Communication

Tuning Surface Wettability of

Poly(3-sulfopropyl methacrylate) Brushes by
Cationic Surfactant-Driven Interactions

Markus Dobbelin, Garciela Arias, Iraida Loinaz, Irantzu Llarena,

David Mecerreyes,* Sergio Moya*

In this communication, polyanionic poly(potassium 3-sulfopropyl methacrylate) (PSPM)

brushes were switched from hydrophilic to hydrophobic by exchange of the counter cations.
First, poly(potassium 3-sulfopropyl methacrylate) brushes were grown by means of atom
transfer radical polymerization (ATRP) from thiol monolayers of initiating v-mercaptoundecyl
bromoisobutyrate and mixed monolayers of thiol initiator and 1-undecanothiol (blank thiol)
attached to gold surfaces. The kinetics of the polymerization reaction were followed by means
of the quartz microbalance technique with dissipation (QCM-D). The collapse of PSPM brushes
in the presence of cationic surfactants like quaternary ammonium salts (tetraethylammonium
bromide, hexadecyltrimethylammonium bromide) and imidazolium salts (1-dodecyl-3-
methylimidazolium bromide, 1H, 1H, 2H, 2H-
perfluoro-1-decyl-3-methylimidazolium bromide)
was shown by QCM-D. Water contact angle
measurements proved that the wettability of
the surface could be tuned reversibly from hydro-
philic values (<30 8) to hydrophobic ones (>85 8).

Introduction films have indeed been used to protect surfaces, as barriers

Polymer thin films provide a wide platform for tuning
the surface properties of materials, both through their
chemical and topological characteristics. Polymer thin
M. Dobbelin, I. Loinaz, D. Mecerreyes
New Materials Department, CIDETEC, Centre for Electrochemical
Technologies and CIC NANOGUNE Consolider, Parque Tecnolo-
gico de San Sebastian, Paseo Miramon 196, Donostia-San
Sebastian 20009, Spain
E-mail: dmecerreyes@cidetec.es
I. Llarena, S. Moya
CIC BIOMAGUNE, Parque Tecnologico de San Sebastian, Paseo
Miramon 182 C, Donostia-San Sebastian 20009, Spain
E-mail: smoya@cicbiomagune.es
G. Arias
CIQA, Blv. Enrique Reyna, Saltillo, Coahuila, Mexico
for selective permeability, for the anchorage of active
molecules, as anti-bacterial layers or to adjust wetting
properties.[14] As a particular case of polymer thin films,
polyelectrolyte brushes are monolayers of polyelectrolyte
molecules, where the polymer chains are tethered on
one side to a surface while the other end of the chain is
free. The dense arrangement of the polymer chains in a
brush provides the system with very interesting physico-
chemical properties. For example, the conformational state
of the charged tethered chains is highly dependent on
the ionic strength and, in some cases, on the pH.[5] The
repulsive coulombic interactions between their intrinsic
charges leads to an extended (stretched) conformation of
the solvated polymer chains. Upon increasing the ionic
strength, the repulsive interactions are screened and the
brush changes conformation into a collapsed state. When

