Polymer 55 (2014) 3436e3453

Contents lists available at ScienceDirect

Polymer
journal homepage: www.elsevier.com/locate/polymer

Feature article

Light-induced wettability changes on polymer surfaces

Natalie Wagner, Patrick Theato*
Institute for Technical and Macromolecular Chemistry, University of Hamburg, Bundesstraße 45, 20146 Hamburg, Germany

a r t i c l e i n f o a b s t r a c t

Article history: Altering the surface wettability by external stimulation has received great attention recently. While
Received 25 February 2014 different stimuli, such as temperature, pH, etc. can be applied for this purpose, light combines several
Received in revised form advantages. It is a contact-free stimulation, which can be applied locally, thereby allowing a versatile
7 May 2014
patterning. This review article summarizes recent developments in the area of polymers that allow a
Accepted 11 May 2014
Available online 2 June 2014
light-induced change in surface wettability. For this purpose, different photochromic dyes have been
incorporated into polymers, which enable a photo-isomerization upon light irradiation resulting in a
change in polarity. Several examples based on azobenzene or spiropyran will be discussed, but also some
Keywords:
Surface
more exotic examples, such as those based on salicylideneaniline, will be highlighted. The different
Photochromic polymer approaches how to apply these photochromic dyes to various surfaces are presented and discussed.
Wettability Additionally, the combination with other stimuli-responsive moieties will be explored and the paper will
be concluded by mentioning the remaining challenges and by providing a future perspective.
© 2014 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/by/3.0/).

1. Introduction diamond, chitosan, polystyrene, poly(vinylidene fluoride), poly(-

This present review addresses recent developments in the field
of polymer films with light-tunable wettability. We will focus on
examples that allow reversible wettability switching of reactive
surface coatings of various photochromic dyes induced by light-
stimuli. Over the past years, the research in the field of polymer
films has become increasingly important because of the possibility
to create thin films with different thicknesses, chemical composi-
tion and grafting density. Moreover, the use of polymer films also
enables us to control the architecture of polymer films over a broad
range down to nanoprecision. Combined with photolithography,
polymer films can also be used for the production of controlled
patterned domains [1,2].
The most widely used approach for the preparation of polymer
films is the “grafting from” method. This strategy allows creating
dense polymer brushes on an initiator-modified substrate by using
all known polymerization techniques, such as ring opening
metathesis polymerization (ROMP), atom transfer radical poly-
merization (ATRP), reversible addition fragmentation chain transfer
(RAFT) or nitroxide-mediated polymerization (NMP) [3,4].
Furthermore, the “grafting-from” approach can be applied on a
variety of surfaces, including ITO, A2O3, ZnO, carbon black,
* Corresponding author. Tel.: þ49 40 42838 6009; fax: þ49 40 42838 6008.
E-mail address: theato@chemie.uni-hamburg.de (P. Theato).
dimethylsiloxane), poly(methyl methacrylate), and many others
[5e7].
Other currently available approaches for preparation of smart-
surfaces that can be used in various areas, such as in tissue engi-
neering, biosensor technology or drug delivery, are electrospinning,
self-assembly, phase separation and chemical vapor deposition
(CVD) [8,9]. Among those techniques, electrospinning is a method
investigated in detail and had already shown highly promising
results in many biomedical applications [10]. A new developed
method that allows controlling the morphology and geometry of
the nanofibers from a variety of materials is forcespinning™. This
process is based on centrifugal forces or electrostatic forces and can
be used for preparation of nanofibers from solutions or melts
[11,12].
In recent years, synthetic stimuli-responsive polymer films have
gained great interest for monitoring reversible and nonreversible
wetting properties. Not only physical stimuli, such as solvent,
temperature or mechanical strength, but also chemical changes,
such as using environmentally friendly chemicals may lead to a
change in the wettability behavior. In general, external stimuli, such
as light illumination, solvents, electrical potential, temperature and
pH can change the surface properties followed by a change in
surface behavior. Recently, the changing of surface wettability by
ion-pair receptors on self-assembled monolayers and the exchange
of counterions were reported as a new strategy to generate a
reversibly switchable wettability [13e19].

http://dx.doi.org/10.1016/j.polymer.2014.05.033
0032-3861/© 2014 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/3.0/).
 N. Wagner, P. Theato / Polymer 55 (2014) 3436e3453 3437

A reversible electrochemical switching of polymer brushes can Table 1

be obtained by grafting ambience-sensitive polymer brushes from Light-switchable chromophores (Reproduced from Refs. [59e63,151]).

an electrochemically conducting active polymer. In fact, the prop- Light-switchable chromophores

erties can be modulated between electrical conductivity, optical
properties or volume by exchange of ions during a redox process Reversible switching Spiropyran derivatives

[20,21]. Switching from a superhydrophobic to a superhydrophobic

surface can also be achieved by electrochemical oxida-
tionereduction reactions of polyaniline films on a conducting
substrate. Moreover, electroactive self-assembled monolayers on
different substrates are capable to form a multichannel surface Coumarin derivatives
switch by electrical tuning between two redox states. Such systems
are interesting candidates for the production of microfluidics and
biosensors [22e24].
Noteworthy, besides organic materials, a wide number of inor-
ganic materials are used for stimuli-responsive surfaces. Inorganic
oxides are well-known as stable, nontoxic and highly reactive
materials which are able to induce the large wettability changes. In
previous studies, surface wettability of light-responsive inorganic Azobenzene derivatives

oxides, such as ZnO, TiO2 and SnO2 has been reported [25e31].
The group of the stimuli-responsive polymers consists of several
classes of stimuli-responsive polymers, such as biopolymers and
synthetic polymers. The stimuli-responsive biopolymers occur in
nature, for example, in the form of nucleic acids or proteins. In
recent years, thermo-responsive polymers have found increasing Reversible/irreversible Cinnamates derivatives
and significant application, especially in the field of biomedical switching
applications, such as diagnostics, therapeutics and surgery. A wide
range of biocompatible polymers is known, some of which are also
thermo-responsive. Up to today, the best investigated, water-
soluble and thermo-responsive polymer is poly(N-isopropyl acryl-
amide) (PNIPAm). PNIPAm exhibits a lower critical solution tem-
perature (LCST) of 32  C, which is in a physiologically interesting
temperature range [32]. This behavior is caused by reversibly
changing the entropic and enthalpic contribution to the free energy
of thermo-responsive polymers in aqueous solutions. At tempera-
tures below the LCST, the enthalpic effects predominate the Irreversible switching Sulfonium triflate based PAG
entropic effects, expressed by hydrogen bonds between the poly-
mer chain with water molecules, which leads to the extended
solubilized state of the PNIPAm chains and consequently to a hy-
drophilic surface behavior. Upon increasing the temperature above
32  C, the entropic contribution increases, resulting in breaking of o-Nitro-benzyl derivatives
the intermolecular hydrogen-bonds between the polymer chains
and the water molecules. Hence, we obtain a collapsed state of the
polymer chains resulting in hydrophobic surfaces. This change in
surface hydrophobicity is accompanied by further property
changes, e.g. collapsed PNIPAm surface above LCST promote protein
adsorption and cell adhesion [33e43].
Light-responsive polymers belong to the large group of stimuli-
responsive polymers, which respond to the changes of environ-
mental conditions, in this case irradiated light. However, not only a reversible light-responsive behavior is
In the last two decades, synthetic light-stimuli responsive known, but also an irreversible one. Such irreversible effects can be
polymers have gained more attention because of their wide variety obtained in polymers with photocleavable moieties containing
of applications. Such light- or photo-responsive polymers are able photochromic units [54]. Upon exposure to UV light, the obtained
to alter their properties reversibly, especially their wetting polymers bearing light-responsive groups undergo an irreversible
behavior upon irradiation with light of a defined wavelength. These transformation, resulting in more polar species [55]. One repre-
changes are often based on the chromophoric groups of organic sentative of this group is the ortho-nitrobenzyl ester (ONB), which
dyes, such as azobenzene, spiropyran, or salicylideneaniline, to can be used for the preparation of photopatternable polymer thin
mention a few, which undergo a reversible isomerization upon films. Moreover, ONB groups can be employed as photopatternable
exposure to UV light or to visible light [44e47]. Azobenzene- protecting groups of amines and diamines, which can be cleaved off
containing polymers, for example, are the most frequently stud- by exposure to 300 nm [56,57]. An extreme example can be found
ied polymer systems, where the low energy trans-isomeric state in photolithographic applications that utilize resists based on
can be switched reversibly just by using a photo-chemical or diazonaphthoquinone, which can undergo a Wolff-rearrangement
approach to the high-energy cis-isomer. The reverse change from upon light irradiation [58].
the cis-isomer to the trans-isomeric can additionally be triggered In the following sections, we will summarize developments of
thermally. Such alterations can be accompanied by significant photo-switchable surfaces based on the employed photochromic
changes in geometry or polarity [48e53]. moiety.
3438 N. Wagner, P. Theato / Polymer 55 (2014) 3436e3453
2. Spiropyran-functionalized surfaces
Spiropyran derivatives are highly interesting candidates for
the surface functionalization because they can undergo a chem-
ical configuration isomerization induced by light irradiation. As is
already known, spiropyran undergoes a photoinduced trans-
formation between two isomeric forms, the neutral almost
colorless spiropyran form and the colored merocyanine form.
Photoisomerization from the spiropyran to the merocyanine can
be induced by irradiation with UV light (typically 365 nm), while
the reverse isomerization can be triggered by visible light irra-
diation. This photoisomerization may cause changes in the sur-
face free energy, which consequently results in a change in
surface wettability [29]. In 1994, Imanishi et al. used methacry-
late containing a spiropyran group to photocontrol the perme-
ability of a porous polymer membrane. Hence, they carried out a
graft copolymerization of spiropyran-containing methacrylate
and acrylamide on the surface of a porous polymer membrane.
They showed that by visible light irradiation, the permeation
decreased by transformation of the graft chains into a neutral
spiropyran. By UV-light irradiation the permeation of the mem-
brane increased because of the formation of the zwitterionic
merocyanine form [59,64].
In recent times, typical inorganic substrates, such as glass or Si-
wafers, were replaced by polymers like polydimethylsiloxane,
polycarbonate or cyclic olefin copolymers (COC) [65e67]. This
continuous change of substrates makes it a challenge to develop
suitable synthetic protocols to immobilize functionalized polymers
on these very different substrates. Accordingly, the group of Theato
have developed reactive surface coatings using hybrid copolymers
on the basis of poly(methylsilsesqioxane)epoly(pentafluorophenyl
Fig. 1. Wettability switching cycles between low and high surface wetting on a spiropyran-functionalized surface. (A). 5 min irradiation with l ¼ 365 nm; 12 h in the dark; (B). UV/
Vis spectra before and after irradiation of a spiropyran-functionalized coating on glass. (Reproduced from Ref. [72]).
acrylate) that allow preparation of stable polymer coatings on
various substrates [68e70]. Afterwards, these reactive coatings
were modified by a post-modification procedure of various
photochromic dyes, such as azobenzene, salicylidenaniline and
spiropyran. All modifications resulted in light-responsive surface
coatings, with the spiropyran-containing polymer showing the
largest change in wettability of up to 30 in water contact angles
[71,72].
As already mentioned before, spiropyran groups can be iso-
merized by a ring opening-reaction upon UV-irradiation. By the
formation of a zwitterionic merocyanine structure, the dipole
moment can be strongly changed (Table 1). After 12 h in the dark,
which induced the back isomerization into the spiropyran isomer, a
switching to the hydrophobic state took place; the contact angle
could be reversibly switched from 48 to 78 over ten cycles (Fig. 1).
The effect of reversible wettability of photo-responsive spi-
ropyran-containing surfaces could be amplified by increasing the
roughness of the substrates. The roughness of surfaces of silicon
substrate could be monitored by a facile laser etching method
(Fig. 2). Afterwards the spiropyran monomer was polymerized from
the silicon substrate by a “grafting-from” atom transfer radical
polymerization (ATRP) procedure with a-bromoisobutyryl bromide
as an initiator precursor in THF containing CuBr and pentam-
ethyldiethylenetriamine. The water contact angle of the surface of
silicon substrates could be reversibly switched from 138.8 to 42.7
[73].
Similarly, Locklin and coworkers reported on the preparation of
photochromic polymer brushes by grafting from oxide surfaces.
They used the surface-initiated ring-opening metathesis polymer-
ization (ROMP) of monomers containing spiropyran units in the
presence of Grubbs catalyst II [74]. Initially, vinyl-terminated SAMs
 N. Wagner, P. Theato / Polymer 55 (2014) 3436e3453 3439

