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Antibacterial textiles based on poly-pyrrole
nano-coatings
aintech@ain.es
ANTIBACTERIAL TEXTILES
BASED ON POLY-PYRROLE
NANO-COATINGS
María Monteserín, Francisco Martín, Gonzalo G.
Fuentes, Rafael J. Rodriguez
mmonteserin@ain.es

2

MATERIALS
• indice

OUTLINE
-

Introduction
Previous remarks
Objectives
Experimental results
Conclusions
3
Introduction
Bacteria on fabrics
Stains
Degradation

Bad Odours
The proliferation of certain kind of bacteria on
textiles can cause several

undesired effects

Infections
4
Introduction
Bacteria on Fabrics
For some applications of textiles, it is specially important to avoid these
adverse effects:

Biomedical
Textiles

Technical
Sports Clothes

5
Introduction
Technical approaches to develop antibacterial textiles
- New raw materials (expensive, time-consuming)

- Modification of existing textile materials
BULK MODIFICATION

SURFACE MODIFICATION

Fabric

Incorporated
into the fiber
Leaching effect

Coating of
the fiber

Binded to
the fiber

Chemical binding
6
Introduction
Antibacterial agents used on Fabrics

Silver
Chitosan

Quaternary
ammonium salts

Triclosan

N-halamine
7
Introduction
However, many of the commertially available
antibacterial agents used in textiles are either

environmentally toxic, have limited
antibacterial activity or are known to be
potentially cytotoxic.

ALTERNATIVE TEXTILE

MATERIALS AND/OR COATINGS
WITH ANTIBACTERIAL PROPERTIES
8
Objectives

Development of Antibacterial nano-coatings
for technical and biomedical textiles based on
Plasma Polymerized Poly-Pyrrole

9
Previous remarks
Biocompatible – No dangerous for the
human being

•

Easy to manipulate

•

Why
Poly-Pyrrole?
Poly-Pyrrole?

•

Tested antibacterial activity when is
prepared by oxidative chemical synthesis*

Positive charges

Inherent conductive polymer (ICP)
Antibacterial activity

*Varesano A, Synthetic Metals. 2009;159:1082-1089.

10
Previous remarks
Why
Plasma
Polymerization?
Polymerization?
PE-CVD
Plasma Enhanced Chemical Vapor Deposition

- Environmentally friendly technique – no solvents are used
- Low temperatures are achieved during the process, so
textile fibres are not damaged
- Easily industrializable process

11
Previous remarks
What is
Plasma
Polymerization?
Polymerization?
RF discharge

PE-CVD
Plasma Enhanced Chemical Vapor Deposition
Time
Pressure
Discharge power
Monomer flow
Carrier gas

Film structure
&
properties

Pyrrole gas

Textile fabric

Poly-Pyrrole
deposition
12
Previous remarks
Conventionally synthetized
poly-pyrrole

Plasma polymerized
polymers

Drawbacks
of plasma
polymerization

Loss of pyrrole
functionalization

Structure and properties
are highly dependent
on the deposition

parameters
D. Merche et al. Thin solid films 520, 13, 2012, 4219–4236

13
Objectives

CHALLENGE
Trasfer the antibacterial activity observed in
chemically synthesized Poly-Pyrrole to the
plasma polymerized polymer by

minimizing the loss of
funcionalization during plasma
polymerization

14
Experimental results
Deposition of poly-pyrrole coatings
on cotton fabrics
Cotton

HOMOGENEOUS
LOW ROUGHNESS
COATINGS

15
Experimental results
Optimization of the deposition process
-CΞN

Monomer flow rate

Pressure
Gas Mixtures
Discharge power
Doping

Increasing power

Time

Non-conductive
Poly-pyrrole
No antibacterial
activity
Broken
PPy
ring

180000

survey

160000

Intensity (cps)

140000

N1s
C1s
O1s

CKLL

27N
27D
28N
28D
29N
29D
30N
30D

120000

NKVV
100000

OKVV
I3d

80000
60000
40000

Si2p

20000

Pyrrole

0
1200

Si2s
1000

800

600

400

Binding Energy (eV)

200

0

16
Experimental results
Optimization of the deposition process
Iodine Doping

Induce the oxidation of polypyrrole structure
to obtain positive

charges

Non-doped poly-pyrrole
NON-CONDUCTIVE

20

% N+/N

16
12
8

Doped poly-pyrrole

4

CONDUCTIVE

0
50 W

35 W

20 W

N+
Positive charges
17
Experimental results
Measurement of the antibacterial activity
ASTM E 2149-01 procedure for fabrics
- Quantitative method
- Dynamic contact conditions

PPy Coated fabric

Escherichia coli

+
Bacterium inoculum
In buffer solution
shaken at 190 rpm for 1 h

count the
surviving colonies
of bacteria

24 h at 37 °C
18
Experimental results
Measurement of the antibacterial activity
20

% N+/N

16

Good antibacterial
activity

12
8
4
0
50 W

35 W

20 W

50 W

35 W

20 W

90

% Reduction of bacteria

80
70
60
50
40
30
20
10
0

19
Antibacterial activity against K. pneumoniae
Conclusions
CONCLUSIONS

Good antibacterial activity has been observed on cotton
fabrics coated with plasma

Iodine-doping
poly-pyrrole

polymerized poly-pyrrole.

is necessary to induce the antibacterial behaviour of

deposited

by

plasma

polymerization.

