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© 2009 American Chemical Society

Functional Polyelectrolytes†
Kirk S. Schanze* and Abigail H. Shelton
Department of Chemistry and Center for Macromolecular Science and Engineering, University of Florida,
P.O. Box 117200, Gainesville, Florida 32611-7200

Received October 6, 2009

This perspective seeks to identify an area of soft materials research focused on the study of functional polyelectrolytes.
These materials combine the useful properties intrinsic to polyelectrolyte chains, with added functionality provided by
specific molecular (or polymeric) functional groups that are present in the polymer backbone or as a pendant
functionality. Examples are provided to demonstrate how the combined functionality can be used to create films and
assemblies with interesting and useful optical, electro-optical, and electronic properties.

Introduction Functional Polyelectrolytes

Polyelectrolytes are polymers featuring electrolyte groups with-
in the repeat unit structure. Polyelectrolytes can be categorized as
natural (e.g., polynucleic acids and polypeptides), modified nat-
ural (e.g., chitosan and cellulose), and synthetic (e.g., polystyrene
sulfonate and nafion).1 Upon dissociation of the electrolyte groups
in solution, polyelectrolyte chains become charged and the charge
types include cationic, anionic, and zwitterionic (polyampholytes).
Natural and synthetic polyelectrolytes have been the subject of
experimental and theoretical study for nearly a century.2 Interest
in polyelectrolytes is driven by their properties, including water
solubility, ionic conductivity, strong intra- and interchain inter-
actions that give rise to useful solution properties, interaction with
ions in solution, and surface activity. These properties, which are
intrinsic to the polyelectrolyte chain, imbue the materials with
properties that are very useful from an application perspective,
such as additives to modify solution viscosity and induce gelation
or as stabilizers for colloidal suspensions. Because of these
properties, polyelectrolytes are important additives in a number
of products, including soaps, cosmetics, and foods.
Despite the ongoing use of polyelectrolytes, there remains
considerable research interest in these materials.3 One area of
considerable recent research interest in the area of polyelectrolytes
is the study of polyelectrolyte multilayer (PEM) films. Initially
reported by Decher,4,5 the field of PEM films has rapidly
expanded, with many fundamental studies of the process as well
as the use of the multilayer films in areas such as nanoporous
membranes, delivery capsules, and sensors.6,7 The layer-by-layer
(LbL) deposition technique, which provides the basis for the
construction of PEM films, is based on the intrinsic property of
polyelectrolytes to adsorb at charged interfaces and to form
complexes with oppositely charged polyelectrolyte chains.
†
Part of the “Langmuir 25th Year: Molecular and macromolecular self-
assemblies” special issue.
*Corresponding author. E-mail: kschanze@chem.ufl.edu. www: http://
www.chem.ufl.edu/∼kschanze.
(1) Koetz, J.; Kosmella, S. Polyelectrolytes and Nanoparticles; Springer-Verlag:
Berlin, 2007.
(2) Staudinger, H. Die Hochmolekularen Organischen Verbindungen, Kautschuk
und Cellulose; Springer: Berlin, 1932.
(3) More than 1000 research articles in Langmuir contain “polyelectrolyte” in
the title or abstract.
(4) Decher, G.; Hong, J. D.; Schmitt, J. Thin Solid Films 1992, 210, 831–835.
(5) Decher, G. Science 1997, 277, 1232–1237.
(6) Multilayer Thin Films: Sequential Assembly of Nanocomposite Materials;
Decher, G., Schlenoff, J., Eds.; Wiley-VCH: Weinheim, Germany, 2003.
(7) Ariga, K.; Hill, J. P.; Ji, Q. M. Phys. Chem. Chem. Phys. 2007, 9, 2319–2340.
