www.advancedsciencenews.com www.advmat.

de

Photochemically Driven Polymeric Network Formation:

Review
Synthesis and Applications
Eva Blasco,* Martin Wegener, and Christopher Barner-Kowollik*

connected to every other constituting unit

Polymeric networks have been intensely investigated and a large number of and to the macroscopic phase boundary
applications have been found in areas ranging from biomedicine to materials by permanent bonding sites throughout
science. Network fabrication via light-induced reactions is a particularly pow- the macromolecule.[1] Network formation
can arise from covalent bond formation,
erful tool, since light provides ready access to temporal and spatial control,
ionic interactions, or physical interactions,
opening an array of synthetic access routes for structuring the network geom- such as Van der Waals forces or hydrogen
etry as well as functionality. Herein, the most recent light-induced modular bonds. Covalently crosslinked networks
reactions and their use in the formation of precision polymeric networks are are the most common systems and
collated. The synthetic strategies including photoinduced thiol-based reac- typically yield materials with enhanced
properties such as improved strength, flex­
tions, Diels–Alder systems, and photogenerated reactive dipoles, as well as
ibility, and durability. Covalent crosslinks
photodimerizations, are discussed in detail. Importantly, applications of the can be formed by a large number of chem­
fabricated networks via the aforementioned reactions are highlighted with ical reactions, which are initiated by heat,
selected examples. Concomitantly, we provide future directions for the field, pressure, change in pH or light. Photo­
emphasizing the most critically required advances. induced crosslinking is especially attrac­
tive, since light irradiation provides ready
access to temporal and spatial control. In
addition, the wavelength—and therefore
1. Introduction the energy—at which the photoinduced reaction takes place
can also be finely selected. As we will discuss later, highly spe­
As defined by the International Union of Pure and Applied cific energy selection is an important parameter in some appli­
Chemistry (IUPAC), a polymeric network is a highly dense cations, for example in biomedicine, where (harsh) UV light,
macromolecule, in which essentially each constituting unit is specially short wavelengths, can be harmful. Substantial efforts
are being made in order to red-shift (lower energy) the photore­
actions and employ visible or even IR light to induce chemical
Dr. E. Blasco, Prof. C. Barner-Kowollik change.[2]
Institut für Technische Chemie und Polymerchemie Among the various strategies employing light-induced pro­
Karlsruhe Institute of Technology (KIT) cesses, photoinitiated free-radical or cationic polymerization
Engesserstr. 18, 76128 Karlsruhe, Germany
E-mail: eva.blasco@kit.edu; have been thoroughly investigated and found a large number
christopher.barner-kowollik@kit.edu, of applications in various industrial sectors.[3] Monomers based
christopher.barnerkowollik@qut.edu.au on meth(acrylate),[3b] vinyl[3b] ether or epoxy groups[3b] have
Dr. E. Blasco, Prof. C. Barner-Kowollik been frequently employed. In particular, acrylates are known to
Institut für Biologische Grenzflächen be among the most reactive monomers when polymerized via
Karlsruhe Institute of Technology (KIT) a free radical mechanism and are arguably the most employed
Hermann-von-Helmholtz-Platz
1, 76344 Eggenstein-Leopoldshafen, Germany systems. The main advantages of photoinduced radical poly­
Prof. M. Wegener merization of acrylates include rapid reaction rates and spatial
Institute of Applied Physics resolution, ambient temperature operation and solvent-free
Karlsruhe Institute of Technology (KIT) formulations. Nevertheless, one of the main disadvantages is
Wolfgang-Gaede-Straße 1, 76128 Karlsruhe, Germany oxygen inhibition, which is known to lead to tacky surfaces and
Prof. M. Wegener networks with poor structural control.[3b] Commonly, in free-
Institute of Nanotechnology
radical-based systems gelation already occurs at low monomer
Karlsruhe Institute of Technology (KIT)
Hermann-von-Helmholtz-Platz 1, 76344 conversions, limiting the level of structural control that can be
Eggenstein-Leopoldshafen, Germany imparted onto the network.
Prof. C. Barner-Kowollik In recent years, advanced light-induced ligation techniques
School of Chemistry have emerged as a powerful tool not only for small molecule
Physics and Mechanical Engineering generation, yet also for polymer synthesis, opening new possi­
Queensland University of Technology (QUT)
2 George Street, Brisbane, QLD, 4000, Australia bilities for the synthesis of polymeric networks. By using macro­
monomers that are multi-functionalized with photoreactive
DOI: 10.1002/adma.201604005 groups as starting materials, a high level of control over network

Adv. Mater. 2017, 29, 1604005 © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim wileyonlinelibrary.com (1 of 29)  1604005
 www.advmat.de www.advancedsciencenews.com

formation and crosslinking density can be achieved, although

Review

perfect network structures remain elusive. Thiol-based reac­ Eva Blasco completed her
tions, especially radical-mediated, photoinduced Diels–Alder Ph.D. studies in 2013 at
and photodimerization reactions among others are examples of the University of Zaragoza
ready to operate light-induced protocols employed for the prep­ under the supervision of
aration of spatially resolved networks (Figure 1). Dr. M. Piñol and Dr. L. Oriol.
A number of reviews have focused on photoinitiated She obtained an Alexander
crosslinking radical and cationic polymerization and their von Humboldt Postdoctoral
applications.[3] More recently, special attention has been paid to Research Fellowship to
thiol-based chemistries, especially the study of the mechanism work in the groups of
and kinetics of the thiol-ene and thiol-yne reactions.[4] Herein, Prof. C. Barner-Kowollik
however, we focus on the most recent light-induced modular and Prof. M. Wegener at
reactions and their use in the formation of precision poly­ the Karlsruhe Institute of
meric networks alongside selected applications. We note that Technology (KIT) on the preparation of 3D conductive micro-
the examples discussed in the following sections only entail structures. Her research interests include the study of new
the photoinduced formation of networks. Photoresponsive net­ functional materials by employing light-induced reactions.
works as well as photodegradable networks are not considered.
First, the most recently employed synthetic strategies including
thiol-based reactions, Diels–Alder systems, 1,3-dipoles and Martin Wegener obtained
photodimerizations are discussed from a chemical point of his Ph.D. in 1987 at
view. Second, applications of the fabricated networks via the Frankfurt University.
aforementioned reactions are highlighted and critically evalu­ Thereafter, he spent two
ated. Finally, we conclude with a discussion of the outstanding years as a postdoc at AT&T
challenges that in our view are required to drive photoinduced Bell Laboratories (USA).
network formation to the next level from a chemical perspective From 1990 to 1995, he was
and, importantly, we address network design approaches that professor at Dortmund
are currently “science fiction” yet have a chance of becoming University, after which he
“science fact”. was appointed professor
at the Institute of Applied
Physics of Karlsruhe
2. Synthetic Methodologies for the Institute of Technology (KIT) in 1995. Since 2001 he has
Formation of Networks held a joint appointment at Institute of Nanotechnology
of KIT. His research interests comprise optics, optical
2.1. Thiol-Based Chemistry laser lithography, photonic crystals, metamaterials, and
transformation physics.
2.1.1. Thiol-ene

One of the most widely investigated process for the photochem­

ical formation of polymeric networks is the reaction between Christopher Barner-Kowollik
a thiol group and an alkene, known as the “thiol-ene” reaction received his Ph.D. in 1999
(Figure 1b).[4] Thiol-ene reactions can proceed via a radical- (Göttingen University).
mediated step growth mechanism. The mechanism involves After postdoctoral research
the addition of a thiyl radical to a vinyl function, which subse­ with Prof. Tom Davis and
quently abstracts a hydrogen from the thiol group, generating academic positions at the
a thioether moiety and regenerating the thiyl radical.[5] These University of New South
reactions entail the advantages of classical photopolymeriza­ Wales in Sydney, he was
tion systems, such as rapid reaction times as well as solvent- appointed Full Professor in
free polymerization, while featuring specific advantages 2006 at the same institution.
such as high conversion, low oxygen inhibition, and lower He is currently Full Professor
shrinkage compared to the acrylate-based photopolymeriza­ of Soft Matter Materials
tions. Some disadvantages associated with thiol-ene processes Science at the Queensland University of Technology
are unpleasant odors, limited shelf stability due to undesired (QUT) in Brisbane and heads a research group at the
thermal activation and softness (refer to the Thiol-yne section). Karlsruhe Institute of Technology (KIT). His research inter-
Thiol-ene polymer networks are readily formed by UV-light ests include macromolecular precision design in solution
irradiation of multifunctional thiols and enes. Derivatives of and on surfaces via rapid light-induced methodologies,
pentaeritrol functionalized with 3-mercaptopropionate are as well as the design of hybrid and adaptive polymer mate-
frequently used as multifunctional thiols in the preparation rials at the interface of polymer chemistry and materials
of networks (Figure 2). One of the main advantages is their science.
commercial availability. Importantly, a diverse number of

1604005  (2 of 29) wileyonlinelibrary.com © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Adv. Mater. 2017, 29, 1604005
www.advancedsciencenews.com www.advmat.de

Review

Figure 1.  a) Schematic representation of the network formation via photoinduced crosslinking. Note that polymeric networks always contain defects,
remaining photoreactive groups and are to date irregular in their molecular structure. However, residual functionality can be used for subsequent
postmodification reactions; b-d) Variable photoinduced reactions discussed in the current review.

