Hemocompatibility of Plasma Treated Si Incorporated Diamond-like Carbon Films
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Transcript of Hemocompatibility of Plasma Treated Si Incorporated Diamond-like Carbon Films
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Hemocompatibility of Plasma Treated Si
Incorporated Diamond-like Carbon Films
R. K. Roy, M.-W. Moon, K.-R. LeeFuture Convergence Research Laboratories, KIST, Seoul, Korea
D.K. HanBiomaterials Research Center, KIST, Seoul, Korea
J.-H. ShinDepartment of Radiology, Asan Medical Center, Universtiy of Ulsan, Korea
A. KamijoUniv. Tokyo Hospital, Tokyo, Japan
T. HasebeTachikawa Hospital, Keio University, Tokyo, Japan
ICMCTF 2008, San Diego, USA
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Requirements for Bioimplants1. Should not cause infections2. Prevent uncontrolled cell growth3. Maintain their integrity inside the
body4. Interact in a controllable way with
the biological environment
5. Avoid formation of debris
Requirements for Bioimplants1. Should not cause infections2. Prevent uncontrolled cell growth3. Maintain their integrity inside the
body4. Interact in a controllable way with
the biological environment
5. Avoid formation of debris
Surface PropertiesSurface Properties
Bioimplant Materials
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DLC for biomaterials
• Biological Compatibility– Nontoxic, Noncarcinogenic,
Noninflammatory
• Chemical Compatibility– Corrosion Resistance
• Mechanical Compatibility– Surface Hardness, Wear Resistance
Diamond-like Carbon :as a Strong Candidate Coating
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Vascular Stents
• Suppress the formation of blood clots• Prevent the release of metal ions
Clotted Artery
Hemocompatible and Hermetic Coating
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DLC Coated Blood Contacting Implants
CarbofilmTM by Sorin Biomedica, Inc.
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The present work
Systematic study on the effect of surface properties on the hemocompatibility.
• Plasma treatment of Si-DLC coating• Characterization of the surface
– Wetting behavior– Surface chemical bonds
• Hemocompatibility tests– Protein adsorption (Albumin/Fibrinogen
ratio)– Activated Partial Thromboplastin time– Platelet adhesion and activation
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Si-DLC Film
10-14 10-13 10-12 10-11 10-10 10-9 10-8 10-7 10-6 10-5 10-4 10-3 10-2 10-1 100 101
-600
-400
-200
0
200
400
600
800
1000
1200
1400
1600
Po
ten
tial (
mV
vs
SC
E)
Current Density (A/cm2)
Substrate Si-C:H, Bias voltage = -400V a-C:H, Bias voltage = -800V a-C:H, Bias voltage = -400V
Potentiodynamic Polarization in Saline Solution
Thin Solid Films, 475, 291-397 (2005).J. Biomed. Mater. Res. A in press (2007).
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Schematics of RF PACVD system.
