Chemistry, Brunel University, Uxbridge UBH 3PH, UK

Abstract

Polydimethylsiloxane (PDMS) surface modi®cations were carried out using CO2-pulsed laser, without
photosensitizer at ambient condition, to introduce peroxide groups onto the PDMS surface. Such peroxides were
capable of initiating graft polymerization of 2-hydroxyethyl methacrylate (HEMA) onto the PDMS. The modi®ed
surfaces were characterized using a variety of techniques including scanning electron microscopy (SEM), attenuated
total re¯ectance infrared (ATR-FTIR) and the water drop contact angle measurements. Data from in vitro assays
indicated a signi®cant reduction of the platelet adhesion and aggregation for the modi®ed surfaces. # 1999 Elsevier
Science Ltd. All rights reserved.

1. Introduction the performance of existing biomaterials and to

Since 1960, silicone has been widely used for medical
devices and numerous studies have been conducted on
toxicity, stability and tissue responses (Cifkova et al.,
1990; Okada and Ikada, 1991). Although silicone has
been used mostly as soft tissue substitutes, serious pro-
blems have occurred when the silicone devices has
been implanted for a long time (Cifkova et al.,1990;
Neu et al.,1993). One possible method to overcome
these problems is to modify the silicone surface with-
out changing its bulk properties. Since 1991, we have
carried out a series of works to make the polymer sur-
face more biocompatible using laser systems.
(Mirzadeh et al., 1993, 1994, 1995, 1998; Khorasani et
al.,1996). This technique o€ers possibilities to improve
* Corresponding author. Fax: + 98 21 602 6500.
E-mail address: H.Mirzadeh@www.dci.co.ir (H. Mirzadeh)
develop new biomaterials (Hunt et al., 1995; Viville et
al., 1996; Mirzadeh et al., 1998). The advantage of the
laser systems has been reported elsewhere (Hunt et al.,
1995; Viville et al., 1996; Khorasani et al., 1996;
Mirzadeh et al., 1998).
Interaction of blood components with man-made
materials would trigger thrombus formation on the
foreign surface when it comes to contact with blood
(Fujimoto et al., 1993; Mirzadeh et al., 1998).
Poly(HEMA) is known as a hydrogel with high
hydrophilicity and good biomedical properties (Hsiue
et al., 1994; Mirzadeh et al., 1995). It has been
reported that poly(HEMA) has adequate biocompat-
ibility and has many applications where cell adhesion
is not desirable (Fujimoto et al., 1993; Ho€man et
al.,1985; Hsiue et al., 1993, 1994).
Thee interaction of hydrogels with protein is very
low (Fujimoto et al.,1993; Ho€man et al., 1985) there-