Adv. Mater. 2017, 29, 1604005 © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim wileyonlinelibrary.com (3 of 29)  1604005
 www.advmat.de
Review
Figure 2.  Chemical structures of different multifunctional thiols employed in photoinduced thiol-ene/yne reactions.
different types of ene functional groups have been found to
undergo thiol-ene reaction. Typical ene functional groups are
alkene, vinyl ether, norbornene and (meth)acrylates, among
others. The relative reactivities are as follows: norbornene >
vinylether > allylether ≈ allyltriazine > acrylate > N-substituted
maleimide > acrylonitrile ≈ methacrylate > styrene. Figure 3
depicts some of the multifunctional enes employed in photo­
chemical networks fabrication.
Thiol-ene reactions can be initiated by light, peroxides,
thermal initiators or any system generating radicals. Similarly
to free-radical polymerization, the photoinitiation can be based
on excitation of an arylketone followed by hydrogen transfer,
excitation of an aryl aliphatic ketone followed by α-bond
cleavage and the direct excitation of a thiol group and cleavage
of the sulfur–hydrogen bond. One of the most frequently
employed initiation system is the excitation cleavage of photo­
initiators such as dimethoxyphenyl acetophenone (DMPA). In
the current section, we will focus on the use of light-initiated
thiol-ene reactions for the preparation of specific network struc­
tures. A compilation of various studies employing exclusively
thiol-ene reactions as well as a combination of thiol-ene reac­
tion with other competing reactions is discussed below.
Bowman and co-workers have intensively investigated the
mechanism of photoinduced thiol-ene reactions and success­
fully employed them for the preparation of networks featuring
different property profiles.[5] Patterned structures were fabricated
from a tetrafunctional thiol, pentaerythritol tetrakis(3-mercapto­
propionate) (4) and a tetra-ene, triallyl-1,3,5-triazine-2,4,6-
1H,3H,5H-trione (8).[6] The photo-crosslinking was performed
via UV irradiation with 3 light emitting diodes (LEDs) (NS375L-
5RLO, Roithner LaserTechnik, 365 nm) employing DMPA
as initiator. Films patterned with sub-micrometer scale were
prepared by nanoimprint lithography (refer to Applications
section). In addition, enabled by the step-growth nature of
thiol-ene polymerization, these authors demonstrated that it
is possible to finely tune the polymer properties by varying the
1604005  (4 of 29) wileyonlinelibrary.com © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
stoichiometry between the reacting monomers.[7] For instance,
a small excess of thiol groups ensured that unreacted thiol
entities remained—especially on the surface of the structures.
These thiol groups were subsequently addressed for changing
the surface chemistry, while maintaining the topology. In
further studies, the same group reported the attachment of
secondary films to the prefabricated structures via a postfunc­
tionalization reaction employing the unreacted thiols. Our team
has also employed photoinduced thiol-ene reactions for the fab­
rication of 3D reactive microstructures via a two-photon (2P)
process and performed subsequent surface modifications.[8]
The thiol-ene based system used for the study consisted of a 1:1
molar ratio of the well-known pentaerythritol tetrakis(3-mercap­
topropionate) (4) and tetra-ene pentaerythritol tetraallyl ether
(9) as monomers, 7–diethylamino-3-thenoylcoumarin (DETC)
as a 2P photoinitiator and dimethylacetamide as a solvent. The
thiol-ene microstructures were prepared by irradiating the pho­
toresist with a femtosecond laser with a center wavelength of
780 nm. In particular, so-called woodpile photonic crystals with
a rod distance of 2 µm were fabricated. Residual thiol groups
of the prepared microstructures were employed in subsequent
post-functionalization reactions, i.e., thio-Michael additions.
Specifically, maleimides containing fluorescein and bromine
moieties were used for the functionalization. The successful
surface encoding was evidenced via laser scanning microscopy
(LSM) and X-ray spectrometry (XPS), respectively (Figure 4).
Recently, Carter and co-workers have used the thiol-ene reaction
to photochemically crosslink poly(fluorene) derivatives with
vinyl-terminated side-chains of variable lengths with multi­
functional thiol crosslinker.[9] Photo-crosslinked poly(fluorene)
networks were produced by UV irradiating with a hand-held
lamp (254 nm, 1.5 mW cm–2) spin-coated films from vinyl-func­
tionalized poly(fluorene) and di- and tetrafunctional thiols. The
effect of the crosslinkers and polymer architectures in the for­
mation of semiconducting crosslinked thin films was studied
by using Fourier transform infrared (FTIR) spectroscopy,
Adv. Mater. 2017, 29, 1604005
www.advancedsciencenews.com
Figure 3. Chemical structures of multifunctional enes employed in light-induced thiol-ene
reactions.
contact profilometry, and photocalorimetry measurements. In
addition, incorporation of a small amount of fluorenone into
poly(fluorene) photoresists provided a useful colorimetric
Figure 4.  Chemical structure of the photoresist employed for the preparation of our “macroarc” team logo: SEM image (left) and LSM image (right)
after functionalization with fluorescein. Reproduced with permission.[8] Copyright 2013, Wiley-VCH.
Adv. Mater. 2017, 29, 1604005 © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advmat.de
detector to assess the effect of crosslinked
Review
conjugated network architecture on the opto­
electronic properties.
A further interesting functional group
employed as an ene is norbornene (Figure 3).
Norbornene is a highly reactive ene com­
pared to conjugated and electron-poor alk­
enes due to its inherent ring strain. Anseth
and co-workers have particularly employed
the thiol-norbornene photoreaction for the
preparation of hydrogels.[10] While the step-
growth mechanism of the thiol-ene reaction
was well established for solvent-free reac­
tions, this group pioneered the investigation
of the reaction in water-based systems and in
the presence of charged peptides. Different
hydrogels were prepared by employing
norbornene-functionalized PEG (11) and
cysteine-containing peptides (6). High-
resolution magic-angle spinning (HRMAS)
1
H-NMR spectroscopy was used to quantita­
tively evidence the step-growth nature of the
thiol-ene reaction in aqueous media. Since
the thiol-ene photopolymerization is spatially
and temporally controllable as well as cyto­
compatible, it is seen as a versatile tool for
the preparation of functional biomaterials
and the study of the cellular activity in three
dimensions (refer to Applications section). A
similar system was also studied by Lin and
co-workers.[11] PEG hydrogels were prepared
by thiol-ene reaction between a norbornene-
functionalized PEG (11) and bis-cysteine-ter­
minated and chymotrypsin-sensitive peptide
sequence. All the hydrogels were prepared
via UV irradiation (365nm, 5mW cm–2). The
materials displayed good cytocompatibility
with pancreatic β-cells (MIN6) and a high
gelation efficiency (refer to the Application
section for details). The thiol-norbornene
reaction was also employed by Burdick’s
group for preparing photopatternable
hydrogels based on hyaluronic acid.[12] Nor­
bornene-functionalized hyaluronic acid was
crosslinked with dithiothreitol (1) at various
thiol/ene stoichiometric ratios via UV irradiation (320–390 nm,
10 mW cm–2) in the presence of the water soluble photoinitiator
Irgacure 2959. After gelation, secondary reactions between
wileyonlinelibrary.com (5 of 29)  1604005
 www.advmat.de
Review
Figure 5.  Reaction mechanism for chain transfer in the presence of allyl sulfides.
thiol-containing molecules and unreacted norbornenes in
the gel were carried out. Reactions in the presence of dithiol
crosslinkers were conducted to adjust the mechanical proper­
ties, while it was shown that reactions with mono-thiol peptides
had no influence on the final mechanical properties of the gen­
erated gel. In addition, fluorescent thiol-containing dyes were
employed to photopattern the fabricated gels. In a similar study,
Lin and co-workers reported the preparation of hydrogels based
on gelatin.[13] Norbornene-functionalized gelatin was synthe­
sized and subsequently photo-crosslinked via a thiol-ene reac­
tion with different multifunctional thiols, i.e., dithiothreitol (1)
and four-arms PEG-SH (5). The photoreaction was performed
via UV irradiation (Omnicure S1000, 365 nm, 10 mW cm–2)
in PBS using lithium arylphosphinate as photoinitiator. The
degree of crosslinking was tuned by adjusting the thiol con­
centration, gelatin content, or crosslinker functionality. Human
mesenchymal stem cells were employed to demonstrate the
cytocompatibility of the photo-crosslinked hydrogels via photo-
encapsulation. In a recent study, Qin and co-workers employed
norbornene-functionalized PVA (13) and a cysteine containing
peptide, i.e., TRAP6 (thrombin-receptor-agonist-peptide-6),
to form photo-crosslinked hydrogels as well.[14] The materials
were prepared in a PBS solution containing the photoinitiator
Irgacure 2959 employing a UV lamp (Omnicure S2000,
320–500 nm, 20 mW cm–2). The conjugation efficiency was
confirmed by NMR experiments in D2O. Biological experiments
demonstrated the versatility of these materials not only for safe
hemostasis but also for tissue regeneration and wound healing
(see Applications section). Very recently, Liska and co-workers
also employed PVA derivatives for the preparation of biocom­
patible hydrogels.[15] PVA was adequately functionalized to yield
different photoreactive PVA containing vinyl (10) norbornene
(13), and thiol groups (7). The crosslinked gels were prepared
from aqueous solutions of the macromers in the presence of
Irgacure 2959 (Omnicure S2000, 320–500 nm, 20 mW cm–2).
The photoreactivity as well as the mechanical properties of the
photo-crosslinked materials were tested via photo­rheometric
measurements. In a second step, 2P polymerization experi­
ments were carried out. A Ti:sapphire laser system operating
at 800 nm center wavelength and a benzylidene ketone-
based water soluble 2P photoinitiator[16] were used for the
fabrication of 3D microstructures. The experiments showed
the applicability of the synthesized PVA derivatives for 2P
polymerization.
Interesting properties have been observed in networks fab­
ricated via thiol-ene chemistry in the presence of allyl sulfides,
which can act as efficient addition-fragmentation chain transfer
agents (AFCT) (Figure 5).[17] Upon exposure to light, the fabri­
cated networks exhibited stress and/or strain relaxation without
any change in their material properties. The new feature relies
on the presence of residual photoinitiator, which can generate
1604005  (6 of 29) wileyonlinelibrary.com © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
new radicals via photocleavage and react via addition-frag­
mentation chain transfer of mid-chain functional groups. The
reversible cleavage allowed chain rearrangement for rapid
stress relief at ambient conditions without degradation of the
mechanical properties. Very recently, AFCT agents have also
been employed by Liska’s group in the preparation of meth­
acrylate-based networks with improved thermal and mechan­
ical properties. AFCT agents allow the regulation of the poly­
merization process by changing the mechanism from a purely
radical chain growth mechanism to a process involving both
chain growth and step-growth mechanisms. β-Allyl sulfones,[18]
allyl-sulfides[19] and vinyl sulfone esters[20] have successfully
employed as AFCT agents for the preparation of networks with
reduced shrinkage stress, higher homogeneity, increased con­
version and greater toughness. In particular, it was found that
vinyl sulfones show no delay in polymerization and no loss of
mechanical properties.[20] Furthermore, contrary to thiol ene
systems, they also feature a higher chain transfer, allowing the
preparation of more homogenous polymer networks.
Photoinitiated thiol-ene mechanisms have been addition­
ally studied by using multifunctional thiols in combination
with acrylate monomers, vinyl ethers or allyl ethers, among
others.[21] Specific attention has been paid to thiol-acrylate mix­
tures.[5,22] In brief, the reaction mechanism entails of two com­
peting reactions, i.e., acrylate homopolymerization and thiol-
acrylate step-growth reactions (Figure 6). Reactive thiyl radicals
either react with an acrylic double bond or participate in a ter­
mination reaction. The domination of the propagation mecha­
nism by step growth or chain growth directly depends on the
thiol:acrylate ratio, which was found to have a very significant
influence on the polymer network structure and consequently
in the final properties of the material.
Anseth, Bowman and co-workers have prepared degradable
materials from the mixed polymerization of a poly(ethylene
glycol)-poly(lactic acid) (PLA) diacrylate (17) and commer­
cially available multifunctional thiol monomers (3) and (4).[23]
Figure 6. Competing reactions occurring during network forma-