Macromol. Rapid Commun. 2008, 29, 871875

2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/marc.200800071 871

the collapse takes place, the solvent is largely excluded and
the brush acquires such conformations that the chain
density is at a maximum.[69] Recently, it has been shown
that polycation brushes can be used to change the
wettability of surfaces by simply choosing the proper
anions. It has been reported that brushes of poly[2-
(methacryloyloxy)-ethyl-trimethylammonium chloride]
(PMETAC) showed significant changes in their wetting
character when exposed to different anions. Perchlorate
(ClO
4 ) coordinated PMETAC brushes showed an increased
water contact angle from an initial 35 8 in the uncollapsed
state up to 79 8 in the collapsed state.[10] In contrast, when
PMETAC brushes were coordinated with SO
4 anions, their
surface turned to highly hydrophilic.[11] This interesting
anion sensitive behavior is completely reversible and it has
been demonstrated with different anions, such as trifluor-
oborate and amidosulfonates, as well as for other poly-
cationic brushes, such as poly[1-ethyl 3-(2-methacryloyloxy
ethyl) imidazolium chloride].[12] Polycation brushes can be
used to fabricate smart surfaces, whose contact angles
can be easily varied by exposure of the brush to specific ion
solutions.
To the best of our knowledge, unlike polycation brushes,
polyanion brushes have not been studied with regard
to their collapse with specific anions and their capacity
to change the wetting properties of surfaces. In this
communication, we report the tuning of surface wett-
ability by exposing anionic poly(potassium 3-sulfopropyl
methacrylate) brushes to different cationic surfactants,
such as quaternary ammonium and quaternary imidazo-
lium molecules.
Experimental Part
Chemicals
Potassium 3-sulfopropylmethacrylate (SPMA), 2,20 -bipyridine (bpy),
CuICl, CuIICl2, ethyl 2-bromoisobutyrate (2-EBiB), mercaptounde-
cane (blank thiol), tetraethylammonium bromide (TEAB), tetra-
butylammonium bromide (TBAB), tetrahexylammonium bromide
(THAB), hexadecyltrimethylammonium bromide (HDTMAB) and
all other reagents were purchased from Aldrich. v-Mercaptoundecyl
bromoisobutyrate (thiol initiator) and 1-dodecyl-3-methylimida-
zolium bromide were synthesized as described elsewhere.[13,14]
1H,1H,2H,2H-Perfluoro-1-decyl-3- methylimidazolium iodide was
synthesized according to the literature procedure.[15]
Measurements
ATRP and cation exchange reactions were followed using a quartz
crystal microbalance with dissipation (QCM-D) from Q-Sense,
Gothenburg, Sweden. Water contact angles were measured on a
CAM-200 from KSV Instruments Ltd.
Macromol. Rapid Commun. 2008, 29, 871875
872 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
M. Dobbelin, G. Arias, I. Loinaz, I. Llarena, D. Mecerreyes, S. Moya
Quartz Crystal Microbalance with Dissipation
A quartz crystal microbalance with dissipation allows changes in
both frequency and dissipation of an excited quartz crystal to be
followed as a function of time. A QCM crystal consists of a thin
layer of quartz between two electrodes; the crystal is excited by
applying an RF voltage across the electrodes close to the resonance
frequency. The frequency of oscillation is related to the mass of the
crystal, and additions of mass to the surface of the crystal will
decrease the frequency. The dissipation of the crystal is measured
by recording the response of the freely oscillating crystal that
has been vibrated at its resonant frequency. The values of the
dissipation are related to the viscoelasticity of the film. The
dissipation is defined as DD Edissipated/2Estored. The equipment
has a chamber with an 80 mL volume, which is closed at one side
by the quartz crystal. The cell can be filled and the fluid exchanged
using the standard Q-Sense flow system. The quartz crystals,
purchased from Q-Sense, had a main resonance frequency of
5 MHz.[1620]
Typical Procedure for Synthesis of PSPM Brushes
Atom transfer radical polymerization of poly(potassium
3-sulfopropyl methacrylate) (PSPM) brushes from monolayers of
initiating thiols was conducted following well established
methods described in the literature.[1,21,22] The samples for the
water contact angle measurements were grown on gold coated
pre-annealed glass substrates from arrandee (www.arrandee.com)
by immersing them in the polymerization solution for several
hours. Samples for the QCM-D were synthesized from quartz
crystals from Q-Sense. In a typical reaction, 1.24 g of SPMA, 0.75 mL
of distilled water and 1.25 mL of DMF were introduced into a
Schlenk flask and degassed with nitrogen. Aqueous Cu-bpy stock
solution was prepared by adding 2 mL of degassed water to
39.6 mg of CuCl, 53.8 mg of CuCl2 and 312 mg of bpy. 19.5 mg
of 2-EBiB and 0.5 mL of the Cu-bpy stock solution were added to
the SPMA solution for the polymerization.
Typical Procedure for Cation Exchange
For the cation exchange reactions, 10  10
3 M solutions of the
ammonium and imidazolium salts were prepared. The substrates
with PSPM brushes were immersed in the polymerization
solutions for 60 min with stirring and then washed with water.
For the QCM-D measurements, the chamber was filled with the
salt solutions at suitable time periods.
Results and Discussion
The synthetic pathway to PSPM brushes and the sub-
sequent cation exchange procedure by a cationic surfac-
tant is shown in Figure 1. In the first step, PSPM brushes
were grown by ATRP from gold surfaces similarly to
procedures recently reported (Figure 1(a)).[21] The scheme
in Figure 1(b) shows the brush monolayer with K as
the counter ion. In a second step, the K counter ions in the
polyanionic brushes were replaced by voluminous cations,
such as tetraalkylammonium and alkylimidazolium ones
DOI: 10.1002/marc.200800071
Tuning Surface Wettability of Poly(3-sulfopropyl methacrylate) Brushes . . .

