Nonconventional Technologies Review No.

1 / 2007

NEW USES OF NANOCOMPOSIT E MATERIALS WITH POLYMERIC MATRIX

FOR ENVIRONMENTAL MONITORISATION
Alexandra BANU1, Maria MARCU2, PIRVU Cristian3
ABSTRACT
This work shows uses of nanocomposite materials with polymeric matrix in environmental
monitorisation. Conducting polymers are used as immobilising matrix for the synthesis of
nanocomposite materials and also as conducting layers for obtaining electrochemical sensors.
In the table 1 are shown some conducting polymers used for the manufacturing of biosensors
and the method and their detection limit also. As an example, a study of the electrochemical
behaviour of phenolic-type polluting agents on electrodes having their surface modified with
several polythyophenes has been presented.

KEYWORDS : nanocomposites , polymeric matrix , polypyrol , electrodeposition ,

environment monitorisation

like electronics, anticorrosive protection ,

depollution and environment monitoring
(sensors , biosensors).

1. INTRODUCTION
The current tendencies concerning future
using of nanomaterials have been widely
debated at the International Fair for the
Chemical Industry, ACHEMA 2006.
The stress was on he fact that the
processing and production of nanomaterials
will be of over 30 billion euros in 2006 , and
from this value , the production of
nanocomposites will be of over 1.2 billion
euros.
As the nanomaterials business is developed
there has been a larger interest in the
environment and health, in connection with
the development of nanomaterials.
The uses on nanotechnology are developed
in order to increase the performance of
sensors or other monitoring devices, the
production of batteries.
Or light and long lasting chargers and in the
medical field nanostructures able to destruct
cancer cells without having the devastating
effect of chemotherapy or radiotherapy are
investigated.
Out of the new materials created in order to
solve some of the most pressing problems of
the modern society, the energy problem and
pollution, nanocomposites with polymeric
matrix have an unique position, their
research being practical
The composite materials with polymeric
structure have a wide variety of uses in fields

2. SENSORS
Although research concerning sensors based
on modified electrodes are , still , at a
beginning , these are a promising alternative
in the environment monitorisation field. The
advantages of using them in environmental
analysis are due to the special characteristics
of the modified electrodes: acceleration of
electron-transfer reaction, the preferential de
accumulation of the analyte on their surface,
permselective transfer etc.
So, there have been developed catalytic
surfaces able to facilitate the detection of
some polluting agents (with a reduced
electron-transfer kinetics). The importance of
using conducting polymers in analytical
applications has been proved by many
researchers. Another important advantage is
avoiding the pasivisation of the surface (due
to the adsorbtion of some macromolecules on
the surface) through the protective action of
theses films.
The uses in the biosensors field suppose the
functionalisation of the surface with bioactive
compounds.
In the following table a series of polymers
used
as
biosensors
are
shown
.

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Nonconventional Technologies Review No. 1 / 2007

Tabel 1. Characteristics of conducting polymers using by biosensors

Matrix
Polypyrrole
Poly(oaminophenol /
CNT)
Polypyrrole/polyvi
nyllic alcohol
Polyaniline
Polyaniline /
polyvinylsulphonat
ed alcohol

Biosensitive
molecule
Virostat antiAZT
Glucoseoxidase

Analyte

Polypyrol/polyv
inyllic alcohol
film
uricase
Alcohol
dehydrogenas
e

methanol

Imobilisation
method
Electrochemical
entrapping
Electropolymerisat
ion

AZT
glucose

Detection
limit
10 pg/mL
0.01 mM

Resistance
modification

C vitrosPolyaniline

Cholinesterase

Polypyrrole

Anti-BSA

Uric acid
nicotinamide
andenin
nucleotide
Organophosp
horous
pesticides
BSA

Polypyrrole
polyvinylsulphonat
e
PEDOT
PEDOT

DNA

OCP

MIP
Tyrosinase

thyophenpolytetrahydrofura
ne
Poly-tert
thyophen

Detection
method
Electrochemic
al impedance
Amperometric

Solution

amperometric
amperometric

5x10-9

Cross-link

Electrochemical
entrapping
adsorbtion

Ac
impedance
DPV,
cronopotentio
metry

0-75
ppm
1 g/L

Precipitation
Entrapping

amperometric
amperometric

0.1-2 mm
5-500
nm

phenol
oxidase

Morphine
Phenolic
compunds
Phenolic
compunds

Entrapping

spectrofotom
etric

ADN

ADN

covalent

impedance

Electrochemical polymerisation of thin

polythyophen films functionalised with crown
ether [1] allowed the identification of some
alkaly cations like Li , Na , K.

Figure 2. Polythyophene chiral.

This chiralic recognition is a detection method
for the compounds which show chirality.
Figure1.Ion selective polythyophene
3. ELECTRODES
SURFACE

It was observed that the polymers with optical

properties having a chiral primary amine are
sensitive to primary amino-alcohols.