In this perspective, we wish to point out a novel direction in the
area of polyelectrolyte chemistry and materials science that is
focused on the development of a new class of polyelectrolytes that
we define as functional polyelectrolytes. We will define these
materials and give some specific examples from the recent
literature (including articles in the present Langmuir issue) to
highlight research and directions in this growing field. Here we
define a functional polyelectrolyte as being a synthetic polymer or
copolymer that contains ionizable electrolyte groups as well as
additional functionality imparted by the molecular (polymer)
structure. The most common examples of added functionality are
redox activity imparted by the inclusion of easily oxidized or
reduced units and optical properties (light absorption, light
emission, and photochromism) imparted by the inclusion of
specific chromophores or a π-conjugated polymer backbone.
Whereas these are the most common examples of function, others
can be envisioned, including catalytic function and molecular
recognition. For brevity, we choose not to include metal-complex-
based coordination polymers or ionic dendrimers in our discus-
sion of functional polyelectrolytes; however, in many cases, these
materials could be included in this categorization.
As noted above, the area of polyelectrolyte chemistry and
materials science has been very active in Langmuir, and the
present special anniversary issue contains a number of articles
focused on functional polyelectrolytes.
Redox Polyelectrolytes
Redox polyelectrolytes feature a polyelectrolyte chain that
includes a redox-active moiety in the repeat unit structure. Several
excellent examples of these materials are provided in the recent
literature, and here we highlight work on two specific example
systems. The first that we select is the family of poly(viologens)
first reported by Schlenoff and co-workers in the late 1990s.8,9 The
poly(butanylviologen) polymer was used along with poly(styrene
sulfonate) (see Figure 1 for structures) to construct PEM films via
the LbL approach. The LbL films were robust and exhibited the
electrochemical response of the viologen moieties. The results
indicated that the films exhibit good redox conductivity because
the viologen units remain electrochemically active, even for films
with 10 bilayers. In addition to the redox functionality, the
(8) Laurent, D.; Schlenoff, J. B. Langmuir 1997, 13, 1552–1557.
(9) Stepp, J.; Schlenoff, J. B. J. Electrochem. Soc. 1997, 144, L155–L157.

13698 DOI: 10.1021/la903785g Published on Web 11/04/2009 Langmuir 2009, 25(24), 13698–13702
Schanze and Shelton
Figure 1. (a) Redox cycling between oxidized and the one-electron-reduced form of poly(butanylviologen) (PVB). (b) Schematic diagram of
PEM multilayer films of PBV and polystyrene sulfonate showing electron hopping between viologen units in the PEM structure. Reprinted
with permission from ref 8. Copyright 1997 American Chemical Society.
viologen-functionalized PEM films exhibit UV-visible electro-
chromism associated with the absorption difference between the
oxidized (V2þ) and reduced (Vþ•) states of the viologen unit as well
as the ability to catalyze the electroreduction of dioxygen.9 Thus,
the viologen functionality imparts the polyelectrolyte with optical
and catalytic functionality, in addition to redox properties.
Ferrocenyl-functionalized polyelectrolytes have been the sub-
ject of a series of investigations by Vancso and co-workers.10-14
The pair of polyelectrolytes shown in Figure 2 has backbones
based on poly(ferrocenylsilane), and they feature polyelectrolyte
nature imparted by the presence of the ammonium (cationic) and
sulfonate (anionic) side groups. The ferrocene (Fc) functionality
imbues the polyelectrolytes with redox activity, and the combined
redox and polyelectrolyte nature of the materials has been used to
fabricate PEM films and capsules that exhibit the redox response
characteristic of the Fc/Fcþ couple. One recent study provides a
very nice example of how the combined polyelectrolyte and redox
functionality can be used to fabricate structures that have
remarkable stimuli-responsive properties. In particular, Ma and
co-workers used the cationic and anionic ferrocene polyelectro-
lytes to construct polyelectrolyte capsules by using the LbL
approach on MnCO3 template particles.12,15 When the ferrocene
units were in the reduced state (Fc0), the capsules were imperme-
able to a moderate-molecular-weight dextran. However, follow-
ing the addition of Fe3þ, the ferrocene units are oxidized (Fcþ)
and the capsules exhibit remarkable swelling and become perme-
able to dextran (Figure 2). The swelling and increased perme-
ability are attributed to charge repulsion within the ferrocene
polyelectrolytes. In a more recent study, Hempenius et al. repor-
ted a hydrogel that is fabricated from a cross-linked polyelec-
trolyte based on the poly(ferrocenylsilane) backbone (Figure 3).14
The hydrogel undergoes reversible redox-induced swelling/des-
welling due to electrostatic interactions between the anionic
sulfonate units and the Fcþ sites that are produced by oxidation.
