Beruflich Dokumente
Kultur Dokumente
Review article
Department of Analytical and Environmental Chemistry, Vilnius University, Naugarduko 24, 03225 Vilnius, Lithuania
Laboratory of Immunoanalysis and Nanotechnology, Institute of Immunology of Vilnius University, Moletu pl. 29, 08409 Vilnius, Lithuania
c Department of Organic Chemistry, Institute of Chemistry, Gostauto 9, 01108 Vilnius, Lithuania
Received 26 July 2005; received in revised form 16 November 2005; accepted 22 November 2005
Available online 6 May 2006
Abstract
Conducting polymers can be exploited as an excellent tool for the preparation of nanocomposites with nano-scaled biomolecules. Polypyrrole
(Ppy) is one of the most extensively used conducting polymers in design of bioanalytical sensors. In this review article significant attention is
paid to immobilization of biologically active molecules within Ppy during electrochemical deposition of this polymer. Such unique properties of
this polymer as prevention of some undesirable electrochemical interactions and facilitation of electron transfer from some redox enzymes are
discussed. Recent advances in application of polypyrrole in immunosensors and DNA sensors are presented. Some new electrochemical target
DNA and target protein detection methods based on changes of semiconducting properties of electrochemically generated Ppy doped by affinity
agents are introduced. Recent progress and problems in development of molecularly imprinted polypyrrole are considered.
2006 Elsevier Ltd. All rights reserved.
Keywords: Conducting polymers; Polypyrrole; Biosensor; DNA sensor; Immunosensor; Molecularly imprinted polymers; Bioelectrochemistry; Nanotechnology;
Nanobiotechnology
Contents
1.
2.
3.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1. Electrochemical polymerization of polypyrrole versus chemical polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2. Polypyrrole as versatile immobilization matrix in design of biosensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.3. Catalytic biosensors based on polypyrrole . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.4. Immunosensors based on polypyrrole . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.5. Polypyrrole in the design of DNA sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.6. Application of polypyrrole in molecular imprinting technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusions and future developments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1. Introduction
Nanotechnology is rapidly evolving to open new materials
useful in solving challenging bioanalytical problems, including specificity, stability and sensitivity. Here conducting poly-
0013-4686/$ see front matter 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2005.11.052
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this polymer, what is on special interest of affinity chromatography since molecularly imprinted Ppy might be produced, which
might exhibit selectivity to molecules ranging from the small
organics [3133] to high molecular weight biomolecules [22].
Photo induced Ppy synthesis is attractive in photolithographic
application of this polymer, since it allows alterations in synthesized Ppy morphology by change of excitation light wave
length [34] and theoretically it might be applied for the design
of electronic chips. However, because of slow light induced
polymerization rate this polymerization type is still not very
often applied if compared with chemical or electrochemical
polymerization.
By using chemically induced polymerization the Ppy is
mainly produced in the bulk solution and just some amount of
synthesized polypyrrole is covering the surface of introduced
materials. It means that chemically induced polymerization is
not very efficient with respect to deposition of Ppy over some
surfaces. Moreover, Ppy is almost insoluble in usual solvents,
except some cases where it is doped with proper agents increasing solubility of this polymer [35] and it means that deposition
(e.g. by solvent evaporation) of this polymer from the solution
containing dissolved polymer is possible at the stage where the
polymer is still in the form of colloid particles, before its precipitation [30]. However, the major obstacle for use of this deposition
method for designing of Ppy based sensors is a poor adherence of this deposit to the surface, contrary to the film obtained
by electrochemical polymerization. But all these disadvantages
might be avoided if electrochemical polymerization is applied. It
allows deposition of Ppy over electrodes deposited in the electrochemical cell. That is the reason why electrochemical polymerization has found an application as a general deposition method
if thin Ppy layers are requested. By using this method thickness and morphology of deposited layer might be controlled by
application of well-defined potential and known current passing
through the electrochemical cell [36]. Electrochemical deposition of Ppy might be performed from various solvents (e.g.
acetonitrile, water, etc.). From the point of view of nanostructuring of this polymer it is really very important that Ppy synthesis
might be performed from water solution at neutral pH, since
it opens the ways for entrapment and/or doping of polypyrrole
by various biomaterials like small organic molecules, proteins,
DNA and even living cells. However, if buffers with low buffering capacitance are used as polymerization solution, a potential
problem is the local production of a great amount of protons
in the course of the polymerization which may affect the properties of the biomolecules to be entrapped inside the Ppy film.