tion between thiols and acrylates: thiol-ene reaction (left) and acrylate
homopolymerization (right).
Adv. Mater. 2017, 29, 1604005
www.advancedsciencenews.com
The networks were formed rapidly upon exposure to UV light
(Ultracure EXFO, 320–500 nm, 5 mW cm–2), with or without
initiators.[21] By varying the concentration and functionality of
the monomers, a high degree of control over the final mate­
rials properties was achieved. The same authors also reported
the preparation of hydrogels based on PEG and peptides, by
employing the thiol-acrylate reaction.[24] PEG diacrylate (14)
was photo-crosslinked with thiol-containing peptides (Hg
lamp, 365 nm, 7 mW cm–2) for the preparation of biocompat­
ible materials with potential applications in tissue engineering
(see Application section for details). Cameron and co-workers
described the preparation of highly porous polymers via photo­­
induced polymerization of phase emulsions employing
different thiol/acrylate ratios.[25] The synthesized networks
contained residual thiols which were reactive towards a range
of (meth)acrylates (hexafluoroisopropyl acrylate, fluorescein
O-acrylate and poly(ethylene glycol) methyl ether methacrylate).
Recently, Chiappone and co-workers also employed this strategy
to produce solid polymer electrolytes.[26] Three different poly­
mers were prepared by photopolymerization of the three mono­
mers, i.e, pentaerythritol tetrakis(3-mercaptopropionate) (4),
PEG diacrylate (14) and PEG methacrylate in different ratios,
keeping the equimolarity between thiol and (meth)acrylic moie­
ties. The monomer mixtures were cast on a polyethylene sub­
strate, sealed in a quartz tube and irradiated by UV light (Hg
lamp, 30 mW cm–2). Solid polymer electrolytes were fabricated
via incorporation of lithium bis(oxalate)borate salts and used as
electrolyte membranes in Li-ion batteries. The thermal stability
of the fabricated materials was also studied. The polymeric
electrolytes showed good ionic conductivity, particularly in the
polymers with 20 wt% lithium salt, where a conductivity of 2.7
10–5 S cm–1 was reached. Very recently, Allonas and co-workers
reported a new combination involving two processes using
amines instead of thiols, i.e., aza-Michael addition and acrylate
photopolymerization.[27] In order to establish comparison, a
kinetic study together with stability studies were carried out
and compared to the ones obtained with thiols. The employed
formulations contained ethoxylated bisphenol A diacrylate, tri­
methylamine, the photoinitiator Irgacure 819 and 1,5-diamin­
opentano. For comparison, 1,5-pentanedithiol was employed.
All the samples were photopolymerized using a light-emitting
diode (Roithner LaserTechnick LED395-66-60-110, 395 nm,
70 mW cm–2) for 2 min. It was found that the photopolymeriza­
tion process is more effective using the thiol-Michael process
rather than aza-Michael. However, both networks (thiol- and
amino-containing) exhibited similar mechanical properties and
comparable homogeneity.
The thiol-ene reaction has also been combined with other
systems, such as methacrylates,[28] isocyanates,[29,30] acryla­
mides,[31] epoxy[32] and vinyl esters.[33] Methacrylate–thiol-ene
systems showed a mechanism, which is a combination of step
and chain-growth polymerizations.[28] In particular, the thiol-
ene systems thiol-allyl ether and thiol-norbornene, were com­
bined with different dimethacrylates. All photo-crosslinking
processes were conducted using DMPA as the photoinitiator
and irradiated (EXFO Acticure, 320–500 nm, 15 mW cm–2).
FTIR spectroscopy was utilized for kinetic analysis. It was
shown that thiyl radicals exhibited an addition rate to meth­
acrylates that exceeds the addition rate for allyl ethers by a factor
Adv. Mater. 2017, 29, 1604005 © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advmat.de
of five. Therefore, methacrylate homopolymerization and chain
Review
transfer are dominant in the early stages, whereas the thiol-
ene reaction is predominant in the latter stages. The hybrid
nature of the networks resulted in reduced shrinkage stress
as a consequence of the delayed gelation and the presence of
non-reacted thiol-ene monomer in the initial stages of the reac­
tion, which act as a diluent. Due to the improved properties
that arise from combining the advantages of methacrylate and
thiol-ene system, the ternary methacrylate-thiol-ene systems are
proposed as potential dental restorative materials (refer to the
Application section).
Thiol-isocyanate-ene ternary networks were studied by
Bowman and co-workers.[29] The networks were prepared by
combination of thiol-ene (light initiated) and thiol-isocyanate
thermal reactions. The thiol-isocyanate ligation consists of the
base-catalyzed addition of primary thiols to isocyanates to gen­
erate a urea linkage. This reaction proceeds rapidly without side
products and with much higher efficiency using mild catalysts
at low concentrations compared to alcohol-isocyanate reac­
tions. However, one of the main drawbacks is the sensitivity
of the isocyanate group to water under ambient conditions,
which limits the stability upon storage. By combining thiol-
ene and thiol-isocyanate reactions and depending on the cata­
lyst employed, it was shown that the reactions follow different
pathways: When using a thermally active base catalyst, sequen­
tial reactions take place, whereas employing a photolatent base
catalyst, which generates an amine upon light irradiation, leads
to simultaneous reactions. Specifically, a conventional base
catalyst, i.e., triethylamine, and the photoinitiator, DMPA, were
used for sequential curing of thiourethane/thiol-ene hybrid
networks. For simultaneous systems, a photogenerated amine
catalyst was used to trigger the thiol-isocyanate and thiol-ene
reactions simultaneously via UV-light irradiation (Hg lamp,
10.2 mW cm–2). Difunctionalized thiols, tetra-ene (9) and dif­
ferent isocyanates (19–22) were employed as monomers. It
was found that the hybrid networks prepared by both methods,
i.e., thermal catalysis (sequential reactions) and photocatalysis
(simultaneous reactions), exhibited identical thermal proper­
ties supporting the formation of uniform and highly dense
networks. The same authors prepared further thiol-isocyanate-
acrylate ternary networks by the combination of thiol-isocyanate
coupling, thiol-acrylate Michael addition, and acrylate homopo­
lymerization.[30] A wide range of physical/mechanical proper­
ties were achieved by simple changes in the component con­
centrations and the reaction sequence. For example, sequential
thiol-isocyanate and thiol-acrylate Michael reactions followed by
photopolymerization of residual acrylates resulted in more uni­
form networks with lower and narrower glass transitions.
Ternary polymer networks based on dopamine acrylamide,
pentaerythritol triallyl ether (ene) and pentaerythritol tetra(3-
mercaptopropionate) (thiol) (4) were also studied.[31] The
networks were fabricated via UV irradiation (320−500 nm,
20 mW cm–2) of DMF solutions containing the three mono­
mers and maintaining a 1:1 thiol/total alkene functional group
stoichiometry. DMPA was used as photoinitiator. It was found
that the presence of the catechol moiety of dopamine signifi­
cantly modified the thermal properties of the fabricated net­
works due to hydrogen bonding interactions. In addition, an
improved macroscopic adhesion of the dopamine-containing
wileyonlinelibrary.com (7 of 29)  1604005
 www.advmat.de
coatings to a range of substrates, including glass, aluminum,
Review
steel, and marble, was achieved simply by systematically
varying the amount of dopamine acrylamide in the network.
Combination of thiol-ene photoreaction and epoxy poly­
merization led to networks with enhanced properties as well.
Sangermano and co-workers reported the preparation of
a hybrid thiol-ene/epoxy polymeric network through a
UV–thermal dual curing process.[32] The approach involves the
photopolymerization of a thiol-ene system followed by a cationic
polymerization catalyzed by alkylsulfonium salts, generated
during the UV-induced process. The employed formulations
consisted of an equimolecular mixture of thiol and allyl groups
and epoxy monomer in different wt%. Benzophenone and tri­
phenylsulfonium hexafluoroantimonate were used to initiation
the thiol-ene and epoxy polymerizations, respectively. The sam­
ples were irradiated with a Hg lamp (280 mW cm–2) and the
obtained hybrid materials showed better thermal and mechan­
ical stability.
Recently, Liska and co-workers have demonstrated the ability
of thiol-ene to enhance photoreactivity of vinyl esters.[33] Photo­
curable vinyl esters have been introduced as suitable alterna­
tives to (meth)acrylates in biomedical applications due to their
lower cytotoxicity and skin irritancy as well as biodegradability.
Nevertheless, one of the main drawbacks is their low reac­
tivity. Mixtures of bifunctional vinyl esters (23) and (24) and
the tetrathiol pentaerythritol tetrakis(3-mercaptopropionate) (4)
were irradiated in a UV chamber (Uvitron UV 1080 with Uvitron
IntelliRay 600 halide lamps, 600 W, UV-A: 125 mW cm–2, Vis:
125 mW cm–2) in the presence of Irgacure 2959. Photody­
namic scanning calorimetry (DSC) and FTIR measurements
evidenced the increase of the photoreactivity of the vinyl esters
due to the presence of thiols. In addition, the system led to a
significantly tougher material with the same level of biocom­
patibility as commercial vinyl esters and one or two orders of
magnitude less toxic than conventional (meth)acrylates. Thus,
the combination of thiols and vinyl esters has been hailed as a
promising alternative to (meth)acrylate chemistry.
2.1.2. (Photo)Thio-Michael Addition
In contrast to the common thiol-ene reaction, which proceeds
via a radical-mediated anti-Markovnikov addition, thio-Michael
addition is a base- or nucleophile-catalyzed reaction. There­
fore, temporal or spatial control is not accessible by employing
the same conditions as for radical thiol-ene processes. Never­
theless, photoinduced control over thio-Michael reactions has
been achieved by the photorelease of bases or nucleophiles
(Figure 1b). Bowman and co-workers reported new photocaged
amines, i.e., nitrobenzene derivatives in which the absorption
of a photon has the potential for freeing an amine and cata­
lyzing the thio-Michael reaction.[34] The use of these photocaged
catalysts demonstrated the capability of photo thio-Michael
addition for photopatterning and spatiotemporal controlled net­
work formation. A mixture of pentaerythritol tetrakis(3-mercap­
topropionate) (4), trimethylolpropane trimethacrylate (15) and a
photocaged amine was employed for the experiments. The pho­
tocaged amines consisted of photocleavable nitrophenyl deriva­
tives, which under UV irradiation generated the corresponding
1604005  (8 of 29) wileyonlinelibrary.com © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
nitrosoderivatives and free amines. The photoresists containing
the photocaged amines were irradiated through a photomask
with a Hg lamp (320−390 nm, 20 mW cm–2). After irradia­
tion, the crude mixture was washed with solvents to remove
the unreacted, non-crosslinked material and a pattern was
visually confirmed, proving spatial control of the photo thio-
Michael addition. The same group has recently developed a
new efficient visible-light sensitive photobase generator for
thio-Michael addition.[35] UV responsive catalysts require high
photon energy and may also cause irreversible damage to
UV-sensitive cells or tissues in biochemical applications. The
photobase generator the authors pioneered consisted of a strong
base (tetramethyl guanidine, TMG) protected with a visible-light
active sensitizer, i.e., coumarin. Model reactions between dif­
ferent monothiols and divinyl sulfone were performed in order
to study the catalytic activity of the photobase. The experiments
were carried out by employing a Hg lamp with a 400−500 nm
bandpass filter (50 mW cm−2). The photocatalyst was assessed
in the context of the thiol-Michael reaction of pentaerythritol
tetrakis(3-mercaptopropionate) (4), and divinylsulfone, allowing
for the fabrication of networks. It was further demonstrated
that coumarin-containing photobases efficiently catalyze other
anion-mediated reactions under relatively mild conditions, such
as thiol-epoxy and thio-isocyanate reactions.
2.1.3. Thiol-yne
The reaction between a thiol and an alkyne has also been estab­
lished as a powerful synthetic method (Figure 1b).[4e,36] The
reaction mechanism has been shown to be analogous to the
thiol-ene photopolymerization, with the added advantage that
each alkyne functional group is capable of consecutive reac­
tion with two thiol functional groups.[37] A thiyl radical adds
to the alkyne triple bond to form a vinyl sulfide radical. This
radical abstracts one hydrogen from a thiol, regenerating the
thiyl radical and forming a vinyl sulfide. Subsequently, the thiyl
radical can be added to the double bond of the vinyl sulfide gen­
erating a dithioether radical, which abstracts a hydrogen atom
from a thiol, thereby regenerating the thiyl radical and forming