WITH

MODIFIED

The study of the electrochemical behaviour of

phenolic-type polluting agents on platinum
electrodes having their surface modified with
several polythyophenes like : poly(3methylthyophen) , polybithyophen , PEDOT ,

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PBSBT prove the fact that the modified

electrodes behave better in comparison to the
platinum ones.

Figure 3. Cyclic voltammograms of

anodic oxidation of phenol on electrode
surface modified with: polythyophene,
poli (3-metiltiofen), polibityophene,
PEDOT, PBSBT.

B
Figura 4. AFM images of platinum
electrode surface modified PEDOT (A) and
PEDOT/NaPSS (B).

In the last years there has been an intense

publishing on the uses of electrodes having
their surface modified withl conducting
polymers in order to prevent the electrode
from being blocked during the detection of
different organic compounds [2,3].
Out of the organic conducting polymers,
polythyophene and its derivatives have drawn
the attention since they are the most stable
organic conducting polymers.
Pirvu and his co-workers [4] obtained
spectacular results on the PEDOT/NaPSS
electrode , on which , the blocking process of
the electrode wouldnt manifest , the
voltammograms showing an oxidation peak
reproductive for 20 cycles.
This behaviour of the phenol oxidation on the
PEDOT/NaPSS electrode was attributed to
the hydrophilic character created to the
surface by the presence of the sulphonic
groups
in
the
structure
of
polystyrenesulphonate which prevents the
adsorbtion of the phenolic products on the
surface and, this way, avoids the blocking of
the electrode.

The result was a calibration of the

PEDOT/NaPSS electrode through SWV on
the 1-50 ppm concentration domain with a
slope of 0,370,006A/1 ppm phenol.
Another polymer used for the sensors
manufacturing is polypyrole , which is one of
the most used polymers in the syinthesis of
conducting polymeric composites.
Recently, a group of researchers identified
polypyrole as a new substratum for the
raising support of the mammal cells, thisone
showing a potential use as an intelligent
biomaterial [5]. The use of these polymers as
biomaterials implies a high control of the
substratum, which is not accessible for other
polymers. By using the dynamic control of
polymers, the cellular growth on the surface
of the material can be selectively shapened.
Polyzaharides considered dopant anions for
polypyrole , named haluronic acid (HA) and
heparine
(Hep)
can
be
used
for
manufacturing the composite skeleton for the
cartilaginous tissue , for adhesive cells and
bone regeneration.

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Both polypyrole and polythyophenes can be

used as immobilising matrix of the
manufacturing
of
biosensors
like
imunosensors , ADN sensors etc.
The used the use of conducting polymers as
biomaterials implies a high control of the
layer, which is not accessible to other
polymers.
REFERENCES
[1] P, BAUERLE, S.SCHEIB, Adv. Mater., 5.848853 , 1993.
[2]. GOTO, H.; YASHIMA, E. J. Am. Chem. Soc. 124,
79437949. 2002,
[3] M. A. HERAS , C. PIGANI, C. PIRVU, R.
SEEBER, F. TERZI, C. ZANARDI, Electrochimica
Acta, , 2005, 50(7-8), 1685-1691
[4] L. PIGANI, C. PIRVU, R. SEEBER, F. TERZI, C.
ZANARDI, Electrochimica Acta, 2006, available
online
[5] S. PANERO, G. ABBATI, D. RENIER, V.
CRESCENZI, PCT, Int. Appl. (2003) WO
2003000309
[6]
V.V.KUZNETSOV,
M.R.PAVLOV,
K.V.
KUZNETSOV, V.N. KUDRYAVTSEV Russian
Journal of Electrochemistry, Vol.39, 12, 2003,
1338-1341

Figure 5: Cyclic voltammograms of PPypolysaccharides samples in (1M) KCl

solution. Scan rate 20 mV s-1.
These characterisitcs are imposed in the
polypyrole / polysaciride by measuring the
parameters of the surface influencing the
cellular attachment on the material, the
electrochemical properties of the surface
substratum
through
rugosity
and
hydrophobicity , and by comparing with
growth speed of the cells on polypyrole /
polysaciride with those obtained in standard
conditions.

AUTORS

4. CONCLUSIONS
1) Associate Professor Alexandra BANU,
University POLITEHNICA of Bucharest,
ROMANIA
E-mail: a_banu_2000@yahoo.com
2) Dr. Eng. Maria MARCU, Institute of
Physical Chemistry Ilie Murgulescu,
Bucharest, ROMANIA
E-mail: m_marcu2000@yahoo.com
3) Lecturer Cristian PIRVU,
University
POLITEHNICA of Bucharest, , ROMANIA
E-mail: cpirvu@yahoo.com

Polypyrole and polythyophenes are the most

used
conducting
polymers
for
the
manufacturing
of
sensors
used
at
environment monitorisation.
The use of electrodes having their surface
modified with conducting polymers lead to the
prevention of the electrode being blocked
during the detection of organic compounds.
The electrochemical methods can be
successfully used as polymerisation methods
and have a high potential in recognition
layers development.

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