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Pietro Favia (Sci. Resp.) Eloisa Sardella, Roberto Gristina, Giorgio Senesi,
Loredana Detomaso, Riccardo d’Agostino
Department of Chemistry, University of Bari, Institute of Inorg. Methods and Plasmas (IMIP) CNR
Via Orabona 4, 70126, Bari, ItalyPh +39 080 5443430, fax +39 080 5443431
e-mail: [email protected]
Non equilibrium plasma processes for biomedical applications
and nanotechnology
FIRB program“NANOBIO”
Ravello, December 5-7, 2002kick off meeting
University of BariProf. Riccardo d'AGOSTINOProf. Pietro FAVIAProf. Francesco FRACASSI
IMIP Bari, CNRDr. Fabio PALUMBODr. Roberto GRISTINADr. Giorgio SENESI
Technician, CNRVincenzo COLAPRICO
Post DocDr. Eloisa SARDELLADr. Antonella MILELLADr. James DELATTREDr. Juan MORALES CORONA
Ph.D studentsErnesto MESTOAntonella FORNELLILoredana DE TOMASOFiorenza FANELLI
On a grantG. Iacoviello, V. Bonasia,R. Di Mundo, L. Iacobelli
5 undg students
OUR GROUP
SecretariatGrazia RETTORoberta GIORDANO
University of BariProf. Riccardo d'AGOSTINOProf. Pietro FAVIAProf. Francesco FRACASSI
IMIP Bari, CNRDr. Fabio PALUMBODr. Roberto GRISTINA (biol.)Dr. Giorgio SENESI
Technician, CNRVincenzo COLAPRICO
Post DocDr. Eloisa SARDELLADr. Antonella MILELLADr. James DELATTREDr. Juan MORALES CORONA
Ph.D studentsErnesto MESTOAntonella FORNELLILoredana DE TOMASOFiorenza FANELLI
On a grantG. Iacoviello, V. Bonasia,R. Di Mundo, L. Iacobelli
5 undg students
OUR GROUPBiomedical applications of plasmas
SecretariatGrazia RETTORoberta GIORDANO
Dr. Marco Morra (NobilBio Ricerche) consultant for NANOBIO Firb
PLASMA PROCESSESPE-CVD deposition of thin films
organic-inorganic
TREATMENTS grafting of groups, crosslinking
DRY ETCHING ablation of materials
RF generator13.56 MHz
pump
pressure gauge50 - 1000 mTorr
gasinlet
PLASMA
optical window(spectroscopy)
PARALLEL PLATEPLASMA REACTOR
Understanding relationships between
plasma chemistry (emission spectroscopy)surface chemistry (surface analysis)
and surface properties
for industrial applications
REACTORS AVAILABLE INMANY CONFIGURATIONS
parallel plate, triode,roll to roll, powders,
small tubes, …
REACTOR ENGINEERING
OES
Plasma treatments inside small caliber tubes(catheters, VGs, … )
surfaceanalysis
ESCACA
AFM
biologicallab
NOBIL BIO RICERCHEDr. Marco Morra, Dr. Clara Cassinelli
SURFACE MODIFICATIONAND SURFACE CHARACTERIZATION
OF BIOMEDICAL MATERIALS AND DEVICES
NOBIL BIO RICERCHE is an indipendent company that providescontract services for the surface characterization and modification of
biomedical devices and materials.
NOBIL BIO RICERCHE Str. S. Rocco 3214108 Villafranca d'Asti, Italy
Ph: +39 0141 942446, Fax: +39 0141 943840e-mail: [email protected]
www.nobilbio.it
Nobil Bio Ricerche founded in 1993
A small, privately-owned company, operates in the field of biomedical devicesand materials. The expertise includes study, characterization and modificationof surface properties of medical devices and materials, and their chemico-physical and biological characterization. Nobil Bio Ricerche operates on a contract-service basis for a number of biomedical companies.Contract activities include:
- studies aimed to improve surface properties of existing devices or to developnew surface modification treatments.
- characterization of composition/properties of medical devices and materials- custom surface treatments.
Typical works include surface modification of IOLs, prevention of post-surgicaladhesion to surgical meshes, surface modification of blood filters, immunologicplates, coronary catheters and stents.The facilities include a chemico-physical lab equipped with SEM, AFM, different spectroscopies, and two plasma reactors ((micro-wave and radio-frequency) in a class 10,000 clean room. Biological tests are performed in a microbiological lab, that allows growth culture of mammalian and bacterialcells, and the study of their interactions with medical materials and devices.