Doping

during

polymerization has been shown a much more effective method to induce
oxidation of poly-pyrrole.
20
Thank you for your attention

MATERIALS

María Monteserín, PhD
mmonteserin@ain.es

21
ANTIBACTERIAL TEXTILES
BASED ON POLY-PYRROLE
NANO-COATINGS
María Monteserín, Francisco Martín, Gonzalo G.
Fuentes, Rafael J. Rodriguez
mmonteserin@ain.es

22

MATERIALS

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Imagine nano 2013-2

  • 1. Antibacterial textiles based on poly-pyrrole nano-coatings aintech@ain.es
  • 2. ANTIBACTERIAL TEXTILES BASED ON POLY-PYRROLE NANO-COATINGS María Monteserín, Francisco Martín, Gonzalo G. Fuentes, Rafael J. Rodriguez mmonteserin@ain.es 2 MATERIALS
  • 4. Introduction Bacteria on fabrics Stains Degradation Bad Odours The proliferation of certain kind of bacteria on textiles can cause several undesired effects Infections 4
  • 5. Introduction Bacteria on Fabrics For some applications of textiles, it is specially important to avoid these adverse effects: Biomedical Textiles Technical Sports Clothes 5
  • 6. Introduction Technical approaches to develop antibacterial textiles - New raw materials (expensive, time-consuming) - Modification of existing textile materials BULK MODIFICATION SURFACE MODIFICATION Fabric Incorporated into the fiber Leaching effect Coating of the fiber Binded to the fiber Chemical binding 6
  • 7. Introduction Antibacterial agents used on Fabrics Silver Chitosan Quaternary ammonium salts Triclosan N-halamine 7
  • 8. Introduction However, many of the commertially available antibacterial agents used in textiles are either environmentally toxic, have limited antibacterial activity or are known to be potentially cytotoxic. ALTERNATIVE TEXTILE MATERIALS AND/OR COATINGS WITH ANTIBACTERIAL PROPERTIES 8
  • 9. Objectives Development of Antibacterial nano-coatings for technical and biomedical textiles based on Plasma Polymerized Poly-Pyrrole 9
  • 10. Previous remarks Biocompatible – No dangerous for the human being • Easy to manipulate • Why Poly-Pyrrole? Poly-Pyrrole? • Tested antibacterial activity when is prepared by oxidative chemical synthesis* Positive charges Inherent conductive polymer (ICP) Antibacterial activity *Varesano A, Synthetic Metals. 2009;159:1082-1089. 10
  • 11. Previous remarks Why Plasma Polymerization? Polymerization? PE-CVD Plasma Enhanced Chemical Vapor Deposition - Environmentally friendly technique – no solvents are used - Low temperatures are achieved during the process, so textile fibres are not damaged - Easily industrializable process 11
  • 12. Previous remarks What is Plasma Polymerization? Polymerization? RF discharge PE-CVD Plasma Enhanced Chemical Vapor Deposition Time Pressure Discharge power Monomer flow Carrier gas Film structure & properties Pyrrole gas Textile fabric Poly-Pyrrole deposition 12
  • 13. Previous remarks Conventionally synthetized poly-pyrrole Plasma polymerized polymers Drawbacks of plasma polymerization Loss of pyrrole functionalization Structure and properties are highly dependent on the deposition parameters D. Merche et al. Thin solid films 520, 13, 2012, 4219–4236 13
  • 14. Objectives CHALLENGE Trasfer the antibacterial activity observed in chemically synthesized Poly-Pyrrole to the plasma polymerized polymer by minimizing the loss of funcionalization during plasma polymerization 14
  • 15. Experimental results Deposition of poly-pyrrole coatings on cotton fabrics Cotton HOMOGENEOUS LOW ROUGHNESS COATINGS 15
  • 16. Experimental results Optimization of the deposition process -CΞN Monomer flow rate Pressure Gas Mixtures Discharge power Doping Increasing power Time Non-conductive Poly-pyrrole No antibacterial activity Broken PPy ring 180000 survey 160000 Intensity (cps) 140000 N1s C1s O1s CKLL 27N 27D 28N 28D 29N 29D 30N 30D 120000 NKVV 100000 OKVV I3d 80000 60000 40000 Si2p 20000 Pyrrole 0 1200 Si2s 1000 800 600 400 Binding Energy (eV) 200 0 16
  • 17. Experimental results Optimization of the deposition process Iodine Doping Induce the oxidation of polypyrrole structure to obtain positive charges Non-doped poly-pyrrole NON-CONDUCTIVE 20 % N+/N 16 12 8 Doped poly-pyrrole 4 CONDUCTIVE 0 50 W 35 W 20 W N+ Positive charges 17
  • 18. Experimental results Measurement of the antibacterial activity ASTM E 2149-01 procedure for fabrics - Quantitative method - Dynamic contact conditions PPy Coated fabric Escherichia coli + Bacterium inoculum In buffer solution shaken at 190 rpm for 1 h count the surviving colonies of bacteria 24 h at 37 °C 18
  • 19. Experimental results Measurement of the antibacterial activity 20 % N+/N 16 Good antibacterial activity 12 8 4 0 50 W 35 W 20 W 50 W 35 W 20 W 90 % Reduction of bacteria 80 70 60 50 40 30 20 10 0 19 Antibacterial activity against K. pneumoniae
  • 20. Conclusions CONCLUSIONS Good antibacterial activity has been observed on cotton fabrics coated with plasma Iodine-doping poly-pyrrole polymerized poly-pyrrole. is necessary to induce the antibacterial behaviour of deposited by plasma polymerization. Doping during polymerization has been shown a much more effective method to induce oxidation of poly-pyrrole. 20
  • 21. Thank you for your attention MATERIALS María Monteserín, PhD mmonteserin@ain.es 21
  • 22. ANTIBACTERIAL TEXTILES BASED ON POLY-PYRROLE NANO-COATINGS María Monteserín, Francisco Martín, Gonzalo G. Fuentes, Rafael J. Rodriguez mmonteserin@ain.es 22 MATERIALS