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Corona Pla Bun MatteoGherardi2
Corona Pla Bun MatteoGherardi2
OUTLINE
Tissue engineering & electrospun scaffolds
Surface modification
Plasma sources
Chemical functionalization
Conclusions
HYSTORICAL NOTE
Pioneer in plasma science Pioneer in surface chemistry
IRVING LANGMUIR
Doctoral dissertation on glowing 1932 Nobel prize for chemistry
platinum wire and hot gases at (studies on surface adsorption)
low pressure
Studies on surface catalysts
Studies on thermoionic emission
Introduced the concept of monolayer
Studies on electricity effects on gases
-> coined the term PLASMA Co-invented the Langmuir-Blodgett film
(technique to produce organic monolayers)
Invented the electric probe
(Langmuirs probe)
Molecular
structure Nanostructure
Self assembly
Solvent
Polymer
Dissolution Gelation Solvent removal
Phase separation
Science, 2005, 310, 1135-1138
Cells assume a
Cells flatten
spread morphology
MORPHOLOGICALLY
BIOMIMETIC
Electrospinning
Natural ECM
ELECTROSPINNING
Electrospinning
Liquid polymer solution fed through a capillary
tube into a region of high electric field
Polymer nanofibers
Non-woven mat
Disdvantages
Sub-micrometric fibers
Collector
Use of organic solvents
Poor control over 3D structure
High voltage
power supply
LAB & INDUSTRIAL
SCALE PROCESS
SURFACE MODIFICATION OF ELECTROSPUN NANOFIBER
TARGET: SURFACE FUNCTIONALIZATION AND MODIFICATION
OF SURFACE PROPERTIES (HYDROPHILICITY)
SURFACE MODIFICATION
Introduction of functional groups on the surface Biocompatibilization
Can be followed by functionalization
Plasma treatment
Superficial treatment, does not affect bulk properties Surface
Nanofibers
Chemical treatment modification
Adapt for modification of thick scaffolds
Functionalization
May lead to polymer degradation (protein, enzyme,)
CO-ELECTROSPINNING Functional
Nanoparticles/polymeric fragments added to the solution agents
Th << Te
Electrons
Heavy particles
LOW PRESSURE vs ATMOSPHERIC PRESSURE PLASMAS
Radicals
Electrons
Radiation
Ions
Treated material
Treatment uniformity
PLASMA SOURCES
DBD roller
Nylon Working gas: Air
dielectric Dielectric layer on both electrodes
to prevent transition to arc
Large area treatment
Easily scaled-up
Negligible surface
modification
Treatment uniformity
PLASMA SOURCES
LINEAR CORONA
Working gas: He, Ar, N2
Large area treatment
Easily scaled-up
SS
electrode
Insulator
No dielectric layer
SS
electrode
Insulator
No dielectric layer
RR RR
PV PV
us ns
PV: 40kV PV: 40kV PV: 20kV
F = 1000Hz RR = 1000Hz RR = 1000Hz
Plasmasource
DEFINITION OF OPTIMAL OPERATIVE CONDITIONS
DISCHARGE & TEMPERATURE UNIFORMITY
Plasmasource
DEFINITION OF OPTIMAL OPERATIVE CONDITIONS
DISCHARGE & TEMPERATURE UNIFORMITY
Plasmasource
Bottom view
Number of filaments
Filaments motion
DEFINITION OF OPTIMAL OPERATIVE CONDITIONS
DISCHARGE & TEMPERATURE UNIFORMITY
Schlieren
Bottom view
Number of filaments
Filaments motion
DEFINITION OF OPTIMAL OPERATIVE CONDITIONS
DISCHARGE & TEMPERATURE UNIFORMITY
Diffuse
Filamentary
PV = 23 kV, RR = 1000 Hz, gap = 6 mm
DEFINITION OF OPTIMAL OPERATIVE CONDITIONS
DISCHARGE UNIFORMITY iCCD IMAGING
Exposure time = 3 ns, images not overlapped
PIMAX 3, Princeton Instruments
t = 0 ns t = 0 ns
5 6
t = 14 ns t = 11 ns
6 7
t = 16 ns t = 13 ns
7 8
t = 20 ns t = 16 ns
DEFINITION OF OPTIMAL OPERATIVE CONDITIONS
MORPHOLOGICAL ANALSIS - SEM
4000x
300x
1000x
Visible damages after non-optimized plasma treatment No damages after optimized plasma treatment
CHEMICAL FUNCTIONALIZATION
Carboxyl (COOH) groups are the most used reactive group to covalently attach molecules using primary amine
Plasma O EDC/sNHS
treated CONH NH2 FITC FITC
C
OH H2N NH2
= Di-aminodutane
FITC FITC
(Normalized vs pristine)
500
500
2500
2500
Mean intensity (a.u.)
COOH-FITC
400
400
COOH-FITC
2000
2000
300
300
1500
1500 200
200
1000
1000 FITC 100
100
500
500 0
0
2500
2500
Mean intensity (a.u.)
2000
2000 Mean of fluorescence intensity of
COOH-FITC
1000
1000
500
500
00
tt=0
=0 tt=6
=6 tt=24
= 24 tt=48
= 48
Time (h)
time (h)
Materials with lower elastic moduli are required for soft tissue engineering applications
No differences were observed in thermal properties (from TGA and DSC) before and after
plasma treatment, indicating that no significant reduction in PLLA molecular weight occurred
CONTACT ANGLE MEASUREMENTS (WCA)
LINEAR CORONA - LC N2
WCA (deg)
FE-DBD has been found to damage the polymer due to local heating
Rat embryonic stem cells (RESCs) grown on pristine PLLA electrospun scaffolds
showed higher proliferation rate compared to standard 2D conditions
THANK YOU FOR YOUR ATTENTION
ANY
(PLASMA RELATED)
QUESTIONS?