DEPARTMENT: ORGANIC AND MACROMOLECULAR CHEMISTRY

RESEARCH GROUP: POLYMER CHEMISTRY AND BIOMATERIALS

ADVANCES IN THE POLYMER CHEMISTRY

AND BIOMATERIALS GROUP (PBM)

PROF. DR. PETER DUBRUEL & PROF. DR. SANDRA VAN VLIERBERGHE

U
PBM-G ent
Polymer Chemistry & Biomaterials Group
RESEARCH ACTIVITIES @ PBM

Prof. Dr.
Prof. Dr.
Sandra Van Vlierberghe
Peter Dubruel

2
SERVICES WITHIN THE GROUP OF PBM

3
SERVICES WITHIN THE GROUP OF PBM

4
SERVICES WITHIN THE GROUP OF PBM

5
CURRENT MATERIAL RANGE @ PBM
Biodegradable polyesters
- Commercial FDA approved: (PLA, PCL, …)
- In House synthesis: (PDLLA, PLAMA, PMA,…)

degradable sutures

Photocrosslinkable hydrogels (modified gelatin, alginate,…)

T↑

UV irradiation
T↓
Photoinitiator
SOL-GEL
GEL 30-35°C SOL
state UCST state

Acrylate end-capped urethane based (AUP) photocrosslinkable macromonomers (patented toolbox)

Houben et al, Novel urethane based materials, derivatives, methods of 7

their preparation and uses. EP15175956
CROSSLINKING OF HYDROGELS
Hydrogels  as  biomaterials:  
-­‐ Absorb  high  amounts  of  water   UV  
-­‐ Mimic  na5ve  ECM  
-­‐ Ideal  for  biomedical  applica5ons  

Crosslinking  
-­‐ Introduce  chemical  crosslinks,  e.g.  using  photo-­‐ini5ated  polymeriza5on:  
-­‐ E.g.  synthe5c  (PEG-­‐diacrylate)  or  natural  (gela5n  methacrylamide)  
-­‐ Mobility  of  the  end  groups  =>  Crosslinking  in  solu;on  or  in  the  molten  state  

Houben,   A.   et   al.   Indirect   Rapid   Prototyping:   Opening   Up   Unprecedented   Opportuni5es   in   Scaffold   Design   and   Applica5ons.   Ann.  
Biomed.  Eng.  45,  1–26  (2017).   8
USE OF BIOPOLYMERS: ALGINATE

AlgMOD

CaCl2

Alginate
9
 NOVEL PATENTED AUP SYNTHETIC HYDROGEL
Aim: Houben et al, WO
- Develop highly reactive hydrogel precursor 2017/005613
- Produced at environmentally friendly conditions
- Straightforward, industrially applicable synthesis

Diiso-­‐ Diiso-­‐
Acrylate   Spacer   Backbone   Spacer   Acrylate  
cyanate   cyanate  

UV reactivity in the solid state

UV-curable in photoinitiator-free conditions
High solubility in water (up to 9 g/mL)
Biocompatible
Tunable physical properties
Several types of precursors available with different backbones (PEG, PCL, PVA)
10
NOVEL PATENTED SYNTHETIC HYDROGEL
Solid state reactive:
- Measure reaction speed using photo-DSC
- Material is more reactive in solid state
- Molecular flexibility of spacer affects reactivity

Name Spacer
PEO-HEAcr No Spacer
PEO-PPOAcr 6 PO units Exposure time (s)

PEO-PCLAcr 2 Caprolactone units

PEO-PEOAcr 6 EO units

11
NOVEL PATENTED SYNTHETIC HYDROGEL
Solid state reactive:
- Measure reaction speed using photo-DSC
- Material is more reactive in solid state
- Molecular flexibility of spacer affects reactivity

Name Spacer
PEO-HEAcr No Spacer
PEO-PPOAcr 6 PO units
PEO-PCLAcr 2 Caprolactone units
PEO-PEOAcr 6 EO units

12
NOVEL PATENTED SYNTHETIC HYDROGEL
Absence of photo-initiator:
- Toxic effect of PI
- Mixing step Can be avoided
- Leaching of PI

- Rheology:
• Slightly slower reaction
• Same rheological properties

13
NOVEL PATENTED SYNTHETIC HYDROGEL
Extreme water compatibility
- Water swellable hydrogel from
10-100 wt% prepolymer content
- Highly tunable characteristics
- High gel fraction for all compositions

14
POSSIBLE APPLICATIONS OF AUP

15
ELECTROSPINNING OF AUP

16
MECHANICAL PROPERTIES AFTER
ELECTROSPINNING

PCL
PLA esp
AUP (PEG8000) + PEO AUP (PEG20000) esp esp PET esp
2 membra
esp membranes membranes membr membranes
nes3
anes1
Young’s
Modulus 14.3 ± 2.9 8.5 ± 1.8 ~8 ~ 60 ~ 55
(MPa)
Ultimate
1.9 ± 0.2 1.9 ± 0.3 ~2 ~4 ~1
Stress (MPa)
Ultimate
Strain 270.2 ± 18.9 100.0 ± 15.2 ~ 250 ~ 50 ~ 17.5
(%)

1 Dong et al., J Biomed Mater Res Part A 2012:100A:903–910. 2 Veleirinho et al. J Polymer Sci B
Polymer Phys 2008:46:460-471 3 Wang et al. J Biomed Mater Res Part A 2012:100A:441–449.
* Tests were performed in dry state. 20
CO-EXTRUSION ELECTROSPINNING AS
NOVEL TOOL FOR CORE/SHELL
Dual-solution feed system
Fiber inside another fiber → core/shell +
combined characteristics
Similar varying parameters as ES

21
3D PRINTING POSSIBILITIES

- Processing of hydrogels: always from solution

- Polymer is heated above melting point (38°C)
- Solidifies upon extrusion
- Separate curing step after printing

Scaffold after UV- Scaffold after swelling

crosslinking
22