Film Preparation
• Film Deposition– C6H6 + SiH4
– Pressure : 1.33 Pa– Bias voltage : -400V– Film thickness : ~500nm – Si Concentration in the
film : 2 at.%
• Surface Treatment– O2, N2, H2, CF4
– Pressure : 1.33 Pa– Bias voltage : -400V– 10min
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Surface modification of Si-DLC
20
40
60
80
100W
ater
co
nta
ct a
ng
le (
in d
egre
e)
SiDLC( O2treated)
SiDLC(N2treated)
SiDLC(H2treated)
SiDLC(CF4treated)
SiDLCSi Nitinol
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Energetics of Surface
(cos ) lv sv sl
22ll
pl
dllv
22ss
ps
dssv
)(2
cos1
)(2)(2cos1
lslslv
lv
pl
ps
lv
dl
ds
Liquid αl βl
γlv
(ergs/cm2)
Water 4.67 7.14 72.8
Formamide 6.28 4.32 58.2
2 : Fowkes' Eq.d dsl sv lv s l
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Surface Energy
Polar component
0
10
20
30
40
50
60
SiDLC SiDLC (O
2
treated)
SiDLC (N
2
treated)
SiDLC (H
2
treated)
SiDLC (CF4
treated)
Sur
face
ene
rgy
(dyn
e/cm
)
Dispersive component
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Interfacial Tension with Human Blood
α (dyne/cm)1/2
β (dyne/cm)1/2
Human Whole Blood
3.3 6.0
221
22112 )()(
0
5
10
15
20
25
SiDLC(O2
treated)
SiDLC(N2
treated)
SiDLC(H2
treated)
Blo
od B
iom
ater
ial i
nter
faci
al t
ensi
on
(dyn
e/cm
)
SiDLC SiDLC(CF4
treated)
α β
Si-DLC 5.4 ± 0.5 3.3 ± 0.6
Si-DLC (CF4 treated) 5.0 ± 0.4 2.0 ± 0.5
Si-DLC (N2 treated) 5.1 ± 0.2 5.5 ± 0.3
Si-DLC (O2 treated) 4.2 ± 0.1 7.3 ± 0.1
Si-DLC (H2 treated) 5.5 ± 0.3 3.5 ± 0.4
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100 102 104 106
4
8
12
16
Inte
nsi
ty (
x1
0 )
Binding energy (eV)
Si-C
Si 2pSiDLC
Si2O3
SiO2
(b)
280 284 288 2920
10
20
30
40
50
Inte
nsi
ty (
x1
0 2
)
Binding energy (eV)
C=C
C-C
Si-DLC
C 1s(a)
280 284 288 2920
10
20
30
40
Inte
nsity
( x
10
2 )
Binding energy (eV)
C=C
C-CC-OH
H2-Si-DLC
C 1s(c)
100 102 104 106
4
8
12
16
Inte
nsity
( x
10 )
Binding energy (eV)
Si-C
Si-Si
Si2O3
Si 2pH2-Si-DLC(d)
XPS Anaysis
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XPS Analysis
FilmsChemical bonds present on surface
(XPS analysis)
Si-DLC or Si-DLC (H plasma
treated)C=C, C-C, Si-C, Si-O
Si-DLC(CF4 plasma treated)
C=C, C-C, C-CFn, Si-C, Si-O
Si-DLC(N plasma treated)
C=C, C-C, C-N, Si-N, Si-O
Si-DLC(O plasma treated)
C=C, C-C, C-O, Si-O
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100 102 104 106
4
8
12
16
Inte
nsi
ty (
x1
0 )
Binding energy (eV)
Si-C
Si 2pSiDLC
Si2O3
SiO2
(b)
280 284 288 2920
10
20
30
40
50
Inte
nsi
ty (
x1
0 2
)
Binding energy (eV)
C=C
C-C
Si-DLC
C 1s(a)
XPS Anaysis
280 284 288 2920
4
8
12
16
Inte
nsi
ty (
x1
0 2 )
Binding energy (eV)
C=C
C-C C-O C=O
C 1sO2-Si-DLC(k)
100 102 104
20
40
60
80
Inte
nsi
ty (
x10
)
Binding energy (eV)
Si 2pO2-Si-DLC
Si2O3
SiO2
Si-C
(l)
280 284 288 2920
5
10
15
20
25
Inte
nsi
ty (
x1
0 2 )
Binding energy (eV)
C-CFn
CF-CFnCF2 CF3
1
2
C 1sCF4-Si-DLC(e)
100 102 104 106
4
6
8
10
Inte
nsi
ty (
x 1
0 )
Binding energy (eV)
Si-C
Si2O3
SiO2
Si-Si
Si 2pCF4-Si-DLC(f)
Si-DLC Si-DLC (CF4)Si-DLC (O2)
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100 102 104 106
5
10
15
20
25
Inte
nsi
ty (
x10
)
Binding energy (eV)
Si-N
Si-CSiO2
Si 2pN2-Si-DLC(i)
280 284 288 2920
5
10
15
20
25
Inte
nsity
( x
10
2 )
Binding energy (eV)
C 1sN2-Si-DLCC=C
C=N
C=N
C-C
C-N
(h)
100 102 104 106
4
8
12
16
Inte
nsi
ty (
x1
0 )
Binding energy (eV)
Si-C
Si 2pSiDLC
Si2O3
SiO2
(b)
280 284 288 2920
10
20
30
40
50In
tens
ity (
x10
2 )
Binding energy (eV)
C=C
C-C
Si-DLC
C 1s(a)
Si-DLC Si-DLC (N2)
XPS Anaysis
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Plasma Protein Adsorption
• Better hemocompatibility can be expected on the surface with higher ratio of albumin/fibrinogen adsorption.