PE-CVD, Treatment, Etching processesContinuous and modulated processesPlasma and surface diagnosticsPlasma treatments of powdersRoll-to roll reactorPlasma-reactor design
Hydrophilic-hydrophobic surfacesImmobilization of biomoleculesCell-adhesive surfacesCell-repulsive (non fouling) surfacesMicro-patterning of polymersBacterial-resistant coatingsNano-rough functional surfacesConformal thin coatings on nano-structures
Permanently wettable teflonPlasma treatments inside small caliber tubesSuper-hydrophobic surfacesGas barrier coatingsImproving metal adhesion on polymers
“PRODUCTS”from
UNIBAfor the
biomedical field
Ageing trends for N-grafted PTFE with ( ) and without ( ) H2 plasma pre-treatment
0
26
52
78
104
130
0 10 20 30 40 50 60 70Storage Time (days)
θE (
degr
ees)
θE Untreated PTFE
Control of thehydrophobic recovery
in plasma-treated polymers
Pre-treatments(e.g., H2, Ar, …)
may be utilized to cross-linkthe surface of the polymer
before the grafting
HYDROPHILICPOLYMERS
IMMOBILIZED HEPARINE FOR BLOOD-COMPATIBLE
SURFACES
Non activated rabbit plateletsonto HyalS3.5 immobilizedon plasma-processed PE
substrate
plasma-modified functionalized layer
spacerarm
biomolecule
SAME APPROACH FOR PEPTIDES, ENZYMES,
ANTIBODIES, …
IMMOBILIZATIONOF BIOMOLECULES
PE-CVD -COOH functional coatingsPLASMA TREATMENT N-grafted polymer surfaces
cell growth covalent binding of molecules
-COOH
-COOH
-COOH
-COOH
>C=O
-OH
>C=O
-OH
C CO
CH2=CCOOHH
-NH
2
-CN
>C=O
--OH
--NH
2
=NH
-NH
2
-CN
NH3
KEY ISSUESretention of monomer structurelow power, modulated discharges
process controldensity of groups
adhesion to substratestability in water
CELL ADHESIVE SURFACES
-CN
0
5
10
15
20
25
30
35
0 20 30 40 50
C3%
Input Power (W)
AA
C3 component of pdAA films deposited at differentDuty Cicles (3% ; 5% ; 10% ; 20% ; 30% ; 50% ; non modulated )
0
5
10
15
20
25
30
35
0 20 30 40 50
C3%
Input Power (W)
AA
C3 component of pdAA films deposited at differentDuty Cicles (3% ; 5% ; 10% ; 20% ; 30% ; 50% ; non modulated )
FINE CONTROL OF COMPOSITION plasma deposited Acrylic Acid (pdAA) coatings
FROM MODULATED PLASMAS
BE( eV)285289 )
C3
BE( eV)285289 )BE( eV)285289 )
C3
Available also formonomers with –NH2
and other groups
9.6±0.832.0±5.8continuousplasma
C3= 13±3%
39±5.733.0±7.5DC 20%C3= 18±3%
60±2.243.0±5.5DC 3%C3= 26±3%
Spreadcells %
Adhered cellson 0,8 mm2C3%
TUNING CELL-ADHESION/SPREADING WITH –COOH (C3) SURFACE DENSITY OF pdAA COATINGS
(NCTC 2544 keratinocytes, 24 h of culture)
AA 3 sscm; Ar 20 sscm; 230 mtorr; 20 W
PEO-like COATINGSnon fouling, hydrophilic,
cell-repulsive
Feed glycols, crown ethers
CH3O(CH2CH2O)nCH3
Key Parameterretention of the PEO
structure in the coating
Process controlOES monitoring of CO emission
o
o
o
o
PEO -(CH2CH2O)n-
PEO-like
oo
o)n(
OHo
oo o
ooo
oo
o
HO
o o
o
CELL REPULSIVE (non fouling)SURFACES
280282284286288290292
Binding Energy (eV)
15W
C1=41%
10W
C1=68%
5W
C1=81%
0
50
100
150
200
250
300
15 10 5Power (W)
: Spread cells/adhered cells
adhe
red
cells
/0.8
mm
2
70µm
70µm
70µm
cellrepulsive
cellrepulsive
pdAA 70µm
PEO-like 70µm N-groups 70µm
PEO-like0
50
100
150
200
250
num
ber o
f adh
ered
cel
ls/m
m2
N-groups
37%
pdAA
80%
35 µm
ALLIGNED 3T3 FIBROBLASTS (pdAA/PEO-like)
70 µm
MICRO-PATTERNINGOF POLYMERS
G50Pholes=416µbar=84µm
G100Pholes=208µbar=42µm
PS/PEO-like N-groups/PEO-like
NCTC2544 human keratinocytes onto microstructured PS
DEGDME/Ar
100µm
Peo-like
Peo-like
Peo-like
Peo-like
DEGDME/ArNH3
70µm
Peo-
like
Peo-
like
G50Pholes= 416µm
bar= 84µm
3T3 murine fibroblasts on pdAA/PEO-like µ-structured PS
Peo-like
Peo-likepdAA
Peo-like
Peo-likepdAA
70µm
Peo-like
pdAA
Peo-like1day
5 days
2 days
The tracks, in effect, are more likeCHANNELS
The cells can “feel” the chemistry of the channels, but also their
BORDERS
NanocompositeAg/PEO-like coatings
substrate
PEO-like network-(CH2CH2O)n-
Ag clusters
NON FOULING
BACTERIOSTATIC
BACTERIALRESISTANTCOATINGS
super hydrophobic
nano-structured
fluorocarbon coatings
5 µm
NANO-ROUGHFUNCTIONALCOATINGS
Nano roughness of two different PS dwells(2 different manofacturers)
5 µm
0 µm
2.5 µm
5 µm0 µm 2.5 µm
5 µm
0 µm
2.5 µm
5 µm0 µm 2.5 µm
5 µm
0 µm
2.5 µm
5 µm0 µm 2.5 µm
5 µm
0 µm
2.5 µm
5 µm0 µm 2.5 µm
5 µm
0 µm
2.5 µm
5 µm0 µm 2.5 µm
5 µm
0 µm
2.5 µm
5 µm0 µm 2.5 µm
PE-CVD of ultrathin hydrophilic conformal coatings on hydrophobic nanostructured (35 nm height)
polymers for tissue engineering
withoutpre-treatment
withpre-treatment
CONFORMAL THIN COATINGSON NANOSTRUCTURES
GristinaFavia
d’Agostino
SardellaDetomaso
16th International Symposium on Plasma ChemistryTaormina, ITALY June 22-27, 2003