(10) Hempenius, M. A.; Peter, M.; Robins, N. S.; Kooij, E. S.; Vancso, G. J.
Langmuir 2002, 18, 7629–7634.
(11) Hempenius, M. A.; Brito, F. F.; Vancso, G. J. Macromolecules 2003, 36,
6683–6688.
(12) Ma, Y. J.; Dong, W. F.; Hempenius, M. A.; Mohwald, H.; Vancso, G. J.
Nat. Mater. 2006, 5, 724–729.
(13) Ma, Y. J.; Dong, W. F.; Kooij, E. S.; Hempenius, M. A.; Mohwald, H.;
Vancso, G. J. Soft Matter 2007, 3, 889–895.
(14) Hempenius, M. A.; Cirmi, C.; Song, J.; Vancso, G. J. Macromolecules 2009,
42, 2324–2326.
(15) Donath, E.; Sukhorukov, G. B.; Caruso, F.; Davis, S. A.; Mohwald, H.
Angew. Chem., Int. Ed. 1998, 37, 2202–2205.
Langmuir 2009, 25(24), 13698–13702
Perspective
Conjugated Polyelectrolytes
Conjugated polyelectrolytes (CPE) represent an important class of
functional polyelectrolytes. CPEs feature a backbone consisting of a
delocalized, π-conjugated electronic system surrounded by the ionic
electrolyte groups that give the materials polyelectrolyte character.
CPEs were first reported in 1987 by Wudl, Heeger, and co-workers as
an approach to synthesize a self-doped conducting polymer,16 and
research into the properties and applications of CPEs has blossomed
in the past decade.17 This period has witnessed tremendous growth in
interest in CPEs, with a large number of studies that have examined
the fundamental properties of the materials and have explored their
use in a variety of applications including chemo- and biosensors,
polymer electronic devices, and solar cells.18
The properties of CPEs are the result of synergistic effects arising
from the interplay of their dual functionality. In particular, the π-
conjugated backbone imparts the materials with a broad function,
including strong optical absorption and fluorescence, conductivity
for neutral (exciton) and charged (polaron) states, and an amplified
response to external stimuli owing to the delocalized electronic
structure of the backbone. In addition, the polyelectrolyte func-
tionality imparts the materials with the properties intrinsic to
polymer electrolytes, viz., water solubility, ionic conductivity,
strong intra- and interchain interactions, interaction with ions in
solution, surface activity, and a propensity to adsorb at interfaces.
Here we provide a few examples of some of the recent research on
CPEs to highlight the ways in which these novel functional
materials are being used in applications. In addition, we draw the
reader’s attention to two research articles in the present Langmuir
special issue that provide additional examples of the unique
properties and applications of conjugated polyelectrolytes.19,20
An early study by Rubner and Reynolds illustrates how the
combined polyelectrolyte and conjugated function can be used to
construct novel PEM films for optoelectronic device applica-
tion.21 In particular, using a pair of sulfonate (anionic) and
(16) Patil, A. O.; Ikenoue, Y.; Wudl, F.; Heeger, A. J. J. Am. Chem. Soc. 1987,
109, 1858–1859.
(17) Pinto, M. R.; Schanze, K. S. Synthesis 2002, 1293–1309.