a dithioether. The thiol-yne reaction has been exploited for
small molecules, polymer synthesis and modification as well as
in polymeric network formation.[36] Similar to the case of thiol-
ene reactions, multifunctional thiols and alkynes have been
employed for the formation of the networks. Figure 7 depicts
selected examples of alkyne functionalized molecules. As
the thiol-ene reaction, the thiol-yne reaction can be thermally
or photochemically initiated. However, the thermo-initiated
thiol-yne reaction in polymer synthesis is rare due to its low
efficiency compared to the photoinitiated process. In the cur­
rent section, we thus focus on the light-induced radical-medi­
ated thiol-yne reaction as a platform for the fabrication of
networks via light irradiation.
Bowman and co-workers published pioneering work in the
realm of the radical-mediated, step-growth photopolymeriza­
tion of thiol-yne photoresists for the preparation of crosslinked
networks.[38] These authors studied in detail the mechanism and
kinetics of the thiol-yne reaction in the formation of crosslinked
networks and compared them with the analogous thiol-ene
Adv. Mater. 2017, 29, 1604005
www.advancedsciencenews.com
Figure 7.  Chemical structures of multifunctional ynes employed in light-induced thiol-yne and
CuAAC reactions.
reaction. The tetrathiol derived from pentaerythritol (4) was
reacted with bifunctional ene and yne molecules, i.e., 1,9-dec­
adiyne (25) and butanediol divinyl ether, to form polymeric net­
works. The different thiol-ene and thiol-yne formulations were
irradiated with a Hg lamp (EXFO Acticure, 320−500 nm) in the
presence of Irgacure 184 as photoinitiator. It was observed that
the crosslinking density of the fully cured thiol-yne network
was over six times higher than that of the equivalent thiol-ene
network, due to the ability of the alkyne to react with two thiol
groups. The higher density of thiol-yne networks led to an
increase of 70 °C in the glass-transition temperature and dem­
onstrated the potential of thiol-yne based networks as structural
materials. Moreover, residual functionalities, introduced via off-
stoichiometric polymerizations of the monomers, were exploited
for post-polymerization network modification to produce mate­
rials with tunable physical and chemical properties. Lowe and
co-workers reported the reaction of a series of aliphatic dialkynes
and dithiols to generate highly crosslinked hydrocarbon net­
works.[39] The monomer mixture was irradiated in the presence
of Irgacure 184 by employing a Hg lamp as UV-light source
(9.25 mW cm–2). An interesting linear relationship between
the density and the refractive index of the created networks was
found, both of which increase linearly with the weight percent of
sulfur. In further work, Lowe and Bowman reported the prepa­
ration of networks by systematically employing three different
Adv. Mater. 2017, 29, 1604005 © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advmat.de
multifunctional thiols (2–4) and ynes (28–
Review
30) containing two, three and four reactive
groups.[40] The alkyne functionalized mono­
mers were prepared from commercially avail­
able multifunctional thiols containing two,
three and four functional groups and pro­
pargylacrylate, affording the corresponding
mono-, di-, and trifunctional alkyne deriva­
tives, (28), (29) and (30), respectively. All for­
mulations were prepared in a 2:1 thiol/alkyne
ratio and initiated with Irgacure 651. Highly
crosslinked networks were subsequently tai­
lored with increasing Tg, from –10 to 42 °C,
as determined by calorimetry measurements.
The thiol-yne photoreaction was also
employed by Martinez de la Fuente, Sánchez,
Oriol and co-workers for the generation
of biocompatible materials.[41] The system
comprised an alkyne-macromonomer and
a multifunctional tetrathiol, i.e., pentaeryth­
ritol tetrakis(3-mercaptopropionate) (4). The
alkyne-containing macromonomer was pre­
pared from hyperbranched aliphatic polyester
derived from 2,2-di(hydroxymethyl)propionic
acid and 4-pentynoic acid. The photopolym­
erization process was carried out employing
a 405 nm diode laser and UV microscope
lens, which focuses the generated beam onto
the sample. The successful crosslinking was
characterized by variable techniques such as
FTIR spectroscopy and differential scanning
calorimetry (DSC). 2D patterned structures of
different geometries were generated via laser
lithography on glass substrates. Different cell
lines were cultured in the fabricated 2D patterns to investigate
the influence of the topography on the cell adhesion. Recently,
our group has employed the thiol-yne reaction for the forma­
tion of 3D mesostructures with a height of up to 1 mm and
micrometer feature size via 2P photopolymerization employing
the direct laser writing (DLW) technique.[42] The formulation
employed consisted of a tetrafunctional thiol (4), a tetrafunc­
tional alkyne (30), and a 2P photoinitiator. The experiments were
carried out using commercially available DLW equipment (Photo­
nic Professional, Nanoscribe), which possesses a frequency-
­
doubled Erbium fiber laser (80 MHz repetition rate) operating at
the 780 nm center wavelength. In order to demonstrate the lith­
ographic possibilities of the material, microstructures consisting
of body-centered cubic unit cells with different periods were
fabricated via 2P photo-crosslinking (refer to the Applications
section). Importantly, the residual thiols and alkynes groups
in the fabricated structures were employed in subsequent
postmodification reactions, i.e, thio-Michael addition and the
CuAAC reaction, respectively. Firstly, a bromine-malemide was
immobilized via a thio-Michael addition reaction employing
the residual thiol groups. Additionally, the alkyne groups were
reacted with an α-azide functionalized PEG using a CuAAC
reaction. Every reaction was monitored by FTIR spectroscopy
and time-of-flight secondary ion mass spectrometry (ToF-SIMS)
analysis proving the successful orthogonal functionalization.
wileyonlinelibrary.com (9 of 29)  1604005
 www.advmat.de
Serrano and Omenat have reported the preparation of a
Review
photoresponsive liquid crystalline polymer network via thiol-
yne reaction.[43] A dendrimer was used for the first time as a
macromolecular entity to incorporate different functional units
within one single structure, namely, mesogenic azobenzene
photoresponsive units as well as alkyne groups. The anisotropic
network was formed by the photo-crosslinking of a liquid crys­
talline dendrimer with the tetrathiol pentaerythritol tetrakis(3-
mercaptopropionate) (4) via the thiol-yne reaction. Solutions
of the mentioned monomers together with Irgacure 784 were
cast on a glass substrate—previously coated with polyimide
and rubbed—and subsequently irradiated with visible light by
employing a UV lamp (Ultravitalux OSRAM, 300 W) with a
high pass filter of 400 nm. The obtained polymer films were
thermally characterized and appeared stable up to 200 °C. In
addition, a preferential orientation of the molecules along the
rubbing direction was observed. The photoinduced deforma­
tion of the films due to trans-to-cis isomerization of the azoben­
zene moiety was demonstrated, too.
Very recently, Griesser and co-workers studied the formation
of thiol-yne networks from a range of multifunctional alkynes
and thiols (3) and (4).[44] Photo-DSC was employed to monitor
network formation employing the Omnicure s2000 as the light
source (250–445 nm, 80 mW cm–2). It was found that the mate­
rials exhibit low toxicity as well as good mechanical properties
for 3D printing of biomedical materials.
Thiol-yne reactions, together with thiol-ene reactions, were
explored as an efficient platform to produce porous materials.[45]
Du Prez and co-workers prepared polymer beads containing
amine, hydroxyl and carboxyl groups by reacting the tetrathiol
(4) with a range of mono and multifunctional enes and/or ynes
containing the desired functional groups. The crosslinking
reactions were performed in a simple home-made microfluidic
device utilizing thiol and ene/yne monomers at a 1:1 and 2:1 a
ratio, respectively, and DMPA as photoinitiator. Monodisperse
droplets were generated by adjusting the flow rate of both a
continuous and reagent phase in the microfluidic system. The
continuous phase consisted of an aqueous solution containing
a surfactant. The generated droplets were separated and sub­
sequently photopolymerized in a UV chamber (320−400 nm,
2.5 mW cm–2) to form the final polymeric beads. Optical and
scanning electron microscopy images demonstrated the forma­
tion of beads with a spherical shape ranging in size from 210 to
600 mm. Cameron and co-workers described the preparation
of highly porous polymeric materials by employing thiol-yne
and thiol-ene chemistry, too.[45c] Trimethylolpropane tris(3-
mercaptopropionate) (3) and trimethylolpropane triacrylate
(15) as multifunctional ene or octadiyne (25) as diyne, together
with the photoinitiator diphenyl (2,4,6-trimethylbenzoyl) phos­
phine oxide/2-hydroxy-2-methylpropiophenone were employed
for the preparation of the materials. An emulsion consisting
of 25 vol% organic phase consisting of a chloroform solution
of the monomers and photoinitiator and 75 vol% aqueous
phase was prepared, using the polymeric surfactant Hypermer
B246 and subsequently UV irradiated (H bulb, 200 W cm–2)
to induce crosslinked network formation. The highly efficient
reaction led to materials with well-defined morphologies. It
was found that the mechanical properties are dependent on
the porosity and the type of network forming reaction used
1604005  (10 of 29) wileyonlinelibrary.com © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
(thiol-ene or thiol-yne). Thiol-yne porous materials are gener­
ally stiffer than their thiol-ene counterparts due the higher
degree of crosslinking. Simultaneous thiol-yne and thiol-ene
coupling has been employed for the preparation of hydrogels
based on gelatin methacrylamide and tetrafunctional thiol and
alkyne four-arms PEG (5) and (27) (Figure 8).[46] The hydrogels
were formed by dissolving the multifunctional monomers at
different ratios in PBS solution containing the photoinitiator
Irgacure 2959 and subsequently UV irradiation (10 mW cm–2).
It was shown that the mechanical and swelling characteristics
of the prepared hydrogels were tunable by both adjustment of
the monomer composition. These physical properties could
then be utilized to tune the extent of cell adherence and prolif­
eration, making the materials promising in different bio-appli­
cations, such as scaffolds for tissue engineering.
Similarly to the thiol-ene reaction, it was observed that
the addition of AFCTs allows for stress relaxation in thiol-
yne crosslinked networks. Bowman and co-workers studied
the effect of the addition of an AFCT on thiol-yne network
formation.[47a] The allyl sulfide moiety (AFCT) was incorpo­
rated in a thiol-yne system by employing a photoresist com­
posed of an allyl sulfide-based diethynyl monomer (26) and
tetrathiol pentaerythritol tetrakis(3-mercaptopropionate) (4).
It was found that the incorporation of allyl sulfide functional
groups in the polymer backbone of a material possessing a
super-ambient Tg reduces polymerization-induced shrinkage
stress, owing to network connectivity rearrangement via an
AFCT mechanism. Ternary networks of thiol-yne/(meth)­
acrylate have also shown to reduce polymerization-induced
shrinkage stress, while simultaneously achieving high Tg
and large elastic moduli.[47b] If a (meth)acrylate is added to
the thiol-yne system, gelation is delayed causing more volu­
metric shrinkage to occur before gelation relative to the total
volumetric shrinkage, thereby reducing the shrinkage stress.
Particularly, pentaerythritol tetrakis(3-mercaptopropionate)
(4), 1,6-heptadiyne, 1,6-heptadiene and ethoxylated bisphenol
A di(meth)acrylate (18) were employed as monomers in dif­
ferent combinations and Irgacure 184 was used as photoiniti­
ator. In a further experiment, AFCT, i.e., allyl sulfide derivative
(26), were added to the thiol-yne-methacrylate formulations. It
was found that the stress relaxation effect was enhanced by
increasing the AFCT concentration in the formulation. The
ternary system exhibits a polymerization-induced shrinkage
stress level that is less than one third of the stress level of con­
ventional dimethacrylate while possessing excellent mechan­
ical properties.
2.2. Cycloaddition Reactions
Cycloaddition reactions are one of the most exploited synthetic
tools in organic and polymer chemistry since these reactions
are usually fast, efficient and, importantly, often (bio)orthog­
onal. The possibility of initiating these reactions—or their
precursor formation—with light adds extra value, allowing
spatial and temporal control. In the current section, 1,3-dipolar
cycloadditions as well as Diels–Alder [4 + 2] reactions are dis­
cussed. In particular, examples of network formation via
photo­induced metal catalyzed copper(I)-catalyzed azide alkyne
Adv. Mater. 2017, 29, 1604005
www.advancedsciencenews.com www.advmat.de