Fig. 2. SEM image of the as-prepared surfaces. (Reproduced from Ref. [73]).

of 7-octenyl trichlorosilane were deposited on the substrate surface
for introduction of the Ruthenium catalyst, which initiates ROMP.
Afterwards the spiropyran-substituted norbornyl derivatives were
introduced by dipping into the monomer solution in dichloro-
methane (Fig. 3). After 4 h at 50  C, stable polymer brushes were
obtained and then investigated by UV spectroscopy and contact
angle measurements. The ring closed spiropyran form showed no
characteristic absorbance in the visible region. The concentration of
ring-opened merocyanine was enhanced with increasing UV
exposure time reaching finally a photostationary state.
The reversible change in the dipole moment upon UV light irradi-
ation induced isomerization from the nonpolar closed form to the
highly polar, colored open-ring form, which was confirmed by
contact angle measurement. Water contact angle changes from
DCA ¼ 5e15 were obtained without degradation after more than
five switching cycles [75e78].
Very recently they reported on the interaction of zwitterionic
merocyanine (MC) of both cis- and trans-isomers of copolymers
containing spiropyran moieties with different divalent metal ions.
For this purpose, they synthesized two different spiropyran de-
rivatives, spiropyran methacrylate (SPMA) and spiropyran meth-
acrylate, with a methoxy substituent in the 8 position of the nitro
ring (MEO) to investigate the influence of the second chelating
group on the ring in the presence of metal ions.

Fig. 3. The procedure of formation of spiropyran-based polymer brushes by using SI-ROMP from surface oxide. (Reproduced from Ref. [74]).
3440 N. Wagner, P. Theato / Polymer 55 (2014) 3436e3453

In spiropyran molecules, a CeO bond can be cleaved reversibly Table 2

upon UV-light exposure, which leads to the reversible switching Initial rates of charging of rolling steel spheres on polymer films. Angew. Chem.
(Reproduced from Ref. [64]). http://onlinelibrary.wiley.com/doi/10.1002/anie.
between the colorless ring-closed spiro form and the red ring- 201003985/abstract.
opened form, the merocyanine form. Metal ions can interact with
the negatively charged phenolate groups of the zwitterionic form Copolymer Rate of charging [pC s1]

resulting in a merocyanineemetal ion interaction (MCeM2þ). Before UV After UV Unreactive

During the visible light irradiation, the weak MCeM2þ bond can be irradiation irradiation homopolymer

broken so that the ring-closed spiro isomer is formed again SPMAaenBuMAb 8 (2) 60 (30) 9 (4)
[79e83]. SPMAeMMAc 4 (2) 57 (20) 11 (4)
SPMAeStd 2 (2) 106 (46) 0.7 (0.7)
It could be shown by UVeVis absorption spectroscopy, that both
SPMAe4FSte 8 (4) 20 (6) 11 (4)
the SPMA-containing copolymer thin films showed substantially
a
bigger absorbance maxima in comparison to the MEO- and TFEMA- SPMA: nitrospiropyran-containing methacrylic monomer.
b
nBuMA: n-butyl methacrylate.
containing copolymers. (Reproduced from Ref. [84]). c
MMA: ethyl methacrylate.
The UVeVIS spectral changes between each complex are smaller d
4FSt: 4-fluorostyrene.
in the MMA complexes than in the TFEMA complexes, thus TFEMA- e
St: styrene.
containing complexes were studied by FT-IR to investigate the
MCeM2þ complexes (Fig. 4B). In summary, it could be recorded that
the binding of the metal ions in MC is influenced in the MEO- spiropyran resulted in the formation of light-responsive polymer
containing polymers by the phenolate and the methoxy anions. In brush films [86]. The contact angle could be amplified by increasing
the course of this process, the methoxy functional group interacts the roughness by photopatterning of S-CTA modified silicon sub-
with the phenolate anion of the ring-opened merocyanine in a strates. For this, the S-CTA modified substrates were irradiated with
trans-configuration leading to the decline in the electron density in UV-light using Cu-masks following the decomposition of the S-CTA
both the aromatic ring and the nitro group [85]. Hence, symmet- units in the exposed regions.
rical stretching bands of the aryl nitro group shifted from S. Friedle and S. W. Thomas III used spiropyran containing
1519 cm1 to 1527 cm1 for the MCeSn2þ, 1527 cm1 for the polymers to solve the problem of contact electrification, which can
MCeFe2þ and 1526 cm1 for the MCeCu2þ. In contrast to these lead to inhibition of the power of equipment or ignition of a
results, for metal complexes such as MCeZn2þ, MCeCo2þ and flammable vapor. They used a ferromagnetic steel sphere, which
MCeNi2þ, which have a lower interaction with the methoxy sub- was rolled onto the electrically insulating film by a magnetic stir-
stituent, the bands are observed to be at 1521 cm1. Moreover, it ring plate and investigated with its help the effect of the chemical
could be shown that Fe2þ and Cu2þ form bonds in the SPMA- structure on contact electrification. By using reversibly switching
containing copolymers as a cis-MCeM2þ, resulting in large blue the photochromic (Table 1) nitrospiropyran-containing methacrylic
shifts of 174 nm and 147 nm. polymer between different isomeric forms upon UV irradiation, it
In 2012, Choi et al. prepared reactive polymer brushes with could be shown that the hydrophilic merocyanine form developed
adjustable molecular weight and grafting densities by surface a more negative charge than the neutral spiropyran form (Table 2,
reversible additionefragmentation chain transfer polymerization Fig. 5) [23,64].
of pentafluorophenyl acrylate. Such a reactive ester containing
polymer can be used for the functionalization of polymer brush 3. Azobenzene-functionalized surfaces
films with different groups by reaction with amines, for example,
amino-functionalized spiropyran. They utilized dithiobenzoic acid Azobenzene is probably the most well-known candidate used in
benzyl-(4-ethyltrimethoxylsilyl) ester as a surface-immobilized light-responsive surfaces because it can change between two
chain transfer agent (S-CTA). Post-polymerization modification of isomeric forms, trans- and cis-azobenzene, upon exposure to UV
poly(pentafluorophenyl acrylate) brushes with amino-modified light resulting in a change of molecular properties such as surface