(18) Jiang, H.; Taranekar, P.; Reynolds, J. R.; Schanze, K. S. Angew. Chem., Int.
Ed. 2009, 48, 4300–4316.
(19) Ding, L.; Chi, E. Y.; Chemburu, S.; Ji, E.; Schanze, K. S.; Lopez, G. P.;
Whitten, D. G. Langmuir, 2009, 25, DOI 10.1021/la901457t.
(20) Feng, X.; Xu, Q.; Liu, L.; Wang, S. Langmuir 2009, 25, DOI 10.1021/
la901444c.
(21) Baur, J. W.; Kim, S.; Balanda, P. B.; Reynolds, J. R.; Rubner, M. F. Adv.
Mater. 1998, 10, 1452–1455.
DOI: 10.1021/la903785g 13699
Perspective
ammonium (cationic) polyelectrolytes with a poly(parapheny-
lene) backbone (Figure 4), the active layer for a polymer light-
Figure 2. (a) Functional polyelectrolytes containing ferrocene units
used to prepare polyelectrolyte capsules. (b) Confocal fluorescence
microscope image of ferrocene polyelectrolyte capsules surrounded
by solution containing TRITC-labeled dextran (4.4 kD). Capsules
are dark because they are impermeable to dextran. (c) Confocal
image of the same solution after the addition of Fe3þ, which serves to
oxidize the ferrocene units. Capsules are fluorescent because oxida-
tion makes them permeable to dextran. Reprinted with permission
from ref 12. Copyright 2006 Nature Publishing Group.
Figure 3. (Left) Chemical structure of cross-linked polyelectrolyte gel containing ferrocene functional groups. (Right) Photograph of a
hydrogel. Reprinted with permission from ref 14. Copyright 2009 American Chemical Society.
13700 DOI: 10.1021/la903785g
Schanze and Shelton
emitting diode (PLED) was constructed using the LbL deposition
method. In particular, 35 bilayer films consisting of alternating
layers of the cationic and anionic CPEs were deposited onto a
transparent electrode. The assembly process takes advantage of
the polyelectrolyte functionality of the polymers. The optoelec-
tronic device was completed by the evaporation of an aluminum
film, giving rise to PLED device architecture in which the light-
emitting and semiconducting CPE film is sandwiched between
two electrodes. As shown in Figure 4, the device emits blue light
under an applied electrical bias. Several years later, working in
collaboration with Reynolds, we used a sulfonate-type (anionic)
polyelectrolyte with a poly(phenylene ethynylene) conjugated
backbone in conjunction with a cationic C60 derivative to con-
struct PEM films that served as the active layer in a polymer solar
cell (Figure 5).22 Solar cells that contained 50 bilayers of the CPE
and C60 derivative exhibited a relatively good photoresponse,
with a peak absorbed photon-to-electron quantum efficiency of
ca. 10% and a short circuit current of 0.5 mA under simulated
solar illumination conditions (100 mW cm-2).
Several recent studies highlight how the combined poly-
electrolyte and conjugated functionality of CPEs can be used
in unusual ways. Specifically, Whitten and co-workers have
Figure 4. (Top) Chemical structures of anionic and cationic poly-
(paraphenylene) conjugated polyelectrolytes. (Bottom) Current-
voltage (0) and light-voltage (O) plots for polymer light-emitting
diodes constructed using 35 bilayer films of the cationic and anionic
conjugated polyelectrolytes. Reprinted with permission from
ref 21. Copyright 1998 Wiley-VCH.
Langmuir 2009, 25(24), 13698–13702
Schanze and Shelton
Figure 5. Schematic diagram illustrating the structure of polymer solar cells constructed using PEM films consisting of an anionic conjugated
polyelectrolyte with a cationic C60 derivative. Reprinted with permission from ref 22. Copyright 2005 American Chemical Society.