Review
Figure 8.  Fabrication of a bio/synthetic interpenetrating network consisting of gelatin methacrylamide and PEG via simultaneous photoinitiation of
thiol-ene and thiol-yne coupling. Reproduced with permission.[46] Copyright 2014, Elsevier.

cycloaddition (CuAAC), catalyst free nitrile imine-mediated
1,3-dipolar cycloaddition of a tetrazole and an ene (NITEC) as
well as Diels–Alder reactions (based on photocaged dienes) are
reviewed (Figure 1c).
2.2.1. Photo CuAAC
The copper(I)-catalyzed azide alkyne cycloaddition (CuAAC)
has become very popular in the last years[48] and has also been
identified as a key reaction in polymer and materials science.[49]
Briefly, the CuAAC reaction consists of a 1,3-dipolar cycload­
dition between an azide and a terminal or internal alkyne
catalyzed by copper(I) to afford a 1,2,3-triazole. The copper(I)
catalyst is most commonly generated via the reduction of
copper(II) to copper(I), or directly added as a copper(I) salt.
Therefore, temporal and spatial control of the CuAAC reac­
tion cannot be immediately achieved. However, several groups
pioneered the catalysis of the CuAAC reaction via the photo­
chemical reduction of copper(II) to copper(I) (Figure 1c)
opening a host of new possibilities.[50]
Bowman and co-workers showed for the first time the pos­
sibility of spatiotemporal control of the CuAAC reaction by
using standard photolithographic techniques.[51] In particular,
they explored the synthesis and in situ modification of hydro­
gels by employing a photoinitiated CuAAC reaction. Multi­
functional alkyne and azide PEGs (34) and (41) (Figure 9) were
irradiated (400–500 nm, 10mW cm–2) in the presence of copper
sulfate and Irgacure 2959. Under light irradiation, radicals are
generated and copper(II) is reduced to the active copper (I).
The capability of the photo CuAAC reaction to generate pat­
terned devices was demonstrated by employing a photomask.
The experiments readily produced 35 µm wide (4.2 µm deep)
features that were 5 µm wider than the mask, due to Cu(I)
diffusion. Post-modification of hydrogels was also successfully
demonstrated. Gels were synthesized via the thiol-yne reaction
and the excess of alkynes moieties was employed for a subse­
quent photo CuAAC reaction with an azide-functionalized fluo­
rophore producing a fluorescent pattern.
Following experiments performed by Schubert and
co-workers demonstrated that the photoreduction of copper(II)
acetate to copper(I) ions can be carried out without using any

Adv. Mater. 2017, 29, 1604005 © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim wileyonlinelibrary.com (11 of 29)  1604005
 www.advmat.de
Review
Figure 9.  Chemical structures of multifunctional azides employed in photoinduced CuAAC reactions.
additional photoinitiator. Interestingly, the photo-CuAAC
polymerization of multifunctional azides and alkynes without
photoinitiator was only facilitated using copper(II) acetate, and
not other copper(II) salts. Furthermore, it was shown that the
catalyst concentration together with the degree of functionality
played an important role in the controllability of the polymeri­
zation. In further work, Bowman and co-workers reported the
preparation of networks via photo-CuAAC in bulk employing
visible light (400–500 nm, 10 mW cm–2).[52] Several kinetic
experiments were carried out on a model system consisting of
a trifunctional alkyne, i.e.,1-(prop-2-ynyloxy)-2,2-bis(prop-2-yny­
loxymethyl)butane (32) and the bifunctional azides (39) and
(40) with catalytic amounts of photoinitiator Irgacure 819 and
CuCl2/PMDETA. A highly crosslinked poly­­mer based on tria­
zole linkages was successfully formed via visible light irradia­
tion (400–500 nm). The kinetic experiments evidenced that the
photo-CuAAC in bulk occurred via a similar mechanism than
the one proposed in solution.
Very recently, bulk photopolymerization of an extensive
library of synthesized multifunctional azides and alkynes was
carried out in order to develop structure–property relation­
ships as well as kinetic studies for CuAAC-based polymer net­
works.[53] Multifunctional azides (42–46) and multifunctional
alkynes containing an aliphatic (31–33) or an aromatic (35–38)
core were formulated with a copper catalyst and a photoiniti­
ator, irradiated (Hg lamp Acticure 4000, 365 nm) and analyzed
for their mechanical properties. It was found that the triazoles
generated during the polymerization and the carbamates incor­
porated into the azide monomers (42–46) drastically increase
the Tg by 45−49 and 40 °C, respectively, due to secondary inter­
actions between the triazoles and carbamates. The kinetic
studies of CuAAC photopolymerizations showed that the reac­
tions are highly influenced by the resin viscosity and the Tg
of the polymer, both strongly dictated by the monomer struc­
ture. CuAAC photopolymerizations exhibit a rapid initial rate
followed by the attainment of a maximum conversion that is
limited by vitrification. It was also observed that the copper(I)
catalyst persists after irradiation causing the polymerization to
continue without additional light exposure. Although the extent
1604005  (12 of 29) wileyonlinelibrary.com © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
of dark polymerization limits the temporal control of the photo-
CuAAC polymerization, controlled initiation of the reaction is
readily achieved.
Further, a photo-CuAAC reaction was employed for the prep­
aration of shape memory polymers.[54] The network was fabri­
cated via UV irradiating (Black-Ray B-AP, 5 mW cm–2) multi­
functional tetra-yne (30) and bisphenol A diazide (40) mono­
mers in the presence of a radical photoinitiator (DMPA or Irga­
cure 819), which reduces Cu(II) to Cu(I). The shape-memory
properties of the photo-crosslinked material were character­
ized by studying the free strain recovery. It was shown that the
networks exhibited a sharper recovery in comparison to chain
growth networks due to the step-growth nature of the photo-
CuAAC reaction. Additionally, the CuAAC networks have the
advantage of being tunable with regard to their physicochemical
behavior, opening a new range of possibilities that have not been
achieved with “classical” materials based on (meth)acrylates,
thiol-ene, and poly(caprolactone) yet. The photo-CuAAC reac­
tion was also employed in combination with the thiol-Michael
addition to generate well-defined spatiotemporally controlled
and persistent wrinkles on the surface of an elastomer.[55] The
thio-Michael addition reaction was utilized to form a crosslinked
polymer with residual, reactive alkyne moieties, which were sub­
sequently reacted with diazide monomers via a photoinduced
CuAAC reaction to increase the crosslink density. Pentaeryth­
ritol tetrakis(3-mercaptopropionate) (4) and trimethylolpropane
triacrylate (15) were reacted with propargyl acrylate catalyzed by
triethylamine to generate a thiol-acrylate network. In the second
step, bisphenol A diazide (40) was reacted with the residual
alkyne by employing copper sulfate and a visible-light photoini­
tiator (Irgacure 819) (400–500 nm, 2 mW cm–2). The limited
diffusion of the generated Cu(I) restricted the second polymeri­
zation to a thin skin layer at the surface and led to the forma­
tion of well-defined, persistent and reproducible wrinkles on the
surface of the material. The wavelength and amplitude of these
wrinkles were characterized by using scanning electron micros­
copy (SEM) and atomic force microscopy (AFM). This approach
represents a unique methodology for the generation of wrin­
kling on the entire surface of the elastomer.
Adv. Mater. 2017, 29, 1604005
www.advancedsciencenews.com
2.2.2. Nitrile Imine-Mediated 1,3-Dipolar Cycloaddition
of a Tetrazole and an Ene
Recently, Lin and co-workers[56] re-discovered a light-induced
reaction based on the nitrile imine-mediated 1,3-dipolar
cycloaddition of a tetrazole and an ene (NITEC), which was first
reported by Huisgen and Sustmann[57] in 1967 and hardly used
until few years ago. The NITEC reaction consists of the light-
induced generation of nitrile imines, which are examples of
highly reactive 1,3-dipoles (Figure 1c). Starting with a tetrazole-
containing derivative, nitrogen is released upon photon impact
to form in situ a reactive nitrile imine moiety. Nitrile imines
have been seen to react with a range of activated and unactivated
alkenes and alkynes to form a stable pyrazoline-based cova­
lent linkage. Compared to other established ligation reactions,
NITEC exhibits several advantages such as: i) simple tetrazole-
based molecules synthesis, ii) no necessity of a metal catalyst,
iii) fast reaction times, and iv) bio-orthogonality, although the
last feature has been put into question recently.[56f ] Neverthe­
less, it should be pointed out that contrary to radical mediated
reactions, such as thiol-ene/yne reactions, one photon absorp­
tion event per ligation is required. A further appealing property
of the reaction is the fluorescence of the generated pyrazoline
moieties. The fabrication of fluorescent polymeric materials
makes them interesting for imaging applications such as bio-
sensing and tracing. In addition to polymer ligation,[58] protein
and peptide functionalization[59] and surface patterning,[60] the
NITEC reaction has been successfully employed by our group
for the preparation of fluorescence networks.
1,2-polybutadienes (47) with variable molar mass were
crosslinked by employing a difunctional tetrazole-containing
PEG derivative (48).[61] Different parameters such as concen­
tration or reaction time were optimized and the formed net­
works were analyzed via SEC and gravimetric determination
of gel fractions. It was also shown that the crosslinking is not
only taking place via UV irradiation with a lamp (Arimed B6,
320 nm), but also by sun light. A solvent-cast film consisting
of 1,2-polybutadienes and di-tetrazole linker covered with
a shadow mask (representing the KIT logo) was irradiated
with sunlight (Figure 10). The resulting patterned fluorescent
crosslinked material confirmed the achievable spatial control
of the sunlight-induced NITEC crosslinking process. In further
work, fluorescent and covalently crosslinked cellulose networks
Figure 10.  Fluorescent networks of 1,2-polybutadiene crosslinked with a tetrazole dilinker as visualized under a UV-lamp at 365 nm wavelength.
a) Insoluble gel in THF. b) Swollen gel in an inverted tube. c) Photograph of a photopatterned fluorescent network generated by sunlight irradiation
(Karlsruhe, Germany). Reproduced with permission.[61] Copyright 2014, The Royal Society of Chemistry.
Adv. Mater. 2017, 29, 1604005 © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advmat.de
were prepared by employing the NITEC reaction.[62] Tetrazole-
Review
containing cellulose (50) with 2 degrees of substitution
(0.14 and 0.23) were synthesized via a transesterification reac­
tion in an ionic liquid solution. Two bismaleimides (49) based
on a trioxatridecane or a dithiodipropionyl core were used as
crosslinkers to form fluorescent, covalently crosslinked cellu­
lose networks via UV irradiation (Arimed B6, 320 nm). The
films showed a broad emission band from 500−700 nm wave­
length due to the presence of the pyrazoline moiety proving
the success of the NITEC reaction. Using the bismaleimide
with a disulfide moiety as the crosslinker, reductive degrada­
tion of the films was possible. Finally, tetrazole-functionalized
cellulose was crosslinked in a spatially resolved fashion, pro­
viding a strategy for the shaping of films based on renewable
resources. Recently, we have additionally demonstrated the
ability of tetrazoles to react with fullerenes, which can act as
an ene.[63] The NITEC reaction was successfully carried out by
employing small molecule, polymer, and surface-immobilized
tetrazoles. Depending on the tetrazole/fullerene ratio, it was
found that multiple tetrazole molecules can be conjugated to
a single fullerene. Therefore, we have very recently exploited
this strategy for the formation of fullerene containing networks
via NITEC.[64] A linear polymer containing tetrazole moieties as
pendant groups (51) and fullerene (52) as ene were employed
for the formation of hybrid networks by UV irradiation (Arimed
B6, 320 nm). As mentioned, fluorescence measurements are
often used for monitoring of tetrazole reaction due to the for­
mation of a self-reporting fluorescent pyrazoline unit. Never­
theless, fluorescence measurements were not possible within
polymer-fullerene networks, since fullerenes have a strong
absorption and the fluorescence is quenched. The fullerene-
containing networks were thus analyzed by FTIR spectroscopy
and elemental analysis (EA). It was found that in the presence
of a sufficient number of tetrazole units, every fullerene was
linked to on average two tetrazole moieities, which permitted
the formation of a stable network. The constructed fullerene
based networks have potential applications in optoelectronic
devices such as bulk heterojunction solar cells, where the for­
mation of stable fullerene nanodomains is still a challenge.
Zhong and co-workers have also employed the NITEC reac­
tion for the formation of fluorescent hydrogels.[65] The hydro­
gels were prepared from two 4-arm PEG derivatives containing
four methacrylates and four tetrazole moieties, respectively.
wileyonlinelibrary.com (13 of 29)  1604005
 www.advmat.de
Both photoreactive PEG derivatives were dissolved in a phos­
Review
phate buffer at 37 °C with polymer concentrations ranging
from 20 to 60 wt%, and UV irradiated (365 nm, 60 mW cm–2).
Depending on the polymer concentration, the gelation times
varied from ca. 50 s to 5 min., and storage moduli varied from
0.65 to 25.2 kPa. In order to demonstrate the biocompatibility
of the fabricated hydrogels, cell experiments via an indirect con­
tact assay were carried out and demonstrated that the NITEC
PEG hydrogels were non-cytotoxic. In addition, it was observed
that the PEG hydrogels are particularly interesting for con­
trolled protein release.
2.2.3. Photoinduced Diels–Alder Reactions
A powerful example of cycloaddition reactions with a promi­
nent role in organic synthesis are Diels–Alder reactions. The
Diels–Alder reaction consists of a [4 + 2] cycloaddition between
a conjugated diene and a substituted alkene, commonly known
as dienophile, to form a substituted cyclohexene system. Diels–
Alder reactions can be reversible under certain conditions and
the reverse reaction is known as the retro-Diels–Alder reaction.
Similarly to CuAAC, by employing conventional conditions,
i.e., reaction between a diene and a dienophile in the presence
of a Lewis acid, temporal and spatial control cannot be readily
achieved. It must be noted that a Diels–Alder reaction cannot
be photoinduced (forbidden by the Woodward-Hoffmann
rules), rather one of the starting materials (the ene of the diene)
needs to be provided photochemically.
Recently, Bowman and co-workers combined Diels–Alder
and thiol-ene and acrylate chemistry to prepare dually cured
3D microstructures.[66] A crosslinked polymer was initially
formed via a Diels–Alder reaction and a subsequent photoini­
tiated reaction—either thiol-ene reaction or acrylate polym­
erization—selectively converted the Diels–Alder adducts into
irreversible crosslinks. The photo-initiated reactions allowed
for spatial control and the preparation of complex 3D struc­
tures via DLW. In an initial study, a multifunctional furan and
a bismaleimide derivative formed a crosslinked polymer by the
Diels–Alder reaction in the presence of a tetrafunctional thiol (4).
Subsequently, the oxy-norbornene groups reacted with the
thiol groups present in the polymer network via light irradia­
tion (pulsed laser, 740 nm) and irreversible links were gener­
ated. The pattern was subsequently developed by selectively
removing the material of the non-irradiated areas via a retro-
Diels–Alder reaction. In a second study, a thermoreversible net­
work scaffold was prepared similarly via Diels–Alder reaction,
yet this time in the presence of trimethylolpropane triacrylate
(15). It was demonstrated that the initial Diels–Alder occurred
orthogonally to the unreacted acrylates present. Upon irradia­
tion, the material became no longer thermoreversible by gen­
erating a permanent network structure. The advantage of the
above methodology lies in the fact that unexposed material
remains crosslinked and serves as a physical support for subse­
quent layer-by-layer stereolithography, (refer to the Applications
section). After all layers had been photopatterned as desired,
development occurred via thermally induced retro Diels–Alder
of the unexposed material. However, one of the main disadvan­
tages of the methodology is the necessity of a third component
1604005  (14 of 29) wileyonlinelibrary.com © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
employed in a light-induced reaction in order to achieve the
spatial control.
Our group has introduced (for macromolecular chemistry)
a novel procedure for truly photoinduced Diels–Alder reac­
tions by in situ generation of diene species via light irradiation
(Figure 1c). The system is based on hydroxy-o-quinodimeth­
anes (photoenols) which are generated by photoisomeriza­
tion of o-methylphenyl ketones or aldehydes. The generated
photoenols can act as dienes for the conventional Diels–Alder
reaction with different dienophiles, such as maleimides. This
methodology has been demonstrated to be simple and efficient
in light-induced conjugations of polymeric building blocks as
well as surface functionalization.[67] In addition, the reaction
has been employed for the preparation of 3D microstructures
fabricated via a multiphoton process.[68] A multifunctional
monomer containing four active moieties that can undergo
efficient photoenolization (53) and a copolymer consisting of
methyl methacrylate and a maleimide containing methacrylate
(54) were employed for the formation of 3D microstructures
via DLW (Figure 11). The experiments were conducted using
a home-built setup containing a pulsed laser at 700 nm center
wavelength and 80 MHz repetition rate. Specifically, woodpile
photonic crystals were fabricated and characterized by SEM and
FTIR. As discussed in the previous sections, reactive groups
remain throughout the written structure and can be addressed
for subsequent modification of the polymer surface. Spatially
resolved surface patterning was demonstrated by employing
the DLW setup and a bromine containing maleimide. Onto
the surface of a solid structure, the Karlsruhe Institute of Tech­
nology (KIT) logo was patterned employing the DLW setup.
The successful surface modification was verified via ToF-SIMS
by detecting the signal corresponding to Br isotopes, which
drastically increased in the irradiated areas (Figure 12). The
same chemistry has also been employed for surface patterning
of microscaffolds containing benzaldehyde groups with fluores­
cence markers as well as proteins.[69]
We further reported the preparation of photoreactive con­
jugated polymers consisting of functionalized polythiophene-
containing 4-hydroxy-2,5-dimethylbenzophenone (DMBP)
(photoenol) and/or maleimide as side groups (55, Figure 11).[70]
We evidenced the chemical versatility and platform character of
the generated light reactive polythiophenes in a range of exam­
ples by creating variable polythiophene functional 2D and 3D
structures with different morphologies. Single-chain nanopar­
ticles and polymeric networks were formed by cross-linking of
DMBP and maleimide containing polythiophene via UV-light
irradiation (Philips TL 36W, 312 nm) by varying the polymer
concentration. Maleimide-functionalized polythiophene was
employed for spatially resolved functionalization of surfaces.
Very recently, a novel concept for light-induced network forma­
tion was described. Wavelength-selective network formation
was achieved by combining two different photoactive moieties,
i.e., photoenol and tetrazole functionalities which are activated
at different wavelength.[71] 4-arm polymers bearing tetrazoles or
photoenol moieties (56) were synthesized via RAFT polymeriza­
tion and selectively crosslinked with a trifunctional maleimide
(57) (Figure 11). The versatility was further demonstrated via
the combination with DLW, which allowed the fabrication of
3D logos of the Karlsruhe Institute of Technology (KIT) with
Adv. Mater. 2017, 29, 1604005
www.advancedsciencenews.com www.advmat.de

