1. PREPARATION OF POLYURETHANE-BASED BIOMATERIALS
WITH ANTI-BACTERIAL AND ANTI-ADHESIVE PROPERTIES
Biopol 2017
Rana Al Nakib,1,2 Antoniya Toncheva,1 Jean-Marie Raquez,1 Franck Meyer2
1Laboratory of Polymeric and Composite Materials, University of Mons, Place du Parc, 20, 7000 Mons, Belgium
2Laboratory of Biopolymers and Supramolecular Nanomaterials, Université Libre de Bruxelles, Faculty of Pharmacy, Campus Plaine, Boulevard du Triomphe, 1050
Bruxelles, Belgium
Medical devices, as catheters, are of great interest for biomedical technology due to their ability to deliver divers bioactive substances, to transport biologic fluids, to be used as
implants with excellent biocompatibility, and other applications.1 Despite their advantages, they are still the main cause of health care associated infections, as they are
subjected to biofilm formation and platelet aggregation2,3 difficult to eradicate with antibiotics due to the formed multilayer barrier.4,5 Therefore, the material coating the catheter
surface should have high thermal stability, sufficient mechanical properties and an anti-bacterial and anti-adherent properties. Interestingly, thermoplastic polyurethanes (TPUs)
apply to a broad range of such properties due to the ability of varying their hard-soft segment content.6 The purpose of this study is to develop modified polyurethane materials
with repellent behaviors toward bacteria, biomolecules and cells.
Abstract
Hard
Segment
Soft
Segment
TPUs Synthesis (Objective 1) Quaternary Ammonium Salt (QAS) Synthesis (Objective 2)
QAS were synthesized through modifying Br-diols in order to
synthesize positively charged TPUs having anti-bacterial and anti-
adherent properties.
TPUs Characterization Tests
C-N bands support the formation of the urethane group and
confirm the successful poly-condensation. The full conversion
of the NCO groups is proved by the absence of the band
around 2270 cm-1.
¹H-NMR
(ppm)
F
A B
D C
G,H
DMSO
E
J
Absence of
NCO groups
1500 cm-1
FT-IR TGA
-0.2
0.0
0.2
0.4
0.6
0.8
1.0
1.2
Deriv.Weight(%/°C)
0
20
40
60
80
100
Weight(%)
0 100 200 300 400 500 600
Temperature (°C)
Sample: 24-05-17 RAAN A37
Size: 3.2180 mg TGA
File: C:...TGAMay24-05-17 RAAN A37.001
Operator: RAAN
Run Date: 24-May-2017 12:38
Instrument: TGA Q500 V20.10 Build 36
Universal V4.4A TA Instruments
Td (PTHF)
= 414 °C
Td (MDI)= 340 °C
0
5
10
15
20
25
30
35
40
45
0 50 100 150 200 250 300 350
Stress
(MPa)
Strain (%)
MechanicalProperties
Elongation at break
= 267±48 %
Tensile strength
= 35±5 MPa
Young’s Modulus (E)
= 171±15 MPa
.
Perspectives
• Synthesized QAS will be characterized and grafted in the TPUs.
• Quaternary Phosphonium Salt (QPS) will be synthesized as they are known to have a high anti-bacterial effect and together with
QAS will exert a synergistic effect.
• The anti-microbial efficiency of QAS/QPS polymers will be studied by the measurements of the minimum inhibitory concentration.
• Platelet adhesion will be carried out using fresh blood in standard conditions to study the anti-adherent effect.
TPUs structures were confirmed using ¹H-NMR TGA confirmed the high thermal stability of the
synthesized TPUs
Td: degradation temperature
DSC revealed the semi-crystallinity of the TPUs
Tg: glass transition temperature, Tm: melting temperature
TPUs mechanical testing encountered the desired
properties where sufficient elongation was reached
0.1
TanDelta
0.1
1
10
100
1000
LossModulus(MPa)
0.001
0.01
0.1
1
10
100
1000
10000
StorageModulus(MPa)
-100 -50 0 50 100 150 200
Temperature (°C)
Sample: RAAN A46 DI
Size: 4.8580 x 4.9000 x 0.1300 mm
Method: methode E
DMA
File: C:...DMARAAN A46 DI.001
Operator: RAAN
Run Date: 02-Aug-2017 10:32
Instrument: DMA Q800 V20.24 Build 43
Universal V4.4A TA Instruments
DMA
At Tg (-44 °C), E’= 2789 MPa while E’’= 100 MPa, verifying
the high elasticity of the TPUs and a high thermo-
mechanical property
Conclusion
The aim of the present research is to prepare TPUs-based materials with anti-bacterial and anti-adherent properties. TPUs known to have a tunable
thermal and mechanical properties by varying the hard-to-soft segment content. Therefore, well attention should be paid to the used molar ratio as
polymer materials have a huge versatility, ranging from highly elastic soft materials to tough-hard materials.
So far, the results of this study showed that TPUs were synthesized successfully having the desired thermal and mechanical properties (objective
1). Additionally, the synthesized QAS will be characterized to check the successfulness of objective 2 and will be grafted in the TPUs where their
anti-bacterial and anti-adherent effect will be tested.
References Contact Acknowledgement
1. Wildgruber et al. Eur J. Cancer 2016, 59, 113.
2. Francolini et al. J. Fems 2010, 59, 227.
3. Zhang et al. Int J. Antimicrobial Agents 2011, 38, 9.
4. Høiby et al. J. of Antimicrobial Agents 2010, 35, 322.
5. Campoccia et al. J. Biomaterials 2013, 34, 8533.
6. Sáenz-Pérez et al. J. Rcs 2016, 00, 1.
Jean-Marie Raquez: jean-marie.raquez@umons.ac.be
Franck Meyer: franck.meyer@ulb.ac.be
Rana Al Nakib: rana.alnakib@student.umons.ac.be,
ralnakib@ulb.ac.be
Antoniya Toncheva: antoniya.toncheva@umons.ac.be
I would like to thank the Laboratory of Polymeric and Composites
Department of UMons, and the Municipality of Ghazieh, Lebanon
for the financial support of this research.
DSC
-1.0
-0.5
0.0
0.5
1.0
HeatFlow(W/g)
-100 -50 0 50 100 150 200 250
Temperature (°C)
Sample: 29-05-17 RAAN A37 TRI MODU
Size: 10.0000 mg
Method: Heat/Cool/Heat
DSC
File: C:...29-05-17 RAAN A37 TRI MODU.001
Operator: RAAN
Run Date: 29-May-2017 17:29
Instrument: DSC Q200 V24.4 Build 116
Exo Up Universal V4.4A TA Instruments
Tg = -44 °C Tm = 187 °C