Fig. 4. UVeVis absorbance spectra of poly(MMA90-co-SPMA10) (A) and poly(TFEMA90-co-MEO10) (B) in the presence of different divalent metal ions. SP and MC refer to the
absorbance spectra of the polymer thin films in the ring-closed (SP) and ring-opened state (MC). (Reproduced from Ref. [84]).
 N. Wagner, P. Theato / Polymer 55 (2014) 3436e3453
Fig. 5. The steel sphere before and after irradiation of the film with UV light (A). Real-time measurement of a film of SPMA-4FSt (B). (Reproduced from Ref. [64]).
wettability, viscosity, free volume, dipole moment or solubility [60].
Recently, Santer and coworkers reported on azobenzene containing
polymer brushes that were prepared by post-polymerization
modification of poly(methacrylic acid) films with azobenzene
groups. During the exposure to UV light, substituted azobenzene
molecules can reversibly change between trans- and cis-forms,
resulting in an orientation of polymer brushes on the surface.
Irradiation with interference patterns results in surface relief
gratings. Depending on the irradiation time not the height of the
grating can be controlled. Patterns that were inscribed by short
irradiation times could be erased by solvent treatment, while
longer irradiation times led to permanent patterns because a
photochemical scission of polymer chains was observed
[16,29,52,87,88] (Fig. 6).
The correlation between the structure and the wettability of
photoswitchable monolayers containing azobenzene groups on
silicon surfaces has been investigated by Jonas et al. [89]. Usually
azobenzene monolayers alternate upon UV light irradiation from
the hydrophobic cis-isomer to the hydrophilic trans-isomer fol-
lowed by a change in the dipole moment of the azobenzene mol-
ecules. However, they employed azobenzene monolayers on silicon
surfaces that present a pending hydrophilic group, which showed a
different behavior during the exposure to UV light. Even though the
photoisomerization was reversible, it changed from the hydrophilic
trans-isomer to the hydrophobic cis-isomer, because the hydro-
philic substituents on the azobenzene are bended away exposing
more hydrophobic parts [90]. It could be shown that the wettability
of azobenzene self-assembled monolayers can be influenced not
only by the dipole moment, but also by the consistency of the
surface and by the alignment of functional groups (Fig. 7).
3441
In 2012, Rühe and coworkers found that the wettability of sur-
faces can be adjusted by UV or visible light irradiation, so that the
water contact angle changes between different wetting regimes,
such as hydrophobic and Wenzel state or Wenzel state and
superwetting state [91]. Such a change was achieved by using a
nanoscale roughness and a surface covered with azobenzene
functional groups. For this purpose, light-responsive polymer
brushes with trifluoromethyl-modified azobenzene moieties were
synthesized by grafting reactive precursor polymers onto surfaces
(Fig. 8). To generate the polymer monolayers, the substrate surfaces
were first functionalized with (4-(30 -chlorodimethylsilyl) propy-
loxy benzophenone). Afterwards, rough polymer layers were ob-
tained by spin coating from polymer solution in chloroform and
attachment to the silicon surface by irradiation at 254 nm. Covalent
attachment was achieved through the benzophenone groups,
which are known to add onto CeH bonds upon exposure to UV
light. The contact angle of water on all polymers on the planar
silicon substrate could be reversible switched over five cycles [92].
Varying compositions with azobenzene moieties was then ach-
ieved by post-modification of the reactive polymer films.
Studies of these azobenzene containing polymer films on flat
surfaces have shown that greater concentrations of OCF3-Azo in the
polymers lead to a higher values of the contact angle, which were
about 14 higher for all polymer compositions. In accordance with
previous studies, the water contact angle changed depending on
the switching of azobenzene from the trans- to the cis-isomer. The
increased contact angle during the transition from Wenzel wetting
to superwetting amounted to Dq ¼ 130 and the decreased contact
angle during transition from superhydrophobic to Wenzel wetting
amounted to Dq ¼ 170 .
3442 N. Wagner, P. Theato / Polymer 55 (2014) 3436e3453

Fig. 6. The photosensitive azo-PMAA polymer brush (A). The azo-PMAA brush before irradiation (B). The brush after irradiation with the UV during 10 min. (C). After irradiation
during 30 min (D). (Reproduced from Ref. [88]).

Fig. 7. Reversible photoisomerization process of hydrophilic azobenzene monolayer upon UV irradiation. (Reproduced from Ref. [90]).
 N. Wagner, P. Theato / Polymer 55 (2014) 3436e3453
Fig. 8. Synthesis of surface attached monolayers of azobenzene group containing copolymers (A). Contact angle of water on flat (aec) and nanograss covered silicon surfaces (def) (B). (Reproduced from Ref. [93]).

3443
3444 N. Wagner, P. Theato / Polymer 55 (2014) 3436e3453
Another interesting example has been reported by the research
group of Jiang. They prepared [94] containing azobenzene on rough
surfaces, which were generated by photolithography on flat silicon
substrates. The contact angle change of the monolayer between cis-
state und trans-state of azobenzene upon UV and VIS irradiation
was only about 2 . However, at the distance of 40 mm between
micropillars upon photoisomerization, they could obtain a
switching of the contact angle from 150 to 87 after UV irradiation,
which switched back after exposition to visible light.
Electrospinning is a very versatile method and it can be used for
the preparation of many polymer fibers, such as from polymers
loaded with chromophores, nanoparticles etc. Additionally, elec-
trospinning can be used for the production of nanofibers with a
complex architecture, such as coreeshell fibers or hollow fibers
[10]. Currently, nanofibers gained importance for applications in
biomedical areas [95]. They can be employed as scaffolds for
musculoskeletal tissue engineering, vascular tissue engineering,
neural tissue engineering, skin tissue engineering and as carriers
for the controlled delivery of DNA, drugs, and proteins [8,96e98].
Another smart polymer surfaces find also versatile applications
such as in antifouling surfaces, cells engineering, protein chroma-
tography, biochips, and bioassays [99,100].
Very recently, Chen and Besenbacher reported on a method to
generate functional surfaces with controllable wettabilities upon
external stimulus [101,102]. They reported a study of biodegradable
poly(ε-caprolactone) (PCL) fibers that were functionalized by
photo-responsive azobenzene moieties. The functionalized fibers
were prepared by electrospinning using simply a one-pot reaction
utilizing covalent cross-linking of the PCL fibers via benzophenone
chemistry (Fig. 9).
PCL is a well-known biodegradable and biocompatible material,
which was chosen as the polymer carrier. The azobenzene PCL
polymer fibers were obtained by reaction of benzophenone-4-
isothiocyanate with amino-functionalized azobenzene (A-azo)
upon UV irradiation, see Fig. 9 [103]. Then nanofiber mats con-
taining different amounts of azobenzene were prepared by elec-
trospinning and the obtained nanofibers were analyzed by XPS,
ToF-SIMS, SEM, UV/Vis and contact angle measurements. It was
found that contact angel of electrospun azobenzene-contained
mats could be switched from hydrophobic (CA ¼ 120e135 ) to
hydrophilic (CA ¼ 50e95 ) after exposure under UV-light and from
Fig. 9. Electrospinning of PCL-azo and light-responsive nanofibers (A). Reversible switching of hydrophobicity and hydrophilicity on photo-responsible PLC-azo mats and PCL mat
without azobenzene upon UV/Vis irradiation (B). (Reproduced from Ref. [101]).
hydrophobic to hydrophilic after visible light irradiation. This
switching process could be repeated for a four cycles.
Many investigations could prove that besides the chemical na-
ture of surfaces, also the roughness of surfaces affects their wetting
behavior [104]. Comparable with PS/PNIPAAM fibers, which form a
microbead/nanofiber hierarchical structure, electrospun azo-
benzene containing mats showed an increasing wettability when
polymer fibers exhibit a dual-topography structure [93,105].
Accordingly, the study by Chen and Besenbacher documented a
reversible and light-responsive change of the wettability depend-
ing on exposure to UVeVis-light and roughness of the electrospun
fibers. Hence, the most significant change in static contact angle
(Dq ¼ 132.2 ± 2.8 ) was measured on BP-azo/PCL-fibers (6.7%:20%)
with the largest amount of BP-azobenzene after a few reversible
cycles (Fig. 9).
The research on light-responsive polymers with azobenzene
moieties was intensified by Shimizu [106]. They investigated a new
process to produce microwrinkled surfaces, on which the formation
of capillaries was triggered by photopolymerization of an azo-
benzene polymer. First, the photosensitive microwrinkles were
prepared using a poly(pyromellitic dianhydride-co-4,40 -oxydiani-
line) (PAA) solution in N-methylpyrrolidone, which was then
applied to a polydimethylsiloxane (PDMS) surface. After heating, a
polyimide (PI) film could be obtained, which was deformed after
cooling at 25  C on the supporting PDMS substrate. Then, a poly{6-
[4-(4-ethoxyphenylazo)-phenoxy]hexyl methacrylate} (2Az6)
polymer brush was synthesized by ATRP, which is responsible for a
photoresponsive microwrinkled surface [107]. Shimizu et al. could
show that the surface contact angle can be changed upon UV
irradiation resulting in the formation of liquid filaments. Further
they could show that the surface contact angle can be changed
upon UV irradiation from 30 to 10 resulting in the formation of
liquid filaments (Fig. 10).
In 2006, Cho et al. reported on a photoreversible, switchable,
superhydrophobic surface with erasable and rewritable patterns
[108]. In this work, the investigators prepared different porous
organic-inorganic hybrid multilayers on negatively charged silicon
surfaces by using the layer-by-layer technique with polyelectrolyte,
poly(allylamine hydrochloride) (PAH) and SiO2 nanoparticles.
After modification with 3-(aminopropyl) triethoxysilane followed
by treatment with 7-[(trifluoromethoxyphenylazo)phenoxy]
 N. Wagner, P. Theato / Polymer 55 (2014) 3436e3453 3445