Review
Figure 11.  Chemical structures of the systems employed for the formation of networks via a) NITEC and b) photoinduced Diels–Alder chemistry.

dimensions of 40 mm × 15 mm × 5 mm. The microstructures
were written at a fundamental center wavelength of 640 nm.
For both formulations (photoenol and NITEC), the fabricated
structures were well-defined.
2.3. Photodimerization Reactions
Photodimerimerization of cinnamate, anthracene or cou­
marin among others, has also been exploited as a crosslinking
reaction (Figure 1d). One of the appealing properties of this
strategy is its reversibility. This approach allows both the light-
triggered formation and cleavage of covalent networks. One of
the most popular groups is cinnamate, whose photofunction­
ality arises from a [2 + 2] photodimerization potential leading
to insoluble networks due to the formation of crosslinking
bonds (Figure 1d). The design of monomers bearing cinnamate
groups has been widely investigated, and many derivatives of
(meth)acrylates bearing lateral cinnamate moieties have been
prepared. These functionalized polymers exhibited good reac­
tivity and have traditionally been used in the photoalignment
of liquid crystals.[72] Cinnamate-containing polymers are able

Adv. Mater. 2017, 29, 1604005 © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim wileyonlinelibrary.com (15 of 29)  1604005
 www.advmat.de
Review
Figure 12.  a) Light-induced Diels–Alder reaction between residual benzaldehyde precursor molecules on fabricated structures and bromine containing
maleimides; b) ToF-SIMS images of 79 Br, 81 Br, and their sum (from left to right). Reproduced with permission.[68] Copyright 2014, Wiley-VCH.
to induce the alignment of liquid crystals in contact with the
film surface upon irradiation with linearly polarized UV light.
Nevertheless, cinnamate photodimerization is not limited to
the liquid-crystal field, yet cinnamate containing biopolymers
have also been studied. For instance, Matsuda and co-workers
prepared hydrogels based on cinnamate photodimerization.[73]
Copolymers from N,N-dimethylacrylamide and cinnamate-
containing methacrylate were synthesized and irradiated with
a Hg lamp (600W, >280 nm) to produce crosslinked polymers.
It was shown that only a few mol% of cinnamate groups in a
copolymer were sufficient for gelation. As expected, the higher
the content of cinnamate in copolymer, the higher is the
crosslinking density. In addition, the irradiation at lower wave­
lengths (254 nm) resulted in partially reversible gel-sol inter­
conversion. Chaikof and co-workers reported the synthesis and
photo-crosslinking of cinnamate-containing collagen deriva­
tives.[74] The crosslinking reaction was successfully carried out
in a gel and in the solid state via UV irradiation (lamp 6W,
254 nm, 2.25 mW cm–2). It was shown that the collagen gels
and films exhibited enhanced mechanical properties.
An alternative group exhibiting similar photochromic prop­
erties is coumarin. Upon irradiation at 350 nm, coumarin
derivatives undergo also [2 + 2] cycloadditions to yield cyclobu­
tane dimmers (Figure 1d). The photodimerization reaction has
been seen both in solution and in the solid state and it can be
reversed via UV irradiation at a shorter wavelength. Saegusa
and co-workers reported for the first time the preparation of a
hydrogel based on polyoxazoline by means of photodimerization
of the coumarin.[75] The photocoupling reaction was carried out
by irradiating (Hg lamp 450 W, >300 nm) a film from a poly­
oxazoline bearing coumarin moieties as pendant group. The
photocleavage reaction of the polyoxazoline gel was performed
1604005  (16 of 29) wileyonlinelibrary.com © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
by irradiating at 253 nm and the regeneration of the coumarin
was almost quantitative. Zhao and co-worker demonstrated the
reversible photo-crosslinking and photocleavage of 4-methyl­
coumarin terminal functionalized hyperbranched polymer and
compared with an analogous linear polymer.[76] It was found
that the process of photocleavage was much faster than photo-
crosslinking and that the hyperbranched derivative performed a
larger photoreversible extent than the linear one. More recently,
the same authors reported the preparation of well-defined
single-change nanoparticles by the intrachain photodimeri­
zation of coumarin groups upon λ > 310 nm UV irradiation
in a dilute copolymer solution.[77] A poly(N,N-dimethylamino­
ethyl methacrylate) copolymer containing coumarin moieties
as pendant groups was employed. Furthermore, they showed
that such SCNPs could be used as a nanoreactor for the syn­
thesis of AuNPs and the rate of AuNP formation is sensitive
to the intrachain crosslinking density. Joy and co-workers lately
described a novel class of coumarin-containing photorespon­
sive polyesters in which the chromophore is incorporated into
the polymer chain.[78] The coumarin-based polyesters exhibited
chain crosslinking at 350 nm wavelength and subsequently
uncrosslinking at 254 nm irradiation. It was also observed that
irradiation at 254 nm provokes a photoinduced cleavage of
the ester bond leading to polymer chain scission. In addition,
micropatterned surfaces were created by UV irradiation at dif­
ferent wavelengths, i.e., 350 and 254 nm. The coumarin poly­
esters showed mechanical stability in the absence of light and
preliminary studies with cells pointed to the biocompatibility of
the polymers and the irradiation products.
On the other hand, anthracene and its derivatives
can undergo [4 + 4] dimerization upon UV irradiation
(Figure 1d). The generated dimer, called dianthracene
Adv. Mater. 2017, 29, 1604005
www.advancedsciencenews.com
(or sometimes paranthracene), reverts to anthracene thermally
or with UV irradiation below 300 nm. Leblanc and co-workers
employed the reversible photodimerization of this chromo­
phore for the preparation of a PEG hydrogel.[79] An eight-arm
PEG polymer containing eight anthracene units in its periphery
was synthesized and employed in different irradiation tests.
The anthracene functionalized polymer exhibited high photo­
sensitivity at higher wavelengths and underwent rapid and
reversible photo-crosslinking upon exposure to alternating
wavelengths (365/254 nm) in the absence of photoinitiators or
catalysts. It was shown that the physicochemical properties of
the fabricated hydrogels, including swellability, optical absorp­
tion, and topography depends on the exposure time as well as
the wavelength employed.
2.4. Other Crosslinking Reactions
Aryl azides are a further example for a photoreactive group.
When an aryl azide is exposed to UV light (250–350 nm wave­
length), it forms a nitrene group that can initiate addition reac­
tions with double bonds or insertion into C–H and N–H sites
(Figure 1e). Traditionally, this chemistry has been used for
bio-conjugation and the analysis of biomolecular interactions,
i.e., protein-protein interactions or protein-nucleic acid interac­
tions.[80] Recently, Liska and co-workers demonstrated the pos­
sibility of multiphoton-induced photografting with a reactive
aromatic azide compound onto a highly permeable PEG based
matrix.[81] A difunctional aryl azide 2,6-bis(4-azidobenzylidene)-
4-methylcyclohexanone was employed as the photoreactive mol­
ecule embedded into the PEG matrix. The laser beam (pulsed
laser, 73 MHz, 793 nm) was focused on the material and caused
the photolysis of the aryl azide, followed by the generation of
nitrogen and highly reactive electron-deficient nitrene spe­
cies, which was directly immobilized on the PEG network by
insertion into a C–H bond. Since the multiphoton interac­
tion is highly localized, 3D patterns of immobilized molecules
can be prepared. After grafting, the non-reacted azides were
employed for a subsequent reaction with an alkyne fluorophore
via CuAAC. Therefore, the grafted patterns were visualized via
LSM. In a further work, a similar procedure was followed for
3D patterning by employing a novel fluoroaryl azide with an
alkyne moiety, which allows for further CuAAC reactions with
different azide-containing molecules.[82]
Diazonium salts have also been studied as photoreactive
systems in mixtures with anionic compounds, including poly­
anions such as synthetic poly(sodium styrenesulfonate) (PSS)
or natural polyelectrolytes such as DNA. Diazonium salts
interact with anionic groups via ionic recognition. Upon UV-light
irradiation, the ionic interaction between the diazonium group
and the anion becomes a covalent bond, with the advan­
tage that the prior ionic recognition ensures the proximity of
the reactive groups during irradiation (Figure 1e). This meth­
odology has been widely exploited by Cao’s group. In an initial
study, several polyelectrolyte complexes were prepared by
mixing aqueous solutions of an diazo-resin with several poly­
anions, such as PSS, poly(sodium ethylenesulfonate) (PES),
potassium 3-sulfopropyl acrylate (SPA), and potassium 3-sulfo­
propyl methacrylate (SPM).[83] Under irradiation with UV
Adv. Mater. 2017, 29, 1604005 © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advmat.de
light (Hg lamp 80W, 365nm), the authors demonstrated that
Review
the complexes change their crosslinking structure from ionic
links to covalent bonds.The same strategy was also employed
by the same authors for the preparation of self-assembled
multilayers, taking the advantage of the mentioned ionic rec­
ognition.[84] Poly(aniline-co-o-anthranilic acid) and photosensi­
tive diazoresin were self-assembled into a multilayer ultrathin
film via ionic interaction. Under UV irradiation (360 nm,
0.23 mW cm–2), the decomposition of the diazonium group
between bilayers occurs, the ionic bond of the self-assembly
film converts into a covalent bond, and the film became very
stable against polar solvents and strong electrolyte solutions.
Subsequently, the generation of photocurrent was studied and
it was evidenced that the polyaniline containing film is respon­
sible for the photocurrent. In a further report, the same group
prepared fullerene-containing self-assembly multilayer based
on a diazoresin photosensitive polymer.[85] Fullerols were
employed as anions and under irradiation the phenyl cation
formed from the diazonium salt decomposition aligned prefer­
ably with the oxygen anion of fullerol to form covalent linkage.
The fabricated films showed good stability after UV irradia­
tion and photoelectric conversion property, which make them
good candidates as photoelectrochemical cell components.
More recently, the diazonium chemistry have been employed
for the preparation of DNA-containing micropatterned films.[86]
Multilayer films were prepared from DNA and diazonium
containing polymers. The driving force of the assembly stems
from the electrostatic interaction between the positive diazo­
nium group the negative phosphate group of DNA. The films
were subsequently irradiated. Patterned multilayer films were
fabricated by employing a photomask. The micropatterns were
characterized using four different techniques, namely scanning
electron microscopy (SEM), atomic force microscopy (AFM),
X-ray photoelectron spectroscopy (XPS), and fluorescence
microscopy and showed that this technique is promising for
constructing stable, well-defined micropatterns with nanoscale
thickness. Sánchez, Oriol, and co-workers demonstrated the
preparation of polymeric networks employing a trifunctional
diazonium salt derived from triphenylamine without the need
of photoinitiator.[87] Mixtures of poly(sodium sulfonate) and
the trifunctional diazonium derivative were employed for the
preparation of films and irradiated with a Hg lamp (Oriel 6286,
350 W). The spatial control was demonstrated by the genera­
tion of a periodic surface pattern by using photolithographic
line mask and etching with an aqueous NaOH solution the
non-irradiated polymer. The same authors further reported the
reactivity of the same crosslinker with hydroxyl and carboxylate
groups, both of which are commonly found in biopolymers, by
using sodium polyacrylate and poly(vinyl alcohol) (PVA).[88]
Poly­meric networks were obtained from mixtures of the different
polymers and crosslinking via UV irradiation (350–450 nm,
160 mW cm–2). Once the possibility of photo-crosslinking with
polymers containing hydroxyl and carboxyl groups was demon­
strated, the biopolymer sodium hyaluronate (which contains
both functional groups) was employed for the preparation of
networks. 2D patterned structures were generated by direct
laser writing (DLW) using a focused laser beam at 405 nm. The
biocompatibility as well as the cell adhesion of the polymeric
structures obtained by photo-crosslinking of hyaluronic chains
wileyonlinelibrary.com (17 of 29)  1604005
 www.advmat.de
with the trifunctional diazonium salt crosslinker were assessed.
Review
It was found that the cell adhesion can be tuned by modifying
the crosslinker concentration in the formulation.
Hydrazone or oxime formation by the condensation of
hydrazine or hydroxylamine are classic reactions in organic
chemistry. Very recently, Anseth and co-workers demon­
strated the light driven formation of hydrazones, including
the possibility of spatiotemporal control of the reaction.[89] The
photoresponsiveness was introduced by incorporating a photo­
reactive 2-nitrobenzylalcohol moiety, which forms a 2-nitroso­
benzaldehyde when exposed to UV light (365 nm, 20 mW cm–2)
(Figure 1e). The photogenerated aldehyde can react with hydra­
zine to produce hydrazone bonds. The authors employed the
mentioned strategy for the formation of PEG-based hydrogels.
Specifically, 4-arm PEG terminated hydrazine and nitrobenzyl
were used for the hydrogel formation via light-induced hydra­
zone crosslinking. It was shown that this photodriven hydra­
zone chemistry can be used to externally control not only
the gel formation kinetics, but also the final modulus of the
hydrogel scaffold by simple variations in the light intensity
and exposure time. Furthermore, a rapid hydrogel formation at
physiological pH was demonstrated, suggesting the potential of
this gel formation chemistry for mild and convenient cellular
encapsulations.
3. Applications of Photo-crosslinked Networks
Crosslinking processes are a major route to provide stable
materials, which have been used in different areas ranging
from materials science to medicine. The key defining prin­
ciple of employing light as an external stimulus for the fabri­
cation of networks is the available spatial control. As already
noted, acrylic and epoxy-based monomers have been widely
employed for photo-crosslinking and have already found a large
number of applications.[3] Nevertheless, in the current section
we will focus on different applications of materials prepared by
emerging and promising crosslinking strategies, i.e., thiol-ene-
based reactions, cycloadditions, and photodimerization among
other reactions previously discussed in Section 2. First, we will
present different biomaterials with potential application in bio­
medicine, specifically in dental restoration (Section 3.1.1) and
tissue engineering (Section 3.1.2). Subsequently, crosslinked
networks employed in coatings (Section 3.2) and different
lithography methods (Section 3.3) are discussed.
3.1. Biomedical Applications
Biomaterials are functional materials designed for introduc­
tion into living tissues with the purpose of aiding healing,
correcting deformities, and restoring lost functions. During
the last years, much attention has been paid to the develop­
ment of novel biomaterials, opening new possibilities of treat­
ments and applications. The first biomaterials employed were
simple metals and alloys. Nevertheless, polymers, ceramics,
and advanced composite materials are currently commonly
used as well. In what follows, we give a short review of various
studies focusing on two different applications of polymeric
1604005  (18 of 29) wileyonlinelibrary.com © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
networks in biomedicine, namely dental restoration and tissue
engineering.
3.1.1. Dental Restoration
Millions of dental restorations are performed every year, most
of which have a limited lifespan. Therefore, large efforts have
been undertaken to develop a restorative material with tooth-
like appearance and durable properties. Although various alter­
native dental resin systems have been examined, dimethacrylate
monomers are still the predominantly employed monomers
in dental resins.[90] The main drawback of the methacrylate
based resins is polymerization shrinkage stress as well as inho­
mogeneous network formation. To circumvent this problem,
Bowman and co-workers have extensively explored alternatives
to (meth)acrylate-based resins. In particular, they investigated
the feasibility of formulating novel dental restorative mate­
rials by employing the photoinduced thiol-ene polymeriza­
tion with the aim to significantly reduce the shrinkage stress
while maintaining the desired physical properties. As already
described in the synthetic section, triallyl-1,3,5-triazine-2,4,6-
trione (8) and pentaerythritol tetra(3-mercaptopropionate) (4)
was employed as the thiol-ene system and compared with typ­
ical dimethacrylate based dental resin systems.[91] It was found
that thiol-ene formulations based on thiol-allyl systems cure
at a much higher rate, specifically six times faster than that of
based on methacrylate derivatives under identical irradiation
conditions. The results from the simultaneous measurement of
shrinkage stress and conversion showed that the onset of the
shrinkage stress is directly related to the delayed gelation point.
The maximum shrinkage stress developed for the thiol-allyl
system was about 0.4 MPa, which was only approximately 14%
of the maximum shrinkage stress of the methacrylate system.
Nevertheless, the thiol-allyl system did not exhibit the mechan­
ical properties necessary for dental restorative materials. The
achievable Tg, flexural strength, and flexural modulus were sig­
nificantly lower than the corresponding values for methacrylate
based resins. In order to improve the mechanical properties,
the same authors tested ternary thiol-ene-methacrylate systems