Figure 6. Fluorescence microscope image of E. coli bacteria
coated with a cationic poly(phenylene ethynylene) CPE. The
yellow-green fluorescence is from the polymer. Reprinted with
permission from ref 23. Copyright 2005 American Chemical
Society.
demonstrated that suspending a microbial sample in an aqueous
solution containing a cationic CPEs results in the microbe
particles becoming coated with the CPE.23 For example, as shown
in Figure 6, a suspension of E. coli bacteria exhibits bright
fluorescence after being exposed to a solution of a cationic
poly(phenylene ethynylene) CPE. The fluorescence arises because
the bacteria are coated with a thin (monolayer) film; the coating
process likely involves the adsorption of the CPE chains due to
electrostatic interactions between the outer membrane of the
microbial particles and the electrolyte groups on the polyelec-
trolyte chains. In a separate investigation, Ingan€as and co-work-
ers described the use of amyloid fibrils to template the assembly
of “nanowires” consisting of a conjugated polyelectrolyte con-
sisting of a poly(3,4-ethylenedioxythiophene) backbone that is
substituted with anionic sulfonate pendant groups (PEDOT-S,
Figure 7).24 The self-assembly process takes advantage of the
polyelectrolyte nature of PEDOT-S, which allows the CPE to
form a polyelectrolyte complex with the amyloid fibrils. As shown
in the transmission electron microscope image in Figure 7, the
PEDOT-S modified fibrils form a nanoscale network structure.
(22) Mwaura, J. K.; Pinto, M. R.; Witker, D.; Ananthakrishnan, N.; Schanze,
K. S.; Reynolds, J. R. Langmuir 2005, 21, 10119–10126.
(23) Lu, L. D.; Rininsland, F. H.; Wittenburg, S. K.; Achyuthan, K. E.;
McBranch, D. W.; Whitten, D. G. Langmuir 2005, 21, 10154–10159.
(24) Hamedi, M.; Herland, A.; Karlsson, R. H.; Inganas, O. Nano Lett. 2008, 8,
1736–1740.
Langmuir 2009, 25(24), 13698–13702
Perspective
Figure 7. (Right) Transmission electron microscope image of
amyloid fibers coated with PEDOT-S (structure at left). The center
shows the layout of an electrochemically gated transistor structure
constructed using the coated fibers, and the graph at the bottom
shows the current-voltage characteristics of the working transis-
tor device. Reprinted with permission from ref 24. Copyright 2008
American Chemical Society.
Interestingly, when the PEDOT-S fibrils are deposited onto an
interdigitated platinum electrode array a simple gated transistor
structure results, wherein the nanoscale conjugated polyelectro-
lyte-coated fibrils act as the charge-transport medium. Charge
transport arises from the conductive nature of the PEDOT-S
conjugated backbone.
Summary and Outlook
This perspective seeks to identify and categorize a novel area of
soft materials research that is focused on the study of functional
polyelectrolytes. These materials combine the useful properties
intrinsic to polyelectrolyte chains, with added functionality pro-
vided by specific molecular (or polymeric) functional groups that
are present in the polymer backbone or as a pendant function-
ality. In this perspective, we provide examples that demonstrate
how the combined functionality can be used to create films and
assemblies with interesting and useful optical, electro-optical, and
electronic properties.
DOI: 10.1021/la903785g 13701
Perspective
The study of functional polyelectrolytes is relatively new, and
we believe that the future holds considerable promise for the
development of new materials that exhibit a novel “smart”
response to external stimuli. Although it is not possible to identify
in advance how the field will develop, it is likely that the functional
polyelectrolytes will be used for the development of stimuli-
responsive materials with applications in the areas of separations
13702 DOI: 10.1021/la903785g
Schanze and Shelton
and chemical and biological sensing and in the development
of novel coatings for optical and electro-optical device applica-
tions.
Acknowledgment. Research in our laboratories on conjugated
polyelectrolytes is supported by the Defense Threat Reduction
Agency (contract no. W911NF-07-1-0079).
Langmuir 2009, 25(24), 13698–13702