Fig. 10. Schematic illustration of preparation and optical microphotographs of LFs on photoresponsive microwrinkles. (Reproduced from Ref. [107]).

pentanoic acid (CF3AZO) as the photoswitchable agent, they could
obtain photo-responsive polyelectrolyte multilayers (Fig. 11) [109].
The reversibility of wettability was triggered by photo-
isomerization of azobenzene moieties. According to previous arti-
cles, it could be shown, that the water contact angle changes are
due to a change in the dipole moment related to the transformation
from the trans- to the cis-form of azobenzene moieties during UV-
light exposure. After UV irradiation, the contact angle decreased
corresponding to an increase in the dipole moment of the azo-
benzene cis-isomer [110]. The switching of contact angle of this
system was repeated for five cycles, however, the system showed a
minor degradation. In addition, photosensitive substrates with

Fig. 11. SEM images of a substrate formed after nine deposition cycles (A); magnified image (B); cross-sectional view (C). Photomask and water droplet profiles (D). Water droplet
profiles on the patterned substrate upon UV irradiation top (E) and side views (F). (Reproduced from Ref. [108]).
3446 N. Wagner, P. Theato / Polymer 55 (2014) 3436e3453
different wetting properties were prepared, whose structure could
be changed by selective irradiation, resulting in a locally varying
wettability.
Within the last few years, research concerning the stimulation
on the topology of liquid-crystals using the photochromic azo-
benzene has been more and more intensified [111,112]. Broer and
coworkers have reported on a new method to create the surface
topology by low light intensity [113]. They used patterned chiral
nematic networks with isotropic ranges in the cholesteric polymer
films to produce a photo-switchable surface relief [114e116]. The
cross-linkers containing azobenzene moieties were integrated into
a chiral nematic network, allowing to reversibly modify the liquid-
crystal network by photoisomerization of azobenzene [117]. Un-
fortunately, they did not report any contact angles. In fact, upon UV-
irradiation, the molecular structure is less ordered than before
exposure, since the cis-state of the azobenzene was obtained as a
result of the cis/trans-isomerization [118].
4. Other reversible chromophoric switches
4.1. Functionalization with cinnamate groups
Teyssie and coworkers, who studied cinnamate-modified cel-
lulose butyrate polymers, reported another interesting example of
photosensitive surfaces [119]. These photo-alignment materials
have been studied more than other compounds with respect to the
preparation of liquid crystal displays. The cinnamate groups are
well known for their photochemistry, on one hand based on the
(2 þ 2) photo-dimerization, and on the other hand for their cis/
trans-photoisomerization [120,121]. However, it was found that the
transecis-isomerization process prevails and is completely revers-
ible by heating to 130  C. Accordingly, they observed a partial
reversibility of the contact angle changes of around 55 by UV-light
irradiation, which was demonstrated for two cycles of photo-
irradiation (Table 1).
Fig. 12. Contact angle measurements on the honeycomb PSF relief before (A) and after (B) UV light exposure; PESF relief before (C) and after UV-light exposure (D). (Reproduced
from Ref. [125]).
4.2. Switchable wettability of polysulfone (PSF) and
polyethersulfone (PESF)
During the past decade, the polymers with honeycomb reliefs
became more interesting because they can be used for diverse
applications such as photonic and bio-medical applications
[122,123].
Polyarylsulfones are able to switch their wettability reversibly
from hydrophobic to hydrophilic upon UV-light exposure. This
could be explained by photo-oxidation and also as being a result of
disulfonic acid [124].
In 2011, Aurbach and coworkers reported on honeycomb poly-
arylsulfone structures with reversibly switchable wettability,
which were produced by evaporation of chlorinated solvents in a
humid atmosphere. The surface roughness occurred, which is
related to an increase in the contact angle, the so-called Cas-
sieeBaxter wetting regime, a typical regime for honeycomb struc-
tures [102,125e127]. After UV-light exposure, a dramatic change in
the contact angle was observed. Such a wettability behavior of a
surface is known as the CassieeWenzel wetting transition. In
accordance with the literature, such a wetting regime is reversible;
hence the contact angle could be tuned by UV-light irradiation
during several cycles (Fig. 12).
4.3. Photocontrollable diarylethene surfaces
Uchida and coworkers introduced another exciting example of
photosensitive surfaces with a remarkable wetting behavior
[128,129]. They synthesized a new type of diarylethenes, which are
polymorphic crystals with relatively low melting points (95  C)
[130,131]. Diethylarenes show photochromism and can be switched
from an open-ring isomer to a closed-ring isomer upon UV-light
irradiation and vice versa upon irradiation with visible light
[77,121]
 N. Wagner, P. Theato / Polymer 55 (2014) 3436e3453
In Uchida's work, a new diethylarene was synthesized, 1-(2,5-
dimethyl-1,1-dioxa-3-thienyl)-2-(2,5-dimethyl-3-thienyl)-3,3,4,
4,5,5-hexafluorocyclopentene, featuring a sulfone group on one
thiophene ring whose purpose it was to increase the polarity of the
diethylarene structure and to improve wettability. The wettability
behavior of the obtained functionalized surfaces was monitored by
water contact angle measurements. It could be shown, that the
non-irradiated surface featured a needle-like crystal structure and
exhibited superhydrophobic properties (CA ¼ 150 ). During UV
exposure at the eutectic temperature of 67  C, the initial crystals
melted and formed a flat surface, which could be regenerated by
visible light irradiation followed by the formation of new rod-
shaped crystals. At the same time, the contact angle was reduced
from 150.4 to 80.5 . Upon visible light irradiation for 1.5 h the
hydrophilic surface could be converted again to the rough surface
with water contact angle of 150.9 (Fig. 13). Here the switching of
surface wettability was repeated over three cycles [132].
4.4. Diethylcyclopentene-based self-assembled monolayers
The behavior of light-responsive polymers containing a deriva-
tive of photochromic compounds, such as azobenzene, spiropyran
and diarylethene has been studied intensively. But also the surface
modification utilizing self-assembled monolayers has been studied.
Fig. 13. SEM images of microcrystalline surface before UV irradiation (A) after UV irradiation (B); without (C). B, D, F water droplet on the surfaces of A, C and E. (Reproduced from
Ref. [132]).
3447
Recently, the group of Siemeling demonstrated another interesting
example for the production of photo-responsive surfaces with good
thermal stability and thermal irreversibility of photo-isomerization
[133]. They prepared curved self-assembled monolayers of dome-
shaped subphthalocyaninatoboron (SubPc) complexes from
dichloromethane solution by chemisorption on gold substrates.
Characterization of subphthalocyanine monolayers by X-ray
photoelectron spectroscopy showed that such SubPc complexes
containing different amounts of thioether units are able to attach
covalently to the gold substrate surface [134,135].
4.5. Coumarin-functionalized surfaces
Superhydrophobic silica surfaces functionalized with coumarin
dyes are reversibly photo-switchable and can be widely used in
biochemistry and as light-operated switches [108,136e140].
The properties of coumarin derivatives were investigated by
several groups who studied the photobehavior of coumarin com-
pounds upon UV-light exposure. The UV light-dependent photo-
dimerization and photocleavage could be used for this purpose.
Upon 360 nm UV irradiation, four different dimers can be formed:
syn or anti head-to-head and syn or anti head-to-tail [141e143].
Coumarin-modified fumed SiO2etoluene diisocyanate (CMFST)
nanoparticles were prepared, which dimerized under UV exposure
3448 N. Wagner, P. Theato / Polymer 55 (2014) 3436e3453

by a [2 þ 2]-cycloaddition, thereby featuring a reversibly switch-

able wettability between a hydrophobic and superhydrophobic
surface by corresponding static contact angle changing from 102
to 163 [144]. Moreover, it could be shown that the surface
morphology can reversibly undergo a change from semispherical
nanoparticles to ring-like nanoparticles at 365 nm (Table 1). In
addition to the morphology, the wetting behavior changed
reversibly upon irradiation with 365 nm to a superhydrophobic
surface and with 254 nm UV light to a hydrophobic surface, ac-
cording to Wenzel's theory. The surface wettability could be
reversible tuned for five cycles [145].