in a following work.[28c] Thiol-ene mixtures were employed as
reactive diluent in dimethacrylate systems leading to mate­
rials with a higher flexural modulus and strength, while the
polymerization shrinkage stress was efficiently reduced. It
was also found that the optimum thiol-ene stoichiometry dif­
fers from the traditional 1:1 ratio because of thiol consumption
via thiol-ene reaction together with chain transfer involving
the methacrylate polymerization. Increasing the thiol to ene
stoichiometry resulted in further increased methacrylate func­
tional group conversion and decreased volume shrinkage. Nev­
ertheless, they did not exhibit significant changes in flexural
modulus and strength, shrinkage stress, depth of cure, water
sorption or solubility with excess of thiol. More recently, ester-
free thiol-ene formulations have been studied, too.[92] In par­
ticular, tetra(2-mercaptoethyl)silane and tetra-allyl monomer
containing urethane linkages were employed for the prepara­
tion of the crosslinked materials. It was found that the ester-
free thiol-ene formulations had significantly lower viscosities,
water sorption and solubility than the conventional methacrylic
Adv. Mater. 2017, 29, 1604005
www.advancedsciencenews.com
resins. In addition, the polymerization shrinkage stress was
dramatically reduced when the tetra-allyl monomer was used
as the ene in ester-free thiol-ene mixtures. It was also evi­
denced that the toughness values associated with thiol-ene
systems were larger than the methacrylate based ones, while
Young’s modulus, flexural strength, and glass-transition tem­
peratures were reduced. In contrast to conventional resins, the
mechanical properties of the ester-free thiol-ene composites
were shown to be unaffected by extensive aging in water and at
least equaled that of the control after aging in water for just five
weeks. Almost in parallel, Ritter and co-workers studied alter­
native ester-free thiol-ene systems with potential applications in
dental restoration.[93] A library of hydrophobic ester-free thiol-
modified bis- and trisphenol derivatives were prepared. The
bis- and trisphenol derivatives contained four to six thiol groups
and were crosslinked via photoinduced thiol-ene chemistry
with 1,3,5-triallyl-1,3,5-triazine-2,4,6-trione (8). The well known
ester-containing pentaerythritol tetra(3-mercaptopropionate) (4)
was employed as reference. Better flexural strength and mod­
ulus of elasticity were achieved with the new thiol–ene system
employing the hydrophobic ester-free phenol derivatives. In
particular, after storage in water, the flexural strength and mod­
ulus of elasticity were twice as large compared to the reference
system. The same authors also examined thiol-functionalized
triazine-based monomers as possible candidates for dental res­
toration.[94] Once again, the thiol monomer, i.e., triazine-based
monomers, were photo-crosslinked with the triallyl derivative
(8) and compared with the thiol-ene system containing pentae­
rythritol tetra(3-mercaptopropionate) (4). It was found that the
system containing the triazine outperformed the widely used
ester-derivative, which became especially obvious after storage
in water. An improvement of the flexural strength and modulus
of elasticity by more than 50% was achieved. Furthermore,
the performance of the system in dental filled composites was
also investigated and compared with composites containing a
standard dimethacrylate matrix. The triazine-based compos­
ites showed higher values for the flexural strength and elastic
moduli and simultaneously, the shrinkage stress was reduced.
Hence, the authors proposed the use of thiol-containing tria­
zine derivatives as promising candidates to fabricate dental
composites exhibiting low-odor and low-shrinkage, but also
good mechanical properties.
3.1.2. Tissue Engineering
Hydrogels are hydrophilic polymer networks, which consist of
a three-dimensional (3D) polymer network and large amounts
of water. They are soft, wet materials with the characteristics of
both solids (well-defined shapes) and liquids. In general, hydro­
gels exhibit poor mechanical performance and, therefore, they
are employed in almost every application after being chemi­
cally crosslinked. Due to their hydrophilic character and poten­
tial to be biocompatible, crosslinked hydrogels have been of
great interest as biomaterials. Furthermore, due to their large
water content, hydrogels also possess a degree of flexibility very
similar to natural tissue. Hence, one of the common applica­
tions of crosslinked hydrogels is their use as scaffolds in tissue
engineering.[95]
Adv. Mater. 2017, 29, 1604005 © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advmat.de
PEG-based photo-crosslinkable hydrogels are one of most
Review
widely employed biomaterials for tissue engineering. As dis­
cussed in the synthetic section, Anseth and co-workers have
developed a methodology for the preparation of PEG hydrogels
via photo-crosslinking of norbornene-functionalized PEG and
thiol-containing peptide sequences to form hydrogels for many
different purposes. For instance, hydrogels fabricated from
PEG and chympotrypsin degradable peptide were employed as
extracellular matrix mimic.[10] Cleavage of the chympotrypsin-
sensitive peptide crosslinks led to an enzyme dependent
decrease in the elastic modulus over time, indicating that the
crosslinks were cleaved in a controlled fashion. In addition,
adult human mesenchymal stem cells (hMSCs) were encapsu­
lated in the thiol-ene based hydrogels in order to demonstrate
the cytocompatibility of the material. It was shown that it is
possible to spatially control the degree to which cells interacted
with the hydrogels. The authors noted that this possibility of
spatial control could open new possibilities in the design of
strategies for inducing tissue formation or to study specific
biological processes. In a further study, peptide-functionalized
photo-crosslinked PEG hydrogels were employed to study 3D
mobility of hMSCs.[96] Specifically, the peptide-functionalized
PEG hydrogels were used to encapsulate hMSCs, while varying
the crosslinking density and the adhesive ligand density. It was
shown that hMSC migrating through the lowest crosslinking
density and highest adhesivity had more sustained polariza­
tion, higher migrating speeds and higher cell spreading. The
same authors have also studied protein encapsulation[97] and
protein delivery[10] employing thiol-ene photo-crosslinked
PEG hydrogels. Hydrogels were formed via photo-polymeri­
zation using acrylate chain-growth and thiol-ene step-growth
mechanisms from different photoreactive PEG.[93] First, non-
gelling solution polymerizations were carried out to study
the loss of protein function during the crosslinking process
using acrylates and thiol-ene systems. It was observed that the
acrylate reaction led to some loss of protein bioactivity. Nev­
ertheless, when lysozyme, chymotrypsinogen, collagenase,
bovine serum albumin, human serum, and TGFβ were encap­
sulated in the photo-crosslinked thiol-ene gels and subse­
quently released into PBS buffer, greater than 80% recovery
was observed. This behavior could be due to the oxygen inhi­
bition in the acrylate reaction or the more rapid kinetics of
the thiol-norbornene reaction. In addition, TGFβ was encap­
sulated in PEG hydrogels formed via a thiol-ene reaction, and
no statistically significant loss of bioactivity was detected rela­
tive to the non-encapsulated growth factor. Further, enzyme-
responsive photo-crosslinked PEG hydrogels for controlled
protein release at sites of inflammation were investigated.[10]
Hydrogels were formed from norbornene-functionalized PEG
and human neutrophil elastase (HNE)-sentive peptide via pho­
toinduced thiol-ene crosslinking. HNE triggered gel degrada­
tion was studied and the HNE-responsive hydrogels exhibited
surface erosion. The degradation kinetics were influenced by
changes in the peptide reaction constant, concentration of
HNE, and concentration of peptide within the gel. The advan­
tages of surface eroding platforms were exploited to release
various size proteins on the same time scale dictated by gel
formulation. It was also seen that lysozyme retained 93% of
its bioactivity post thiol-ene photopolymerization. This delivery
wileyonlinelibrary.com (19 of 29)  1604005
 www.advmat.de
Review
Figure 13.  a) Chemical structures of network components: norbornene-functionalized PEG and cysteine-containing peptides; b) Mechanism of the
radical-mediated thiol-ene reaction to produce step growth networks; c) Scheme of cells (neurons) encapsulated in the gel formulations prepared by
thiol-ene chemistry. Reproduced with permission.[10c] Copyright 2013, The Royal Society of Chemistry.
platform was presented as a promising alternative for treat­
ment of disease where inflammation has been implicated
such as diabetes, rheumatoid, arthritis, and cancer. Photo-
crosslinked PEG hydrogels have also been studied as a sup­
porting system capable for the culture and axonal outgrowth of
both aggregated and dissociated mouse embryonic stem cell-
derived motor neurons (ESMNs) (Figure 13).[10b] PEG-based
hydrogels promoted neuronal survival and axon outgrowth
through cell–extracellular matrix interactions. The hydrogels
were employed as a 3D platform for culturing both aggregated
and single mammalian motor nerve cells, permitting larger
cell survival as well as a robust extension of motor axons. In
addition, the optical transparency of the hydrogel allowed
simultaneous imaging of live cell functions.
Lin and co-workers have studied different photo-crosslinked
PEG hydrogel for a variety of tissue engineering applications.
In a first study, they explored the ability of PEG hydrogels pre­
pared via photoinduced thiol-ene reaction for 3D culture of
pancreatic β-cells.[11] It was found that the cells encapsulated
in the hydrogel formed naturally spherical clusters and were
then retrieved via rapid chymotrypsin- mediated gel erosion.
The recovered cell spheroids released insulin in response to
glucose treatment, demonstrating the cytocompatibility of
thiol-ene based hydrogels and the enzymatic mechanism of cell
spheroids recovery. More recently, the same authors reported
the preparation of PEG[98] and PEG-peptide[99] hydrogels by
employing visible light (400–700 nm), which is very important
for bioapplications, since UV light can be harmful for cells or
tissues. The photogenerated PEG hydrogels exhibited a high
cytocompatibility by using hMCS and pancreatic MIN6 β-cells.
In the case of PEG-peptide hydrogels, a detailed studied of the
degradation was carried out by employing different peptides,
including chymotrypsin-sensitive peptide.
Bryant and co-workers compared photopolymerizable
thiol-ene PEG and acrylate-based PEG hydrogels for cartilage
1604005  (20 of 29) wileyonlinelibrary.com © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
development.[100] The photo-crosslinked PEG-based hydrogels
were employed for bovine chondrocytes encapsulation and
cultured under free swelling or dynamic compressive loading.
While the acrylate system chondrocytes showed high levels
of intracellular reactive oxygen species, high variability in cell
deformation and low compressive modulus, a similar behavior
was not found for the thiol-norbornene system. In addition, it
was found that the thiol-ene system led to hyaline-like cartilage
production especially under mechanical loading with positive
staining for aggrecan and collagen II and minimal staining
for collagens I and X and collagen catabolism. These experi­
ments concluded that the polymerization mechanism and
consequently the network structure have large effects on the
final properties of the cartilage, especially under mechanical
loading.
Apart from PEG derivatives, other biocompatible polymers,
e.g., gelatin or PVA among others, have also been studied for
the formation of photo-crosslinked hydrogels with applications
in tissue engineering. Lin and co-workers employed gelatin-
based hydrogels for cell encapsulation.[13] Gelatin-hydrogels
were fabricated via thiol-ene photopolymerization from nor­
bornene-functionalized gelatin and different multi-thiol mole­
cules. The cytocompatibility of the gelatin-based hydrogels
was tested via in situ photoencapsulation of hMSCs. It was
found that the crosslinked hydrogels exhibited a faster and
higher degree of cell spreading than the analogous prepared
via free radical polymerization from methacrylate-function­
alized gelatin. Recently, Qin and co-workers developed a suit­
able biomaterial based on PVA for rapid local hemostasis.[101]
Thrombin-receptor-agonist-peptide-6 (TRAP6) was covalently
attached to polyvinyl alcohol (PVA) and photo-crosslinked with
norbornene-functionalized PVA via thiol-ene reaction. Cyto­
toxicity studies using C2C12 myoblasts indicated that both
PVA precursors were non-toxic. Additionally, it was demon­
strated that hemostatic activity of TRAP6 was retained in its
Adv. Mater. 2017, 29, 1604005
www.advancedsciencenews.com
conjugated form, too and it was comparable to free TRAP6
solutions with equal concentrations. For potential clinical appli­
cations, TRAP6-containing photo-crosslinked hydrogels were
developed for local platelet activation and hemostasis, showing
that the hydrogel could activate platelets to a comparable extent
as soluble the TRAP6 control. Teasdale and co-workers reported
the preparation of degradable glycine-based photopolymeriz­
able polyphosphazenes for use as scaffolds for tissue regenera­
tion.[102] Degradation studies under aqueous conditions showed
increasing rates in correlation with the polyphosphazene con­
tent. Preliminary cell studies showed non-cytotoxicity of the
polymers and their degradation products, as well as a good cell
adhesion and proliferation of adipose-derived stem cells.
3.2. Coatings
Polymeric coatings play a very important role in advanced
applications by enhancing the functionality and the lifetime of
numerous materials.[103] Durability, corrosion resistance, anti­
fouling or self-cleaning are among the most desirable proper­
ties for polymeric coatings. The most frequently used polymers
are polyesters, polyurethanes, epoxy resins, phenolic resins,
organosilanes, and other silicon containing coatings polymers.
The combination of organic and inorganic components is one
of the most popular strategies to achieve coatings with optimal
properties. Sangermano and co-workers have studied different
hybrid organic-inorganic coatings based on thiol-ene sys­
tems.[104] A thiol-functionalized zirconium oxocluster was firstly
used as inorganic nanosized building block in the thiol-ene
photopolymerization of allyl pentaerythritol and a trifunctional­
ized thiol derivative in a 1:1 molar mixture to form transparent
and defect-free coatings. Transmission electron microscopy
(TEM) analysis imaged well-dispersed inorganic particles
within the polymeric network without the presence of mac­
roscopic agglomerates. Additionally, XPS analysis and SIMS
depth profile proved the presence of a homogeneously distrib­
uted zirconium oxocluster. By increasing the zirconium oxo­
cluster content in the photocurable formulations, an increase of
Tg values, storage modulus and thermal stability was detected.
A thiol-ene system containing tetraethoxysilane as inorganic
precursor and mercaptopropyl trimethoxysilane as coupling
agent, was also studied. As expected, the inorganic filler gener­
ated improved the mechanical properties and increased the sur­
face hardness. The fabricated films were perfectly transparent,
due to an uniform distribution of the generated silica domains
within the polymeric network on a nanometric scale. The
latter was also demonstrated by TEM analysis. Furthermore,
TEM analysis evidenced that an increase of the coupling agent
concentration led to a reduction of the nanosize dimensions of
the inorganic silica domains.
Holey and co-workers reported one of the first examples
of polymeric pigment coating employing the thiol-ene reac­
tion.[105] Since the thiol-ene reaction is relatively insensitive
to oxygen inhibition, the authors proposed a pigmented thiol-
acrylate system as an alternative to pure acrylate formulations.
The formulation employed consisted of di- and tri-acrylates, a
trithiol crosslinker, calcium lithol rubine as a dye and DMPA as
a photoinitiator. The photopolymerization kinetics and optical
Adv. Mater. 2017, 29, 1604005 © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advmat.de
properties of pigmented thiol-ene coatings were investigated
Review
using photo-DSC, real-time FTIR spectroscopy, colorimetry,
and AFM. It was observed that the pigment had no negative
effect on the unique ability of thiol-ene systems to photo-polym­
erize in air and the photopolymerization rate of pigmented
and non-pigmented systems in air significantly increases with
increasing thiol concentration. AFM and colorimetric data indi­
cated that addition of trifunctional thiol had no negative effect
on pigment dispersion and may increase the dispersion quality.
In addition, it was demonstrated that for the thiol-ene based
pigmented system, only 1 wt% photoinitiator was required to
achieve a similar curing rate that the one employing an acrylate
system containing 10 wt% photoinitiator.
Bio-based monomers have also been employed in UV-cur­
able formulations. Rawlins and co-workers reported the prep­
aration of coatings using vegetable oil monomers.[106] Allyl,
acrylate, and vinyl ether derivatives of castor oil were synthe­
sized and photo-crosslinked with multifunctional thiols via
thiol-ene reactions (D bulb, 1.1 mW cm–2). The generated films
contained approximately 40% vegetable oil on a weight basis.
The materials showed a high solvent resistance and hardness
in combination with excellent adhesion and flexibility. In a fol­
lowing work, soy-based UV-curable coatings were formulated
and their coating physiochemical properties were investigated
in detail.[107] Novel soy-based thiols and enes were employed
for the preparation of networks via UV irradiation (F300 UVA,
1180 mW cm–2). It was found that soy-based thiol-ene coatings