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PII: S 0 9 6 9 - 8 0 6 X ( 9 9 ) 0 0 2 1 2 - 1
686 M.T. Khorasani et al. / Radiation Physics and Chemistry 55 (1999) 685±689
fore the grafting of hydrogels onto polymer surfaces
reduces platelet adhesion.
This study was undertaken to reduce platelet ad-
hesion onto the PDMS surface by laser-induced graft
polymerization of HEMA. For evaluating the haemo-
compatible properties of the HEMA grafted PDMS
®lms, the number of adhered platelets onto the PDMS
®lm surface were counted based on the platelet rich
plasma (PRP) method (Tamada et al., 1995).
2. Experimental
2.1. Irradiation procedure
Laser-irradiation was carried out by the peroxi-
dation technique, which has previously been reported
(Khorasani 1996; Mirzadeh et al., 1998). The laser
used was a line-tuneable, TEA CO2 pulsed laser
(Lumonics-103-2) which provides laser beams of the
wavelengths from 9.1 to 10.6 mm. The PDMS (3090
medical grade from Wacker) as vulcanized ®lms were
exposed to the laser pulses in air under the selected
conditions (Fluency 1±5 J/cm2 and repetition rate of
0.4 Hz) and then washed.
2.2. Characterization of the CO2 laser treated PDMS
1. Attenuated total re¯ectance ATR±FTIR using a
Brucker-88 with KRS-5 prism and adequate pur-
ging. The spectra generated from 50 scans.
2. Scanning electron microscopy (SEM), Cambridge S-
360, was performed on the gold coated samples for
morphology measurement.
3. Hydrophilicity was evaluated by measuring the con-
tact angle formed between the water drop and ®lm
surface using a contact angle measuring system
(Kruss G 10).
4. Platelet adhesion experiments were carried out in
vitro using PRP method (Tamada et al., 1995). The
Fig. 1. Schematic illustration of laser-induced graft polymerization. . indicated radical.
procedure for the PRP preparation and platelet
counting has previously been reported (Tamada et
al., 1995; Mirzadeh et al., 1998).
3. Results and discussion
3.1. Peroxide formation and surface graft
polymerization
Graft polymerization of HEMA onto PDMS surface
was performed according to the scheme illustrated in
Fig.1. The infrared laser induces surface oxidation of
the PDMS by vibrational excitation of the 0Si0O0
band through an infrared multiphoton dissociation
(IRMPD) mechanism (Pola et al., 1991; Khorasani
1996). According to this mechanism the radicals pro-
duced by laser irradiation, immediately react with oxy-
gen forming thus peroxy radicals. The hydroperoxide
groups are formed with hydrogen abstraction from the
PDMS chains. The hydroperoxide groups asre decom-
posed thermally as shown in Fig. 1. The radicals pro-
duced initiate the grafting process.
Fig. 2(a) shows the ATR-FTIR spectrum of the
HEMA grafted PDMS surface. The characteristic
absorption bands of HEMA appearing at 1713 cmÿ1
and 3335 cmÿ1 correspond to the HEMA ester and hy-
droxyl groups, respectively. Comparison of this spec-
trum with the unmodi®ed surface [Fig. 2(b)] gives
evidence for the presence of grafted poly(HEMA) onto
the PDMS surface (Hsiue et al., 1993, 1994).
3.2. Hydrophilicity
The untreated PDMS exhibits hydrophobic beha-
viour and poor wettability, whereas the PDMS ®lm
surface has become hydrophilic upon graft polymeriz-
ation of HEMA. The unmodi®ed PDMS ®lm has 1058
water drop contact angle. The laser treated samples,
only by one pulse, without any graft polymerization
 M.T. Khorasani et al. / Radiation Physics and Chemistry 55 (1999) 685±689
Fig. 2. ATR-FTIR spectra of (a) HEMA grafted PDMS (graft level: 3.8 mg/cm2) with the CO2-pulsed laser by 5 pulses and (b)
untreated PDMS.
give the contact angle of 1708. The measurement of the
water drop contact angle of the grafted surface with
one pulse and 30 wt% HEMA solution, shows that the
contact angle decreases to 358. The decrease in contact
angle by graft polymerization strongly con®rm that
graft polymerization of HEMA actually has taken
place, rendering the hydrophobic surface hydrophilic
(Fujimoto et al., 1993; Hsiue et al., 1993).
3.3. Platelet adhesion study
Platelet-surface interaction is a very complex and
dynamic series of events. Platelet adhesion on the sur-
face is invariably followed by the appearance of plate-
let aggregates and platelets spreading and subsequent
thrombus formation that causes the potential danger
of using arti®cial materials in vivo (Okada and Ikada,
1991). Thus, platelet activation and thrombus for-
mation should be considered to accurately assess the
thrombogenicity of biomaterials (Okada and Ikada,
1991). Since platelet adhesion to a biomaterial surface
is important, platelet number counting is one of the
most popular experimental tools for evaluating the
Table 1
Dependence of the platelet adhesion on the HEMA grafted PDMS with various types of graft level
Pulse number Graft level (mg/cm2)
0 0
1 12.5
3 4.9
5 3.8
7 2.55
10 2.5
15 2.45
20 2.40
687
haemocompatible properties of man-made materials
(Fujimoto et al., 1993; Tamada et al., 1995). The num-
ber of platelets adhered on the PDMS ®lms obtained
from the PRP methods are shown in Table 1. The
adhered platelets are related to the laser pulses and
subsequent HEMA graft level due to wettability of the
samples. As shown in Table 1 as well as in the SEM
micrographs [Fig. 3(a)] platelet adhesion has a maxi-
mum on the untreated PDMS while it has a minimum
on the laser-treated PDMS [Fig.3(b), Table 1]. Also,
complete spreading and aggregation of the attached
platelets were observed on the untreated PDMS. This
is consistent with the previous results that the laser ir-
radiation reduces the surface tension of the treated
PDMS (Khorasani et al., 1996; Mirzadeh et al., 1998).
On the other hand, it seems that the platelets attached
on the HEMA grafted PDMS to be intermediate
between the irradiated ®lms and the untreated one
[Fig.3(c)]. As we have previously reported, the CO2-
pulsed laser induced a super-hydrophobic properties
onto the PDMS ®lms (Khorasani et al., 1996). The
results of our present work exhibit that these ®lms
show less platelets adhesion in comparison with the
Platelets/mm2 after grafting Platelets/mm2 without grafting
17949 17949
6235 1890
3920 1760
3743 1610
3468 1420
2401 1100
5730 2350
7749 3000
688 M.T. Khorasani et al. / Radiation Physics and Chemistry 55 (1999) 685±689
Fig. 3. SEM micrographs of the adhered platelets onto the (a)
untreated PDMS, (b) laser treated PDMS without grafting
and (c) HEMA grafted PDMS (graft level: 3.8 mg/cm2) with
the CO2-pulsed laser by 5 pulses.
HEMA-grafted PDMS. In other words super-hydro-
phobic substrates have a higher blood compatibility
than the hydrophilic ®lms.
4. Conclusion
The CO2-pulsed laser generates radicals on the
PDMS surface and that radicals react with oxygen,
then hydroperoxide formes through hydrogen abstrac-
tion from the PDMS chains. The PDMS surface can
be graft polymerized with water-soluble HEMA mono-
mer through thermal cleavage of the hydroperoxide
groups. In vitro assays showed that the introduction of
poly(HEMA) onto a hydrophobic PDMS has provided
an adequate surface for reducing platelet adhesion and
its activation in comparison with the unmodi®ed
sample. The extent of platelet adhesion was correlated
to the laser pulses and subsequent HEMA graft level.
We conclude that the super-hydrophobic PDMS ®lms
show a higher blood compatibility in comparison with
the hydrophilic PDMS as well as the untreated PDMS.
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