5. Irreversible chromophoric switches

5.1. Polymer brushes featuring irreversible changes in wettability

Within the last few years, research on the stimuli-responsive,

well-defined polymer films became more and more interesting
because of their versatile application possibilities, such as in the
microelectronics industry. Hence, it was attempted to prepare
Fig. 14. Photopatterned thin films still contained PFP ester moieties for a subsequent
photochemical acid generation (PAG) containing polymer chains. modification resulting in a color change of the films. (Reproduced from Ref. [155]).
One interesting method was developed by Huck and coworkers,
which was based on using homopolymer brushes without
Remaining PFP groups were then used for further modification with
responsive behavior and strong solvents [62]. Initially, poly(tert-
amines, which resulted in changes of the absorbance (see color
butyl methacrylate) (PtBMA) brushes were deprotected by triphe-
change from purple (in the web version) to red (in the web version)
nylsulfonium triflate (TPSOTf), while homolytic cleavage of a car-
after amine reaction in Fig. 14) as well as wettability.
bonesulfur bond results in a radical cation followed by the
Another interesting approach is based on the preparation of
formation of various photoproducts and triflic acid [146]. After-
homo and copolymers by post-polymerization modification of
wards, the PtBMA brushes were exposed to 254 nm UV-light,
poly(pentafluorophenyl acrylate) with ONB-protected diamines. In
resulting in the large change from hydrophobic to hydrophilic,
this work, a mono-ONB-protected diamine, N,N0 -dimethyl-N-(2-
which indicates the formation of poly(methacry1ic acid) (PMAA).
nitrobenzyl)ethane-1,2-diamine, was used as an irreversible
photo-protected crosslinking agent [156]. As already mentioned
5.2. O-Nitrobenzyl derivatives as photoresponsive surfaces
above, ONB-protected amines are able to liberate the amine under
UV-light irradiation resulting in the formation of the desired amine
Another possibility to obtain irreversible photoswitchable sur-
that is used for cross-linking the reactive films. The resulting
faces consists in using photocleavable units instead of photo-
reactive polymer thin film patterns can be further utilized
chromic units. Such photolabile protecting groups (PGs) frequently
[139,141]. Hence, PFPA-bearing polymers which were modified
contain o-nitrobenzyl (ONB) derivatives, which undergo photo-
with mono-ONB-protected diamine can be patterned with different
cleavage upon UV irradiation. Such ONB derivatives can be cleaved
amines after crosslinking upon UV-light exposure [157e161]. The
off from polymer chains as shown in Table 1 [63,147e150].
patterning behavior was studied on glass substrates with polymers
Huck and coworkers reported on various photoresponsive
containing different amounts of ONB-units by using photolithog-
monomers followed by the production of surfaces thereof, which
raphy. Subsequently, the post-modification step with fluorescence
showed a reversibly switchable wettability [151,152]. For this pur-
dye yielded useful templates for advanced functional patterns
pose, the monomer 4,5-dimethoxy-2-nitrobenzyl methacrylate
(Fig. 15).
(NVOCMA) was synthesized in a one-step reaction, where the
S.W. Thomas III and coworkers reported on a novel method for
methoxy groups increase the photosensitivity due to their electron-
the switching of chargeecharge interactions from attractive to
donating effect. Next, poly(NVOCMA) brushes extending the chro-
repulsive within polyelectrolyte multilayers [162]. The light-
mophore of the monomers were prepared by Si-ATRP and the film
responsive films were prepared with polycation, featuring
thickness could be influenced by the monomer concentration and
cationic moieties connected via a nitrobenzyl ester photocleavable
by the thickness of the monomer layer. The hydrophobic surface of
group. Upon UV irradiation the polycation will be converted into a
the obtained brushes (qadvancing ¼ 75 ) switched to a more hydro-
polyanion with carboxyl acid moieties. During the photolysis of the
philic state (qadvancing ¼ 67 ) after UV irradiation, due to the for-
side chains of photoreactive polymers, the formal charge of the
mation of poly(methacrylic acid) (PMAA).
polyelectrolyte changed to negative and the polyelectrolyte mul-
Another interesting example consists of conjugated polymers,
tilayers disrupted (Fig. 16). Moreover, they showed that the film
which can be used as chemical sensors due to their ability to absorb
thickness of polymer films could be tuned by UV-light exposure
or emit light. Moreover, conjugated polymers can be used as optical
through the change of position of chemical functionality perpen-
sensors because of their delocalized p-electron bonds along the
dicular to the substrate. Such polyelectrolyte multilayers can be
polymer chain, which constitutes the mobile charge carrier
used, for example, as antibacterial surfaces, in drug encapsulation
[153,154].
and in sensors [161e167].
Recently, Pauly et al. used substituted polyphenylacetylenes
(PPA) to create optical sensors by utilizing PPAs bearing penta-
fluorophenyl ester (PFP) reactive units [155]. The PFP units were 6. Photoswitchability and effects of surface topography
then partly modified with a mono-ortho-nitrobenzyl protected
diamine. Upon UV irradiation, the diamine was deprotected and In addition to the chemical properties of the surface the surface
consequently cross-linked the film via neighboring PFP groups. topography plays an important role in the creation of smart
 N. Wagner, P. Theato / Polymer 55 (2014) 3436e3453
Fig. 15. Photolithography of PPFPAeONB. (Reproduced from Ref. [157]).
surfaces. Recently, Schenning et al. utilized the photochromic
properties of spiropyran in photoresponsive hydrogels containing
NIPAAM for preparation of patterned films with changeable surface
relief patterns on methacrylate-functionalized substrates [168].
They prepared photoresponsive hydrogel coatings by using a
polymerization-induced diffusion method. The hydrogels shrink
after visible-light irradiation due to the isomerization of protonated
merocyanine-form to the spiropyran-form under slightly acidic
conditions [29,59,168e170]. First of all, the cross-linking density of
the hydrogel films was modulated by varying amounts of
crosslinking-agent tripropylene glycol diacrylate (TPGDA) by irra-
diation through a photomask with UV-light at 320e390 nm for
50 s. Then, the change of the film color from red to orange and
swelling of the polymer film in acidic water were observed (Fig. 17).
The roughness of the surface topography could be reversibly
switched resulting in reduction of height of the surface relief from
6 mm to 2 mm (Fig. 17).
As result of the photo-induced isomerization of the protonated
merocyanine-isomer to the spiropyran-isomer, the static contact
3449
angle of initial swollen films changed from 90 to 95 after UV-light
irradiation at 395e445 nm.
Yaminsky and coworker recently published another interesting
example. They studied peculiarities and mechanism of surface
topography changes in photochromic cholesteric oligomer-based
films. They combined the correlation of photo- and thermally-
induced helix pitch values and surface topography. The chiral-
photochromic compounds are able to change their helical
twisting power upon UV-light induced E-Z-isomerization [171,172].
First of all, the cholesteric mixtures were prepared from oligomeric
cholesteric cyclosiloxane (SilRed), which forms a left-handed
cholesteric structure over a wide mesophase temperature range
(Fig. 18). Subsequently, the UV-sensitive moieties, isomerizable
derivatives of menthone (Mtn) e and isosorbide (Sorb) e con-
taining C]C double bonds, were introduced in the cholesteric so-
lution in chloroform [173].
UV-light exposure of prepared cholesteric films containing
chiral-photochromic dopants led to changes of the surface relief
due to the change in the helix pitch values over a wide spectral
3450 N. Wagner, P. Theato / Polymer 55 (2014) 3436e3453

Fig. 16. Photolysis of cationic photoreactive polymer. Formation of negative polyelectrolyte follows by interlayer electrostatic interactions in PEM films with PSS. Here PDAC is a
photoinert polycation. Thickness of three types polymer films before and after 3 h of irradiation at l > 295 nm. (Reproduced from Ref. [161]).

range (~350e740 nm). Thereby, not only the height of cholesteric
films but also changes in the shape of domains could be affected by
cooling rate of SilRed films. Hence, slow cooling resulted in
smoother surface relief when comparing the domain shape with
that of films prepared by quenching process.
In 2013, D. J. Broer et al. introduced a new method to dynami-
cally modulate the surface topologies in liquid crystals (LC) net-
works upon exposure to light of relatively low intensity [113,174].
The anisotropic geometric changes of LC networks can occur due to
changes of the molecular order parameters. Therefore, they