(Figure 1(c)). Both processes were

followed using the quartz crystal
microbalance with dissipation.
Figure 2 shows changes in
frequency and dissipation on a
quartz crystal during the poly-
merization in the chamber. The
quartz crystal was first coated
with a monolayer of initiating
thiols from a 10  10
3 M stock
solution of v-mercaptoundecyl
bromoisobutyrate. For the poly-
merization, the chamber was
firstly filled with a mixture of
2 parts solvent and 1 part mono-
mer to remove all oxygen present
in the chamber. This stage was
followed by the addition of the
same deoxygenated mixture of
solvents and monomer, but with
catalyst (CuCl, CuCl2), ligand (bpy)
and initiator (2-EBiB). After the
reaction, the chamber was washed
with ethanol and water. Fre-
quency changes are related to
the mass growth on the surfaces
and can be used to assess when
Figure 1. Schematic of: (a) a mixed initiator and blank thiol monolayer; (b) surface initiating the reaction comes to a conclu-
polymerization of PSPM; (c) cation exchange reaction.
sion. Obtained dissipation values
were typical. QCM-D allows com-
parison of the yield of the reac-
tion for different reaction conditions, such as catalyst,
co-catalyzer ratio, density of initiators, solvent character-
istics or temperature.[11,13,2327]
Once the PSPM brushes had been grown, the cation
exchange process and the collapse of the brush was trigged
by exposing it to solutions of different cationic surfactants,
such as tetraethylammonium bromide, tetrabutylammonium
bromide,tetrahexylammoniumbromide,hexadecyltrimethyl-
ammonium bromide, 1-dodecyl-3-methylimidazolium
bromide and 1H,1H,2H,2H-perfluoro-1-decyl-3-methyl-
imidazolium iodide. As an illustrative example shown in
Figure 3, changes in frequency and dissipation for PSPM
brushes exposed to tetraethylammonium bromide can be
seen. For the cation exchange, the chamber of the QCM-D
was filled with 10  10
3 M tetraethylammonium bromide
(aq). After the addition of the surfactant solution, the
frequency started to increase slowly while the dissipation
went down. Washing with water did not recover the
original frequency and dissipation values. The original
frequency and dissipation values were recovered after
washing the brush with 1 M NaCl (aq) followed by water
Figure 2. Changes in: (a) frequency; (b) dissipation of a quartz (not shown). The observed changes, both in frequency and
crystal during the polymerization of PSPM brushes. dissipation, were consistent with those expected for the

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2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.mrc-journal.de 873
 M. Dobbelin, G. Arias, I. Loinaz, I. Llarena, D. Mecerreyes, S. Moya