In particular cases overoxidized Ppy might be synthesized and
entrapped molecules and/or dopants might be extracted from
the Ppy structure. In such cases so called molecularly imprinted
polymers might be designed. Moreover, electrochemical polymerization is applied for deposition of polypyrrole layers inside
geometrically complicated electrochemical cells [37] and there
is almost no doubt that this polymerization method might be
extremely useful for deposition of Ppy layers inside microfluidic
devices. Furthermore, electrochemically synthesized Ppy has
some attractive features, such as good conductivity and very high
adherence of these films to the mostly for biosensor design used
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Fig. 3. Generalized scheme of electrochemical biosensors based on PQQdependent glucose dehydrogenase. Mox , oxidized form of redox mediator; Mred ,
reduced form of redox mediator.
Fig. 2. Generalized scheme of electrochemical biosensors based on NAD+ dependent glucose dehydrogenase. Mox , oxidized form of redox mediator; Mred ,
reduced form of redox mediator.
Fig. 4. Generalized scheme of electrochemical biosensors based on direct electron transfer able PQQ-dependent alcohol dehydrogenase. H, heme-c moiety.
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In many designs of electrochemical immunosensors secondary antibodies able to recognize analyte complex with immobilized receptor were applied. Since antibodies are usually
not electrochemically active within the desired potential range
redox-active compounds and/or enzymes (mainly horseradish
peroxidase) [99102] that are able to generate electrochemical signal can be applied as labels for indication. Labeled
immunosensor format belongs to indirect analytical signal detection methods. In indirect electrochemical immunoassays the
binding reaction is visualized indirectly via an auxiliary reaction
by a labeling compound. Amperometric transducers in indirect
electrochemical immunoassay are used much more frequently
than others. For amperometric immunoassay the labeling redox
compound should have the following properties: it should be
reversibly electroactive; it should not cause electrode fouling; chemical groups for coupling should be available [103].
Species such as nitrophenol, H2 O2 , and NH3 that can be determined electrochemically are the substrates or enzymatic reaction
products of alkaline phosphatase, horseradish peroxidase, and
urease, generally labeled on immunoreagents. Among these,
because amonia is electrochemically inactive at low potentials
and can only be detected by an ammonia gas-sensing electrode, potentiometry is the only choice for the urease-labeled
immunoassay [104]. Indirect electrochemical immunoassay can
be divided into two major types: non-amplified and amplified.
In non-amplified redox-labeled electrochemical immunoassays
the indication of one antigen or antibody molecule will generate
one signal equivalent. Since the sensitivity of an amperometric
sensor for the redox compound is in the lower micromolar range,
this kind of assay makes sense only if the concentration of the
analyte to be determined is also in that range [105]. For more sensitive immunoassays amplification principles are necessary. One
way to amplify the amperometrical signal is preconcentration
step. During this step concentration of redox-active compound
is increasing many times and only after some time (15 min) the
measurement starts. However, there are often some difficulties
to regenerate the sensor before each measurement.
The major disadvantage of indirect immunosensors is the
necessity to apply additional immunochemicals labeled by electrochemical labels; it makes this method more expensive, time
consuming since additional procedures mainly based on incubation with labeled antibodies are essential for indirect detection
of analyte of interest. On the one hand, such procedures increase
sensitivity, but on the other hand they often decrease selectivity since usually broad-range-selectivity exhibiting secondary
antibodies are applied. In this respect so called label-free
immunosensors are more attractive, since such sensors allow
measurement without any additional hazardous reagents even
in real-time [48]. Label-free conversion of the binding event
into a measurable signal in particular at a low concentration of
the analyte, is one of the major challenges in biosensorics [48].