Fig. 17. Surface topography of a film that was obtained by photopolymerization-induced diffusion (100 mm open, 200 mm dark-line mask) without swelling (A). Surface to-
pographies that were swollen in 2 mm HCl solution before and after exposure to light (B) and averaged cross-sections of the surface topographies (C), as observed by interferometry.
(Reproduced from Ref. [168]).
 N. Wagner, P. Theato / Polymer 55 (2014) 3436e3453
Fig. 18. The oligomeric cholesteric cyclohexane SilRed (A). The UV-sensitive moieties isomerizable derivatives of menthone (Mtn) e and isosorbide (Sorb) e containing C]C double
bonds (B). (Reproduced from Ref. [171]).
combined liquid-crystal networks, which are obtained by in situ
photo-polymerization of a polyfunctional liquid-crystal monomer
in its monolithically oriented state, with photochromic azobenzene
moieties. Hence, they introduced azobenzene-containing cross-
linkers into a structured chiral nematic network. Azobenzene is the
most well-known candidate used in light-responsive surfaces
because it can change between two isomeric forms, trans- and cis-
azobenzene, upon exposure to UV light, which makes it interesting
for many applications such as liquid transport in microfluidics or
light-tracking optical elements in solar energy applications [60].
Here, azobenzene containing chiral nematic networks were
used to induce a photo-mechanical response in thin films, which
were coated on glass surfaces. Additionally, perpendicular molec-
ular alignments were installed allowing the increase in the depth
surface modulation. It was found, that the UV-light exposure of
365 nm leads to a large deformation of the patterned chiral
nematic-homeotropic film containing 4 wt% azobenzene.
Further, it could be shown, that increasing in the concentration
of azobenzene led to the enhancement of the photo-responsive
effect. This could be explained with the cooperative disordering
of the aligned molecules while photo-isomerization from the trans-
to the cis- form. Unfortunately, they also did not report any contact
angles.
7. Conclusion
In this review article, we have summarized many recent
achievements in the field of reversibly switchable polymer films
with a focus on changes in wettability. A range of various external
stimuli can reversibly switch the wettability of reactive polymer
film surfaces. Particularly interesting are light/photo-responsive
polymer coatings, which can be used for versatile applications,
such as in the biomedical industry or in light emitting diodes, etc.
We have underlined many exciting approaches for the generation
of the desired surface properties, which can be tuned by employing
different monomers during the polymer synthesis. Also, various
stimuli-responsive moieties, for example, spiropyran amine, azo-
benzene, 7-[(trifluoro methylphenylazo)phenoxy]pentanoic acid,
cinnamate groups, trifluoromethanesulfonic acid trimethylsilyl
ester, polyarylsulfone, diarylethene, diethylcyclopentene, coumarin
groups and ONB, were introduced onto surfaces either by direct
incorporation during the polymer synthesis or by a post-
polymerization modification. In the latter case, reactive surfaces
3451
with tunable wettability have been obtained on different substrates,
such as PMSSQ, SiO2, cellulose, SiO2eTDI nanoparticles, self-
assembled monolayers of SubPc complexes, polymers with honey-
comb reliefs, ferromagnetic steel spheres and PDMS.
In general, a polymer surface bearing chromophore moieties is
exposed to UVeVis-light irradiation. This leads to different chem-
ical processes on the surface, for example, to alterations of the
dipole moment due to the isomerization into another stable
conformation or formation of dimers by [2p þ 2p] cycloaddition
and other methods. These events on the polymer surface result in
most cases in an increase or decrease of the hydrophobicity or
hydrophilicity. Furthermore, we have summarized many de-
velopments in the field of light-responsive polymer coatings, which
have already been reported elsewhere. Future research should
intensify the study of the synthesis and application of new stimuli-
responsive materials. Moreover, it should be focused on the pro-
duction of surfaces with combined interfacial properties that could
be used as on-off systems.
Noteworthy, in many cases the reported wettability is only
characterized by contact angle measurements using water. In some
cases static contact angles are reported, while other studies report
advancing and receding contact angles. In order to provide a suit-
able comparison, both advancing and receding contact angles
should be reported. If possible calculation of the respective surface
energies would be even more desirable.
References
[1] Aono M, Bando Y, Ariaga K. Adv Mater 2012;24(2):150e1.
[2] Arumugam S, Orski SV, Locklin J, Popik VV. J Am Chem Soc 2012;134(1):
179e82.
[3] Advincula RC, Brittain WJ, Caster KC, Rühe KC. WILEY-VCH Verlag GmbH &
Co KGaA; 2004.
[4] Barbey R, Lavanant L, Paripovic D, Schuewer N, Sugnaux C, Tugulu S, et al.
Chem Rev 2009;109:5437e527.
[5] Jeon NL, Choi IS, Whitesides JM, Kim NY, Laibinis PE, et al. Appl Phys Lett
1999;75(26):4201.
[6] Husseman M, Malmstro €m EE, McNamara M, Mate M, Mecerreyes D,
Benoit DG, et al. Macromolecules 1999;32(5):1424e31.
[7] Matyjaszewski K, Miller PJ, Shukla N, Immaraporn B, Gelman A, Luokala BB,
et al. Macromolecules 1999;32(26):8716e24.
[8] Vasita R, Katti DS. Int J Nanomed 2006;(1):15e30.
[9] Hi Wu, Pan W, Lin D, Li H. J Adv Ceram 2012;1(1):2e23.
[10] Greiner A, Wendorff JH. Angew Chem Int Ed 2007;46(30):5670e703.
[11] Padron S, Dumitru F, Caruntu D, Lozano K. J Appl Phys 2013;113:024318-
1e024318-9.
[12] Sarkar K, Gomez C, Zambrano S, Ramirez M, de Hoyos E, Vasquez H, et al.
Mater Today 2010;13:12e4.
3452 N. Wagner, P. Theato / Polymer 55 (2014) 3436e3453
[13] Ionov L, Sidorenko A, Eichhorn KJ, Stamm M, Minko S, Hinrichs K. Langmuir
2005;21:8711e6.
[14] Feng N, Zhao H, Zhan J, Tian D, Li H. Org Lett 2012;14(8):1958e61.
[15] Zhang G, Zhu X, Miao F, Tian D, Li H. Org Biomol Chem 2012;10(16):3185.
[16] Yang J, Zhang Z, Men X, Xu X, Zhu X, Zhou X. Langmuir 2011;27(12):
7357e60.
[17] Zhang L, Zhang Z, Wang P. NPG Asia Mater 2012;4(2):1e8.
[18] Zhu X, Zhang Z, Wang K, Yang J, Xu X, Men X, et al. New J Chem 2012;36(5):
1280.
[19] Lutz J, Liu S, Sumerlin B, Ray JG, Naik SS, Hoff EA, et al. Macromol Rapid
Commun 2012;33(9):819e26.
[20] Pei Y, Travas-Sejdic J, Williams DE. Langmuir 2012;28(21):8072e83.
[21] Spruijt E, Choi E, Huck WTS. Langmuir 2008;24(19):11253e60.
[22] Xu L, Chen Z, Chen W, Mulchandani A, Yan Y. Macromol Rapid Commun
2008;29(10):832e8.
[23] Sim~ ao C, Mas-Torrent M, Veciana J, Rovira C. Nano Lett 2011;11(10):4382e5.
[24] Sinha AK, Basu M, Pradhan M, Sarkar S, Negishi Y, Pal T. Langmuir