series of surfactants as measured with the contact angle

technique. Initially the brush was hydrophilic with a water
contact angle of 23 8.
Increasing the length of aliphatic chains in the cationic
surfactant increased the contact angle. The tetraethylam-
monium coordinated brush showed a water contact angle
of 38 8 (not shown). For longer aliphatic chains, the water
contact angles reached values of 40 8 for hexadecyltri-
methylammonium bromide and 56 8 for 1-dodecyl-3-
methylimidazolium bromide. Hydrophobicity increased
even more when we made the brush collapse with a
fluorinated surfactant (1H,1H,2H,2H-perfluoro-1-decyl-
3-methylimidazolium), to around 69 8. The increase in
hydrophobicity was nevertheless not as steep as with
polycation brushes using fluorinated salts.[10] This is
probably due to the characteristics of the sulfonate groups
Figure 3. Changes in: (a) frequency; (b) dissipation of a quartz
crystal during the exposure of a PSPM brush to 10  10
3 M
whose charges are more diffuse and less easy to screen
tetraethylammonium bromide (TEAB) solution. than the quaternary ammonium groups of PMETAC
brushes. It was then thought that using a brush with
more accessibility for the surfactant molecules to the
brushes during the collapse. The reduction in frequency interior of the brush could be a good strategy to obtain a
can be related to a loss of water from the system, while the brush with contact angles over 80 8. It has been shown by
decrease in dissipation can be understood as the result of Ruhe et al. that the grafting density strongly influences the
conformational changes in the polymer chains during degree of binding of surfactants to a brush and the degree
collapse; the brush passes from being a soft interface with of binding of alkyl ammonium salts to polymethacrylic
high dissipation when the chains are extended to a solid acids increases with decreasing grafting.[28] Therefore, we
material when the chains collapse. In order to remove the synthesized a less dense poly(potassium 3-sulfopropyl
surfactant, the surfactant sulfonate interaction must be methacrylate) brush by diluting the amount of initiator on
weakened using NaCl in a high concentration. the surface. Thus, the initiator molecules were assembled
In some cases, washing with ethanol was necessary on the substrates from a 10  10
3 M thiol solution bearing
after the treatment with NaCl to fully remove the 5% of initiator, while the remaining percentage of the
surfactant and return it to its original
state. The slow speed of the collapse
process contrasts with that reported
for inorganic salts.[11] We assume that
this is due to the accessibility of the
surfactant in the brush. For the series
of surfactants we employed, collapse
was always observed, but the kinetics
of the process varied significantly
from one molecule to the next. Experi-
ments are ongoing to properly under-
stand the nature of this process.
The collapse, as we have shown,
implies a reduction in the water
content of the brush. The loss of water
in the system and the pairing of the
charges of the pendant groups and
the organic cations, respectively, will
affect surface properties and the
wetting characteristics of the surface.
Figure 4. Changes in wettability corresponding to a gold surface modified with poly(sulfo-
In Figure 4(a) we can observe the propyl methacrylate) brushes with different counter ions. Line (a) is a gold surface initially
changes in the wetting character of modified with 100% v-mercaptoundecyl bromoisobutyrate and (b) is a mixture of 5%
the PSPM brush when treated with a v-mercaptoundecyl bromoisobutyrate/95% blank thiol (non-initiating).

Macromol. Rapid Commun. 2008, 29, 871875

874 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/marc.200800071
Tuning Surface Wettability of Poly(3-sulfopropyl methacrylate) Brushes . . .
thiols was non-initiating. The initial poly(potassium
3-sulfopropyl methacrylate) brush showed, in this case,
a contact angle of 36 8, which was 13 8 more than the brush
from the 100% initiator modified surface (Figure 4(b)).
When we performed the treatment with the surfactants, in
all cases higher water contact angles were observed, and in
the case of the fluorinated surfactant the contact angle
reached a value of 89 8.
Conclusion
We have shown that the surface wettability of polyanionic
PSPM brushes can be tuned by cation exchange with ionic
liquid-like surfactants and ammonium surfactants. The
growth and collapse of the brush was followed with
QCM-D. A characteristic increase in frequency and
decrease in dissipation due to a reduction in water content
and conformational changes of the brushes were observed
when coordinated with different cations. Interestingly,
higher water contact angles were obtained when applying
the cation exchange to the less dense brushes. This
situation was explained by better accessibility of the
surfactant in the brush. By choosing the proper counter
cations, the water contact angle of poly(3-sulfopropyl
methacrylate) brushes could be increased reversibly
from 36 8 up to 89 8. This observation highlights the use
of brush density in the design of complex surfaces with
tailored properties.
Acknowledgements: S. E. Moya is a Ramon y Cajal fellow and
would like to thank this program as well as project (Ma
T2007-60458) from the Spanish Ministry of Science and Education.
The authors wish to thank the Gobierno Vasco and the Diputacion
de Gipuzkoa for financial support through the NANOTRON Etortek
project. They also acknowledge Marie Curie RTN THREADMILL
(MRTN-CT-2006-036040) for financial support.
Received: February 1, 2008; Revised: February 27, 2008; Accepted:
February 28, 2008; DOI: 10.1002/marc.200800071
Keywords: atom transfer radical polymerization (ATRP); mono-
layers; polyelectrolytes; surfaces; surfactants
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2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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