• ELISA analysis after treating the samples with albumin (3mg/ml) and fibrinogen (0.2mg/ml) solution.
0.0
0.5
1.0
1.5
2.0
SiDLC (H2
treated)
SiDLC(O2
treated)
SiDLC(N2
treated)
SiDLC (CF4
treated)
SiDLC
Alb
umin
/ f
ibri
noge
n ra
tio
5 mins
60 mins
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aPTT Measurement
• Activated partial thromboplastin time (aPTT) determines the ability of blood to coagulate through the intrinsic coagulation mechanism. The longer aPTT time is obtained on better hemocompatible surface.
• Soaking for 60min in platelet poor plasma (PPP: 7x103/l) using human whole blood from healthy volunteer.
25
26
27
28
29
30
SiDLC(O2
treated)
SiDLC(N2
treated)
SiDLC(H2
treated)
SiDLC(CF4
treated)
aPT
T (
sec)
1 hour
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Platelet Adhesion Measurement
• Soaked for 60 min in PRP (1.5x105/ml) from human whole blood from healthy volunteer.
• Adherent platelet are fixed and dehydrated for observation under OM and SEM.
Si-DLC Si-DLC(CF4) Si-DLC(N2) Si-DLC(O2)0
10
20
30
40
50
60
70
80
90
100
Pla
tele
t Ad
he
sio
n A
rea
Ra
tio (
%)
Specimen
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Platelet Activation
Goodman and Allen et al.
On a-C:H surface
Lose discoid shape
Develope thin pseudopodia
Become large, spiny sphere covered by pseudopodia
Fully spread
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Platelets on Si-DLC
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Platelets on Si-DLC (N2)
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Platelet on Si-DLC (O2)
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Nitrogen or Oxygen Plasma Treatment
25
26
27
28
29
30
SiDLC(O2
treated)
SiDLC(N2
treated)
SiDLC(H2
treated)
SiDLC(CF4
treated)
aPT
T (
sec)
1 hour
0.0
0.5
1.0
1.5
2.0
SiDLC (H2
treated)
SiDLC(O2
treated)
SiDLC(N2
treated)
SiDLC (CF4
treated)
SiDLC
Alb
umin
/ fib
rinog
en r
atio
5 mins
60 mins
Si-DLC Si-DLC(CF4) Si-DLC(N2) Si-DLC(O2)0
10
20
30
40
50
60
70
80
90
100
Pla
tele
t A
dh
esi
on
Are
a R
atio
(%
)
Specimen
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XPS Analysis
FilmsChemical bonds present on surface
(XPS analysis)
Si-DLC or Si-DLC (H plasma
treated)C=C, C-C, Si-C, Si-O
Si-DLC(CF4 plasma treated)
C=C, C-C, C-CFn, Si-C, Si-O
Si-DLC(N plasma treated)
C=C, C-C, C-N, Si-N, Si-O
Si-DLC(O plasma treated)
C=C, C-C, C-O, Si-O
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Which surface bond is significant?
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Conclusions
• Hemocompatibility of Si-DLC film was improved by the surface treatment using nitrogen and oxygen plasma.– Large surface energy (large polar component)– Low interfacial energy with blood
• Both C-O and Si-O bonds on the plasma treated Si-DLC surface play a significant role in improving the hemocomptatibility.
R. K. Roy et al,Diam. Rel. Mater (2007). Submitted to Acta Biomater. (2008).
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Acknowledgement
Financial Support from 'Center for Nanostructured Materials Technology' under '21st Century Frontier R&D Programs' of the Ministry of Science and Technology of Korea (code #: 06K1501-01610), and Taewoong Medical Co. Ltd.