This topic is quite well solved in surface plasmon resonance
sensors what was reviewed previously [18]. Electrochemical
label-free analyte detection methods are developing not so fast
but they are very useful if colored and/or not transparent samples are under investigation or detection of analyte should be
performed in the body of patient. The majority of label-free
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Then within Ppy entrapped molecules are removed by solvent and the molecularly imprinted polymer is ready for use
[29]. Such polymer possesses nano-pores and nano-cavities that
are complementary to removed dopant. Furthermore, chemical functionalities of the monomer residues become spatially
positioned around the cavity in a pattern that is complementary to the chemical structure of the print molecule. These
imprints constitute a permanent memory for the print species
and enable the imprinted polymer to selectively rebind the print
molecule from a mixture of closely related compounds. Sensors based on molecularly imprinted Ppy for serotonin and
1-naphthalensulfonate [177], amino acids [31,175], caffeine
[32,163], atropine [178], sacharide [179], glycoproteins [22]
were reported. Both chemically and electrochemically synthesized Ppy can be applied in the development of molecularly
imprinted polymers. The electrochemical properties of Ppy
strongly depend on their redox state. At positive potentials
overoxidation of polypyrrole occurs. It leads to the partial degradation of polypyrrole polymeric backbone and introduction of
carboxylic, carbonilic and hydroxilic groups into polymeric
backbone that determines semi-permeability as well as ability to recognize imprinted molecules [38]. The best results are
achieved if during electrochemical deposition overoxidized Ppy
is imprinted by small molecular weight molecules [3133,176].
Moreover, attempts to imprint Ppy by large molecular weight
rigid structure possessing proteins were reported as well as, in
this case viral envelope proteins possessing rigid structure were
imprinted within overoxidized polypyrrole [22].
The conversion of the binding event into a measurable signal
in particular at a low concentration of the analyte, the prevention
or elimination of non-specific interactions, the regenerability,
and reusability among other topics are the major challenges
in molecularly imprinted polymer based biosensors. In such
sensors differences in capacitance and/or resistance arising in
electrochemical system during interaction of affinity agents can
be converted into signals that are easily monitored [180]. Here
pulsed amperometric detection can be applied as basic electrochemical detection method [21,22].
3. Conclusions and future developments
Polypyrrole is the most extensively used among other conducting polymers for the construction of different types of bioanalytical sensors. The background presented illustrates that
polypyrrole is a very attractive, versatile material, suitable for
preparation of various catalytic and affinity sensors and biosensors. Both electrochemically and chemically induced pyrrole
polymerization methods has potential application in the development of analyte-recognizing/converting layers.
In several studies it was shown that Ppy is able to transduce
analytical signal generated by some redox enzymes directly if
redox center of enzyme is deeply buried in the protein globule.
Polypyrrole modified by covalently attached redox groups might
be applied to facilitate electron transfer. From the other side, the
presented overview shows that polypyrrole might be applied
as immobilization matrix in the design of various affinity sensors like immunosensors, DNA sensors and sensors based on
molecularly imprinted polymers. The use of polypyrrole in conjunction with bioaffinity reagents has provident to be a powerful
route that has expanded the range of applications of electrochemical detection and its future development is expected to
continue. The interaction between the proteins, mainly negatively charged at neutral pH, and the delocalized positive charges
along the polypyrrole chains induces changes in capacitance of
this nanostructured material. Consequently, such interactions,
evidenced from electrochemical measurement are the basis of
bioaffinity signal. The use of a wide range of counterions will
provide significant change in affinity at the Ppy ion-exchange
sites. The application of nanoelectrode (e.g. carbon nanotubes)
technologies already established in electronic-nose devices
will be beneficial to polypyrrole based immunosensors. Further exploitation of this technology to immobilize bioaffinity
reagents with the polymer matrix may enable the design of
smaller, more compact and portable biosensing systems.
Current achievements show that electrochemical affinity sensor based on molecularly imprinted polypyrrole could have a
great potential for direct electrochemical sensing. It is straight
forward that in the future molecularly imprinted polymer based
sensors will require deliberate control of the molecular structure
at the surface of the electrode to exhibit higher affinity to analyte. As the surface microstructure becomes more complicated,
more chemical methods of molecular structure construction will
be required. These methods will use molecular technology
instead of bulk technology mainly used at present time. In addition, for the construction of more complex nanostructures, some
degree of molecular self-assembly will be needed and conducting polymers become more complex, versatile and will find the
new applications. New nanotechnological approaches to overcome these challenges are still in their infancy and application of
conducting polymers, in particular cases polypyrrole, will find
proper place in future molecular technology.
Acknowledgement
This work was partially financially supported by Lithuanian
State Science and Studies Foundation project number C 03047
and COST program D33.
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