2011;27(18):11629e35.
[25] Tian D, Zhang X, Zhai J, Jiang L. Langmuir 2011;27(7):4265e70.
[26] Tian D, Zhang X, Tian Y, Wu Y, Wang X, Zhai J, et al. J Mater Chem
2012;22(37):19652.
[27] Wang D, Wang X, Liu X, Zhou F. J Phys Chem C 2010;114(21):9938e44.
[28] Wang J, Mao B, Gole JL, Burda C. Nanoscale 2010;2(10):2257.
[29] Kettunen M, Silvennoinen RJ, Houbenov N, Ruokolainen J, Sainio J, Pore N,
et al. Adv Funct Mater 2011;21(3):510e7.
[30] Liu S, Han G, Shu M, Han L, Che S. J Mater Chem 2010;20(44):10001.
[31] Drelich J, Chibowski E, Meng DD, Terpilowski K. Soft Matter 2011;7(21):
9804.
[32] Schild HG. Prog Polym Sci 1992;17:163e249.
[33] Zhao X, Liu Y, Lu J, Zhou J, Li J. Chem Eur J 2012;18(12):3687e94.
[34] Kuroki H, Tokarev I, Minko S. Annu Rev Mater Res 2012;42:343e72.
[35] Azzaroni O. J Polym Sci A Polym Chem 2012;50(16):3225e58.
[36] Xin B, Hao J. Chem Soc Rev 2010;39(2):769.
[37] Svetushkina E, Puretskiy N, Ionov L, Stamm M, Synytska A. Soft Matter
2011;7(12):5691e6.
[38] Estillore NC, Park JY, Advincula RC. Macromolecules 2010;43(16):6588e98.
[39] Turan E, Demirci S, Caykara T. Thin Solid Films 2010;518(21):5950e4.
[40] Gras SL, Mahmud T, Rosengarten G, Mitchell A, Kalantar-zadeh K. Chem Phys
Chem 2007;8(14):2036e50.
[41] Muthiah P, Hoppe SM, Boyle TJ, Sigmund W. Macromol Rapid Commun
2011;32(21):1716e21.
[42] Sun T, Qing G. Adv Mater 2011;23(12):H57e77.
[43] Moon HJ, Ko DY, Park MH, Joo MK, Jeong B. Chem Soc Rev 2012;41(14):4860.
[44] Mo € ller S, Pliquett U, Hoffmann C. RSC Adv 2012;2(11):4792.
[45] Fries K, Samanta S, Orski S, Locklin J. Chem Commun 2008;47:6288.
[46] Rosario R, Gust D, Hayes M, Jahnke F, Springer J, Garcia AA. Langmuir
2002;18(21):8062e9.
[47] Kessler D, Choi J, Schattling P, Jochum FD, Pyun J, Char K, et al. ACS Appl
Mater Interfaces 2011;3(2):124e8.
[48] Das J, Frechet JMJ, Chakraborty AK. J Phys Chem B 2009;42(113):13768e75.
[49] Chen T, Amin I, Jordan R. Chem Soc Rev 2012;41(8):3280e96.
[50] Choi J, Schattling P, Jochum FD, Pyun J, Char K, Theato P, et al. Chem Soc Rev
2013;42:7468e83.
[51] Ichimura K. Science 2000;288(5471):1624e6.
[52] Pinto LFV, Kundu S, Brogueira P, Cruz C, Fernandes SN, Aluculesei A, et al.
Langmuir 2011;27(10):6330e7.
[53] Jin C, Yan R, Huang J. J Mater Chem 2011;21(43):17519.
[54] Wang P. Asian J Org Chem 2013;6(2):452e64.
[55] Schumers J, Fustin C, Gohy J. Macromol Rapid Commun 2010;31(18):
1588e607.
[56] Zhao H, Sterner ES, Coughlin EB, Theato P. Macromolecules 2012;45(4):
1723e36.
[57] Cameron JF, Frechet JMJ. J Am Chem Soc 1991;113(11):4303e13.
[58] Madou M. Fundamentals of microfabrication. Boca Raton, Florida: CRC Press;
2002.
[59] Chung DJ, Ito Y, Imanishi Y. J Appl Polym Sci 1994;51:2027e33.
[60] Siewierski LM, Brittain WJ, Petrash S, Foster MD. Langmuir 1996;12:
5838e44.
[61] Ichimura K, Akita Y, Akiyama H, Kudo K, Hayashi Y. Macromolecules
1997;30:903e11.
[62] Brown AA, Azzaroni O, Huck WS. Langmuir 2009;25(3):1744e9.
[63] Blanc A, Bochet CG. J Org Chem 2002;67(16):5567e77.
[64] Friedle S, Thomas III SW. Angew Chem Int Ed 2010;49:7968e71.
[65] Palumbo F, Di Mundo R, Cappelluti D, d'Agostino R. Plasma Process Polym
2011;8:118e26.
[66] Sung D, Yang S, Park JW, Jon S. Biomed Microdevices 2013;15(4):691e8.
[67] Roy S, Das T, Yue CY. ACS Appl Mater Interfaces 2013;5(12):5683e9.
[68] Kessler D, Theato P. Macromolecules 2008;41(14):5237e44.
[69] Kessler D, Theato P. Macromol Symp 2007;249e250(1):424e30.
[70] Wiss KT, Kessler D, Wendorff TJ, Theato P. Macromol Chem Phys
2009;15(210):1201e9.
[71] Kessler D, Teutsch C, Theato P. Macromol Chem Phys 2008;209(14):
1437e46.
[72] Kessler D, Jochum FD, Choi J, Char K, Theato P. ACS Appl Mater Interfaces
2011;3(2):124e8.
[73] Wang D, Jiao P, Wang J, Zhang Q, Feng L, Yang Z. J Appl Polym Sci
2012;125(2):870e5.
[74] Samanta S, Locklin J. Langmuir 2008;24(17):9558e65.
[75] Jeon NL, Choi IS, Whitesides JM, Kim NY, Laibinis PE, et al. Langmuir
2003;19(12):5104e14.
[76] Kong B, Lee JK, Choi IS. Langmuir 2007;23(12):6761e5.
[77] Juang A, Scherman OA, Grubbs RH, Lewis NS. Langmuir 2001;17(5):1321e3.
[78] Berron BJ, Graybill EP, Jennings GK. Langmuir 2007;23(23):11651e5.
[79] Hirshberg Y. J Am Chem Soc 1956;78:2304e12.
[80] Fries KH, Sheppard GR, Bilbrey JA, Locklin J. Polym Chem 2013:2014.
[81] Winkler JD, Deshayes K, Shao B. J Am Chem Soc 1989;111:769e70.
[82] Suzuki T, Kawata Y, Kahata S, Kato T. Chem Commun 2003:2004e5.
[83] Chibisov AK, Go €rner H. Chem Phys 1998;237:425e42.
[84] Fries KH, Driskell JD, Samanta S, Locklin J. Anal Chem 2010;82:3306e14.
[85] Wojtyk JTC, Kazmaier PM, Buncel E. Chem Mater 2001;13:2547e51.
[86] Choi J, Schattling P, Jochum FD, Pyun J, Char K, Theato P. J Polym Sci A Polym
Chem 2012;50(19):4010e8.
[87] Ko€ nig T, Goldenberg LM, Kulikovska O, Kulikovsky L, Stumpe J, Santer S. Soft
Matter 2011;7(9):4174.
[88] Lomadze N, Kopyshev A, Rühe J, Santer S. Macromolecules 2011;44(18):
7372e7.
[89] Pei X, Fernandes A, Mathy B, Laloyaux X, Nysten B, Riant O, et al. Langmuir
2011;27(15):9403e12.
[90] Zakrevskyy Y, Richter M, Zakrevska S, Lomadze N, von Klitzing R, Santer S.
Adv Funct Mater 2012;22(23):5000e9.
[91] Schuh C, Lomadze N, Rühe J, Kopyshev A, Santer S. J Phys Chem B
2011;35(115):10431e8.
[92] Raghuraman GK, Dhamodharan R, Prucker O, Rühe J. Macromolecules
2008;19(41):873e8.
[93] Wang N, Zhao Y, Jiang L. Macromol Rapid Commun 2008;29(6):485e9.
[94] Jiang W, Wang G, He Y, Wang X, An Y, Song Y, et al. Chem Commun 2005;28:
3550.
[95] Bhardwaj N, Kundu SC. Biotech Adv 2010;28(3):325e47.
[96] Langer R, Vacanti JP. Science 1993;260:920e6.
[97] Koh CJ, Atala A. J Am Soc Nephrol 2004;15:1113e25.
[98] Wang ZG, Wan LS, Liu ZM, Huang XJ, Xu ZK. J Mol Catal B Enzyme 2009;56:
189e95.
[99] Wischerhoff E, Bade N, Laschewsky A, Lutz JF. Adv Polym Sci 2011;240:1e33.
[100] Cohen Stuart MA, et al. Nat Mater 2010;9:101e13.
[101] Chen M, Besenbacher F. ACS Nano 2011;5(2):1549e55.
[102] Jennissen HP, Mat-wiss U. Werkstofftech 2012;43(8):743e50.
[103] Dormtin G, Prestwich GD. Biochemistry 1994;33(19):5661e73.
[104] Que re
 D. Annu Rev Mater Res 2008;38:71e99.
[105] Jeong HE, Kwak MK, Park CI, Suh KY. J Colloid Interface Sci 2009;339(1):
202e7.
[106] Monobe H, Ohzono T, Akiyama H, Sumaru K, Shimizu Y. ACS Appl Mater
Interfaces 2012;4(4):2212e7.
[107] Tian Y, Watanabe K, Kong X, Abe J, Iyoda T. Macromolecules 2002;35(9):
3739e47.
[108] Lim HS, Han JT, Kwak D, Jin M, Cho K. J Am Chem Soc 2006;128(45):
14458e9.
[109] Prescher D, Thiele T, Ruhmann R, Schulz G. J Fluor Chem 1995;74:185e9.
[110] Jiang W, Wang G, He Y, Wang X, An Y, Jiang W, et al. Chem Commun
2005;28:3550.
[111] Broer DJ, Gossinks RG, Hikmet RAM. Angew Makromol Chem 1990;183:
45e66.
[112] Elias AL, Harris KD, Bastiaansen CWM, Broer DJ, Brett MJ. J Mater Chem
2006;16(28):2903.
[113] Liu D, Liu D, Bastiaansen CWM, den Toonder JMJ, , et alden Toonder JMJ,
Broer DJ. Angew Chem Int Ed 2012;51(4):892e6.
[114] Heynderickx I, Broer DJ. Mol Cryst Liq Cryst 1995;263:415e27.
[115] Broer DJ, Heynderickx I. Macromolecules 1990;23:2474e7.
[116] Lub J, Broer DJ, Hikmet RAM, Nierop KGJ. Liq Cryst 1995;18(2):319e26.
[117] Terentjev EM, Hotta A, Clarke SM, Warner M. Philos Trans R Soc Lond A
2003;361(1805):653e64.
[118] Statman D, J anossy I. J Chem Phys 2003;118(7):3222.
[119] Raghuraman GK, Dhamodharan R, Prucker O, Rühe J, Pe ralta S, Cantin S, et al.
Colloid Polym Sci 2012;290(5):423e34.
[120] Liu J, Chung YC, Lin MT. Angew Makromol Chem 1994;219:43e54.
[121] Hocking MB. Can J Chem Eng 1969;171(47):4567e76.
[122] Ko€rstgens V, Hsu C, Paneque D, Wiedersich J, Müller-Buschbaum P. Appl
Phys Lett 2008;93(4):41916.
[123] Pitois O, Francois B. EPJ B 1999;8:225e31.
[124] Bormashenko E, Pogreb R, Whyman G, Bormashenko Y, Jager R, Stein T, et al.
Langmuir 2008;24(12):5977e80.
[125] Domb AJ, Bormashenko E, Balter S, Pogreb R, Aurbach D. Polym Adv Technol
2011;22(1):94e8.
[126] Marmur A. Soft Matter 2006;2(1):12e7.
[127] Rosario R, Gust D, Garcia AA, Hayes M, Taraci JL, Clement T, et al. J Phys Chem
B 2004;108(34):12640e2.
[128] Irie M. Chem Rev 2000;100(5):1683e4.
 N. Wagner, P. Theato / Polymer 55 (2014) 3436e3453
[129] Saint-Jalm S, Miniewicz A, Karpinski P, Jarek-Mikulska U, Gao X. J Mol Liq
2012;168:21e7.
[130] Izumi N, Minami T, Mayama H, Takata A, Nakamura S, Yokojima S, et al. Jpn J
Appl Phys 2008;47:7298e302.
[131] Uchida K, Izumi N, Sukata S, Kojima Y, Nakamura S, Krayushkin MM, et al.
Angew Chem Int Ed 2006;45(39):6470e3.
[132] Uyama A, Yamazoe S, Shigematsu S, Morimoto M, Yokojima S, Mayama H,
et al. Langmuir 2011;27(10):6395e400.
[133] Weidner T, Baio JE, Seibel J, Siemeling U. Dalt Trans 2012;41(5):1553e61.
[134] Krayushkin MM, Barachevsky A, Irie M. Heteroat Chem 2007;18:557e67.
[135] Gonza lez-Rodríguez D, Martínez-Díaz MV, Abel J, Perl A, Huskens J,
Echegoyen L, et al. Org Lett 2010;12(13):2970e3.
[136] Fu Q, Rao GVR, Basame SB, Keller DJ, Artyushkova K, Fulghum JE, et al. J Am
Chem Soc 2004;126:8904e5.
[137] Motornov M, Sheparovych R, Lupitskyy R, MacWilliams E, Minko S. Adv
Mater 2008;20:200e5.
[138] Minko S, Müller M, Motornov M, Nitschke M. J Am Chem Soc 2003;125:
3896e900.
[139] Malm J, Sahramo E, Karppinen M, Ras RHA. Chem Mater 2010;22:3349e52.
[140] Kekkonen V, Hakola A, Kajava T, Sahramo E, Malm J, Karppinen M, et al. Appl
Phys Lett 2010;97(4):044102-1e044102-3.
[141] Babin J, Pelletier M, Lepage M, Allard JF, Morris D, Zhao Y. Angew Chem Int
Ed 2009;48:3329e32.
[142] Kehrlo € sser D, Ta
€rger J, Kim HC, Hammp N. Langmuir 2010;26(6):3878e82.
[143] Jiang J, Qi B, Lepage M, Zhao Y. Macromolecules 2007;40(4):790e2.
[144] Li L, Pan S, Pang X, Chen H, Hu D, Ke L, et al. Soft Matter 2012;8(28):7357.
[145] Parry V, Berthome  G, Joud J. Appl Surf Sci 2012;258(15):5619e27.
[146] Ito H, Ueda M. J Am Chem Soc 1988;21:1475e82.
[147] Kessler M, Glatthar R, Giese B, Bochet C. Org Lett 2003;5(8):1179e81.
[148] Alvarez K, Vasseur J, Beltran T, Imbach J. J Org Chem 1999;64(17):6319e28.
[149] Patchornik A, Amit B, Woodward RB. J Am Chem Soc 1970;92(21):6333e5.
[150] Ilichev YV, Schwo € rer MA, Wirz J. J Am Coll Surg 2004;126(14):4581e95.
[151] Brown AA, Azzaroni O, Fidalgo LM, Huck WTS. Soft Matter 2009;5(14):2738.
[152] Gaplovsky M, Ilichev YV, Kamdzhilov Y, Kombarova SV, Mac M,
Schworer MA, et al. Photochem Photobiol Sci 2005;4(1):33e42.
[153] McQuade DT, Pullen AE, Swager TM. Chem Rev 2000;100(7):2537e74.
[154] Bouffard J, Watanabe M, Takaba H, Itami K. Macromolecules 2010;43:
1425e9.
[155] Pauly AC, Theato P. Polym Chem 2012;3(7):1769.
[156] Lai Y, Huang J, Gong J, Huang Y, Wang C, Chen Z, et al. J Electrochem Soc
2009;156(11):D480.
[157] Zhao H, Theato P. Polym Chem 2013;4(4):891.
[158] Doh J, Irvine DJ. J Am Coll Surg 2004;126(30):9170e1.
[159] Taylor PG, Lee J, Zakhidov AA, Chatzichristidi M, Fong HH, DeFranco JA, et al.
Adv Mater 2009;21(22):2314e7.
[160] Georgianna WE, Lusic H, McIver AL, Deiters A. Bioconjug Chem 2010;21(8):
1404e7.
[161] Koylu D, Thapa M, Gumbley P, Thomas SW. Adv Mater 2012;24(11):1451e4.
[162] Liu D, Bastiaansen CWM, den Toonderb JMJ, Broer DJ. Soft Matter 2013;9:
588e96.
3453
[163] Nolte AJ, Rubner MF, Cohen RE. Langmuir 2004;20(8):3304e10.
[164] Ariga K, Hill JP, Ji Q. Phys Chem Chem Phys 2007;9(19):2319e40.
[165] Lichter JA, van Vliet KJ, Rubner MF. Macromolecules 2009;42(22):8573e86.
[166] Geest BG, Koker S, Sukhorukov GB, Kreft O, Parak WJ, Skirtach AG, et al. Soft
Matter 2009;5(2):282e91.
[167] Kim B, Park SW, Hammond PT. ACS Nano 2008;2(2):386e92.
[168] Stumpel JE, Liu D, Broer DJ, Schenning APHJ. Chem Eur J 2013;19:10922e7.
[169] Leewis CM, de Jong AM, van IJzendoorn LJ, Broer DJ. J Appl Polym Sci
2004;95(12).
[170] Satoh T, Sumaru K, Takagi T, Kanamori T. Soft Matter 2011;7:8030e4.
[171] Sinitsyna O, Bobrovsky A, Yaminsky I, Shibaev V. Colloid Polym Sci 2014.
[172] van de Witte P, Brehmer M, Lub J. J Mater Chem 1999;9:2087e94.
[173] Shibaev V, Bobrovsky A, Boiko N. Prog Polym Sci 2003;28:729e836.
[174] Liu D, Broer DJ. Liq Cryst Rev 2013;1(1):20e8.
Patrick Theato studied chemistry at the University of
Mainz and the University of Massachusetts, Amherst, and
obtained his doctoral degree from the University of Mainz
in 2001. After postdoctoral studies at Seoul National Uni-
versity supported by Feodor Lynen Postdoctoral Research
Fellowship and at Stanford University, he completed his
Habilitation at the University of Mainz in 2007. From 2009
to 2013 he held a joint appointment at Seoul National
University within the WCU program. In 2011, he accepted
a prize senior lectureship at the University of Sheffield.
Shortly after he moved to University of Hamburg as an
associate professor for polymer chemistry. His research
interests include post-polymerization modifications, func-
tional polymers, fibers and nanoobjects, smart polymers
and surfaces, and polymers for energy generation, conver-
sion and storage.
Natalie Wagner studied Chemistry at the University of
Hamburg (Germany) and received her Diploma in 2010 in
the research group of Prof. Hans-Ulrich Moritz for her
work “Investigations of the dynamic swelling method
for preparing monodisperse polymer particles”. After-
wards, she continued her scientific career as a candidate
in the group of Prof. Patrick Theato, with her research
focusing on inorganic-organic hybrid polymers. She is
particularly interested in post-polymerization modifica-
tion of reactive surfaces yielding stimuli-responsive
surfaces. In the summer of 2012, she was awarded a schol-
arship by NRF Korea and DAAD, which allowed her to
conduct a research project in the group of Prof. Kookheon
Char at Seoul National University, Korea.