having lower functionality (thiols and enes) have poor UV cur­
ability and coating properties, which was attributed to the lower
crosslink density. In contrast, soy-based thiols and enes with
higher functionality can be UV-cured and better coating film
properties were obtained. The soft coating films showed good
adhesion and impact resistance, yet very poor solvent resistance.
In order to further enhance the soy-based thiol-ene coating
film properties, selected hyper-branched acrylates with poly­
ester cores were incorporated into the thiol-ene formulations.
Keratin-containing coatings were successfully investigated by
Bongiovanni and co-workers.[108] Keratin extracted from wool
was used as a natural reinforcing agent for cross-linked poly­
mers obtained by photopolymerization of thiol-ene systems
(Hg lamp, 28 mW cm–2). The obtained keratin-based photocured
coatings showed significant improvement in terms of thermal
stability, crosslinking density, Tg values, and mechanical proper­
ties. Moreover, a clear increase of the bio-degradability of the
starting thiol-ene polymer matrix was induced by the presence
of the keratin biopolymer as reinforcement.
Yang, Wicks and co-workers prepared UV-curable polyu­
rethane coatings in aqueous dispersions.[109] Multifunctional
thiol- and ene-terminated polyurethane were employed for the
formation of the coatings via UV irradiating (Hg lamp 80 W,
600 mW cm–2) a dispersion of the polymers in water in the
presence of the water soluble initiator Irgacure 2959. FTIR
spectroscopy, photo-DSC and dynamic mechanical analysis
(DMA) measurements were employed for the analysis of the
composition, solution stability, and the mechanical properties
of the coatings. It was found that the UV-cured films prepared
via thiol-ene polymerization exhibited outstanding physical
properties with improvements in comparison with current
UV-curable urethane-acrylate based systems. Hence, this method
wileyonlinelibrary.com (21 of 29)  1604005
 www.advmat.de
allowed for the preparation of high performance UV-curable
Review
polyurethane aqueous coatings based on thiol-ene chem­
istry. Kahraman and co-workers prepared coatings showing
enhanced thermal and flame retardant properties.[110] In their
study, allyldiphenyl phosphine oxide containing thiol-ene based
photocured coatings were employed. The photopolymerization
kinetics of thiol-ene based formulations were investigated by
real-time FTIR spectroscopy. The incorporation of allyl-func­
tionalized phosphone oxide into the polymer chains was con­
firmed by monitoring the conversion of acrylate double bonds
and measuring the gel content of the crosslinked films. As
expected, since the amount of phosphine oxide was increased,
thermal and flame retardant properties of the coatings were
also increased as expected.
As mentioned above, one of the most important properties
of coatings for many applications is their antifouling char­
acter. Hult and co-workers studied thiol-ene based hydrogel
coatings based on PEG for marine antifouling purposes.[111]
A library of hydrogel coatings with different structural com­
position was efficiently completed by modifying the PEG
length, vinylic end-group, and the thiol crosslinker. Particu­
larly, thiol-methacrylate and thiol-allyl systems were studied
as antifouling coatings. Methacrylate-based systems exhib­
ited predominantly homopolymerization, whereas allyl-based
systems reacted more selectively through thiol-ene couplings
reaction. It was found that the ester-free hydrogels possessed
higher hydrolytic stability, while the presence of longer PEG
chains accelerated the degradation process. Protein adsorp­
tion with bovine serum albumin (BSA) and bioassays with
the marine bacteria were carried out in order to evaluate the
antifouling properties. For all experiments, it was found that
longer PEG lengths improved the antifouling properties. Chen
and co-workers reported the preparation of polymer coatings
via chemical vapor deposition polymerization process.[112] The
coatings provided a facile and general route to support thiol-
ene and thiol-yne reactions on a variety of substrate materials.
It was demonstrated that surface functions can be readily acti­
vated via an adequate design of thiol-terminated molecules
such as PEG or peptides (GRGDYC). In addition, controlled
and low-fouling protein adsorptions together with cell attach­
ment experiments showed the associated biological functions.
More recently, PEG-nanogel coatings were prepared by Elbert
and co-workers.[113] In a first step, nanogel solutions were gen­
erated by using the CuAAC to partially polymerize solutions
of multiarm azides and alkyne-functionalized PEG. Subse­
quently, coatings were fabricated using a second reaction, i.e.,
Figure 14.  Schematic illustration of a standard lithography procedure for 2D patterning: a) the photoresist is placed onto a substrate; b) the mold
is pressed onto the phototoresist and irradiated with UV light to induce photo-crosslinking; c) the mold is lifted off the substrate and the replicated
pattern remains on the substrate.
1604005  (22 of 29) wileyonlinelibrary.com © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
UV-induced thiol-yne, for the attachment of the nanogel solu­
tions to mercapto-silanated glass. Protein adsorption was ana­
lyzed by single-molecule counting with total internal reflection
fluorescence (TIRF) microscopy and cell adhesion assays. It
was found that by using high concentrations of a kosmotropic
salt in the nanogel formation, the packing density increased
and the protein adsorption was drastically reduced. Moreover,
it was demonstrated that the developed “pure” PEG coatings
exhibited significantly lower levels of protein adsorption com­
pared to other previously studied coatings, and seemed to
comprise superior surfaces for in vitro biological diagnostics
or other applications requiring strong short-term resistance to
protein adsorption.
3.3. Lithography
In the last years, many strategies have been developed for the
fabrication of micro and nanometer-scale structures, where a
high precision is required. Lithography is a standard method
of printing, which allows the preparation of high-resolution
patterns with feature sizes in the range of 100 nm to several
micrometers. Nanoimprint lithography (NIL),[114] soft litho­
graphy,[115] electron-beam lithography,[116] and dip-pen litho­
graphy[117] for the creation of 2D patterns and multiphoton
lithography[118] for the fabrication of 3D structures, are few
examples of the current methodologies. In this section, we will
focus on photopolymerizable materials based on the chem­
istry previously discussed, which have recently been devel­
oped for the fabrication of 2D and 3D patterns via lithographic
techniques.
3.3.1. 2D Lithography
Nanoimprint lithography is one of the most widely employed
methods for the fabrication of nanometer scale 2D patterns.[115]
The patterns are created by mechanical deformation of imprint
resist and a subsequent crosslinking process. The imprint
resist is typically a polymer based formulation that is usually
cured by UV light during the imprinting (Figure 14). Carter
and co-workers reported for the first time the use of a thiol-ene
based photoresist for nanoimprinting.[6a] Mixtures consisting of
a stoichiometric amount of pentaerythritol tetrakis(3-mercapto­
proprionate) (4) and different enes were employed for the exper­
iments in order to modulate the final mechanical properties of
Adv. Mater. 2017, 29, 1604005
www.advancedsciencenews.com
the material. The photoresists were first coated on a substrate,
compressed with the mold and photocured at 365 nm on the
substrates. The substrates were previously functionalized with
an acrylate-containing silane to ensure adhesion. The composi­
tion of the mold was optimized in order to enhance the release
properties by incorporating 2,2,2-trifluoroethyl methacrylate.
AFM was used to assess the fidelity of the imprint process and
it was found that the thiol-ene based material possessing higher
modulus material exhibited much better resolution and fidelity
in the replicated patterns. Features 45 ± 2 nm in height and 168
± 2 nm in width were achieved.
Step and flash imprint lithography (SFIL) is a novel and
low cost approach to generate relief patterns with sub-100 nm
linewidth.[119] The main differences between SFIL and other
imprint lithography techniques are the nature of the photo­
resist—low viscosity and liquid—and the template, which
must be transparent and rigid. The low viscosity of the liquid
photoresist allows working at lower temperature and pres­
sure, which decreases production costs, and the employment
of a rigid transparent template permits flood exposure of the
photo­polymer to achieve curing. Bowman and co-workers have
investigated thiol-ene mixtures as an appropriate photopolym­
erizable material for SFIL.[7] The photopolymerizable thiol-ene
resist was sandwiched between a nanopatterned mold and the
substrate and exposed to UV light (365 nm). After irradiation,
the mold was separated and AFM and SEM evidenced the for­
mation of nanopatterned replica formed using the thiol-ene for­
mulation. The average width of the imprinted lines was found
to be 110 ± 11 nm. Additionally, a monofunctional acrylate was
used to attach linear polymer films to the created structures
by employing the unreacted thiol present on the surface of the
replicas. The use of the surface presenting thiols as anchoring
molecules possessed the potential of controlling the number of
anchoring groups on the surface by changing the excess of thiol
present while preparing the replicas and therefore, controlling
the chain density on the surface. In this case, the formed rep­
licas were modified with polymers with thicknesses of up to
45 nm. Clark and co-workers employed a similar thiol-ene photo­
resist for the organization of liquid crystals on sub-micrometer
scale topographic patterns via SFIL.[6b] A small amount of thiol-
ene based resist was placed onto a glass substrate, pressed
against and exposed to UV light (365 nm). Sub-micrometer
lines, squares and checkerboard patterns were successfully cre­
ated. The organization of liquid crystal was studied using depo­
larizing transmission light microscopy and a planar bistable
organization was observed for 2 and 4 µm wide square grid and
with 600 nm scale square and checkerboard patterns.
In soft lithography, an elastomeric mold—generally a
poly(dimethylsiloxane) (PDMS) stamp—with patterned struc­
tures on its surface is employed to generate structures with
feature sizes in the range of sub-micrometers. Hawker and
co-workers developed an easy method for the preparation of
sub-100 nm features via soft imprinting.[120] In particular, PEG
and poly(siloxane)-based photoresists were examined as suit­
able materials for soft imprinting. Thiol-functionalized PEG
and poly(siloxane) were crosslinked with different multifunc­
tional enes via photoinduced thiol-ene chemistry. The modular
nature allowed for the physical and mechanical properties of
the features to be tuned by selecting the appropriated starting
Adv. Mater. 2017, 29, 1604005 © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advmat.de
materials. The same authors have also developed a new stamp
Review
for soft lithography based on poly[(3-mercaptopropyl)methyl­
siloxane].[121] The stamps were prepared by crosslinking triallyl
cyanurate (4) and ethoxylated bisphenol A dimethacrylate (18)
via thiol-ene chemistry. The materials were found to be stable
up to approximately 225 °C and, as characterized by TGA, do
not undergo any phase transitions between –80 and 200 °C
as well as being optically clear and transparent above 300 nm.
These properties, along with the suitable mechanical proper­
ties, yielded materials suitable for soft lithography applications.
Moreover, surface chemical modification with a fluorinated
silane was performed in order to minimize photoresist adhe­
sion. The stamps were tested to accomplish pattern replica­
tion and features from the micrometer to sub-100 nm scale
were successfully achieved. Yin and co-workers developed
a novel hybrid photoresist based on thiol-ene photopolym­
erization, which was employed as a mold for nanoimpriting
lithography.[122] The photoresist consisted of a mercaptopropyl
polyhedral oligomeric silsesquioxane and a trimethacrylate
derivative as the crosslinker. The hybrid material exhibited a
variety of characteristics desirable for nanoimprint lithography,
such as good coating ability, reduced viscosity, low shrinkage,
increased thermal stability, and rapid photopolymerization in
the presence of a trace of photoinitiator. By using poly(methyl
methacrylate) (PMMA) as the transfer film, the polysiloxane-
based photoresist was employed in the fabrication of a pat­
terned silicon substrate resulting in a high-resolution pattern
with feature sizes in the range of 100 nm to several microme­
ters. In a following investigation, the same authors reported the
use of a fluorinated photoresist as soft molds.[123] In this case, a
of fluorinated mercaptopropyl polyhedral oligomeric silsesqui­
oxane was crosslinked with 2,2,3,3,4,4,5,5-octafluoro-1,6-hexyl
diacrylate. The obtained fluorinated hybrid also exhibited low
viscosity, a low bulk volumetric shrinkage and a good resist­
ance to oxygen inhibition as well as high transparency to UV
light and resistance to organic solvents. The good mechanical
properties and low surface energy of the fluorinated polymers
provided a clean mold release. Therefore, the obtained molds
could be used repeatedly without any surface treatment and
exhibited a high resolution patterning capacity with feature
sizes in the range of 200 nm to several micrometers.
Bowman and co-workers demonstrated mechano-photopat­
terning on a photoresponsive elastomer based on thiol-ene
chemistry.[124] Mechano-photopatterning consists of photopat­
terning of a elastomeric network under mechanical strain and
provides a facile approach to fabricate complex topographical
features using elementary irradiation schemes. A photo­
responsive material deformed in two dimensions and irradiated
through a mask, results in a transparent material with topo­
graphy that reflects the concentric rings of the mask. In this
work, addition–fragmentation chain transfer (AFCT)-capable
functional groups were incorporated in the backbone of an
elastomeric covalent adaptable network. Particularly, the photo­
resists consisted of of pentaerythritol tetrakis(3-mercaptopro­
pionate) (4) and ethylene glycol bis(3-mercaptopropionate),
together with 2-methylene-propane-1,3-bis(thioethyl acrylate).
The latter derivative contains allyl sulfide groups facilitating
bond rearrangement via radical mediated AFCT. A film of
the material was uniaxially strained and irradiated (Hg lamp,
wileyonlinelibrary.com (23 of 29)  1604005
 www.advmat.de
365/405 nm) through a photomask to project a hexagonal array
Review
onto the sample. The irradiated regions underwent photo­
induced plasticity, resulting in a well-defined hexagonal pattern
commensurate with the mask.
3.3.2. 3D Lithography: Direct Laser Writing (DLW)
Multiphoton lithography, more commonly known as the
direct laser writing (DLW) technique, is one of the most pow­
erful tools to obtain 3D microstructures with high resolution.
The DLW approach relies on a multi-photon absorption pro­
cess in a material which is transparent at the wavelength of
the laser employed for the writing. By scanning and properly
modulating the laser, photo-crosslink occurs only at the focal
spot of the laser and can be controlled to create an arbitrary
3D microstructure. To date, several negative photoresist sys­
tems have been employed for DLW, most of them based on
free radical polymerization (acrylate-based photoresist) or
photoinduced cationic polymerization (epoxy photoresists).
In the last years, our group has pioneered novel and alterna­
tive phototriggered reactions to induce photo-crosslinking
and create 3D microstructures via DLW. In our first study, 3D
microstructures were fabricated employing the photoinduced
thiol-ene polymerization.[8] The photoresists employed con­
sisted of a two-photon (2P) photoinitiator and multifunctional
thiols and olefins. The experiments were performed using a
Nanoscribe “Photonic Professional” setup containing a femto­
second laser emitting pulses at 780 nm wavelength. The laser
power and the writing speed were set to 8 mW and 100 µm s–1,
respectively. Woodpile photonic crystals with 22 layers and a
rod distance of 2 µm each consecutive layer and a spacing of
700 nm in axial direction were fabricated. The written struc­
tures exhibited a base dimension of 20 µm × 20 µm and a
height of 12.8 µm. The remaining photoreactive groups of the
structures were employed for subsequent functionalization,
as discussed in Section 2.2.1. Griesser and co-workers have
also used photoinduced thiol-ene reaction for the preparation
3D macrostructures.[125] Here, residual double bonds in ring-
opening metathesis polymerization (ROMP) poly(norbornene)
derivatives enabled photoinduced crosslinking via a thiol–ene
reaction. A tetrafunctional thiol derivate (4) was employed as
crosslinker and 1,5-bis(4-(dimethylamino) phenyl penta-1,4-
diyn-3-one (N-DPD) as a 2P photoinitiator. The experiments
were carried out with a Nanoscribe “Photonic Professional”,
too. Rod-like structures were inscribed in a 100 mm thick
polymer layer with a laser power of 7.5 mW and a rate of
100 µm s–1. The obtained structures had a diameter of 10 µm
with an average structure height of 2 µm. Liska and co-workers
employed flexible thiol-ene based hybrid materials based on
epoxy and acetoxy polysiloxane matrix for the preparation of
optical waveguides.[126] An amplified ultrafast Ti/sapphire
laser system from Spectra Physics (Mai Tai–Spitfire combi­
nation) was employed for their experiments providing pulses
in the range of 800 nm wavelength and a pulse duration of a
130–150 fs. An optimization of the ratio of thiol/ene moieties,
thermal analysis, as well as investigations regarding the refrac­
tive index of the materials, were reported. The latter is quintes­
sential for successful waveguiding.
1604005  (24 of 29) wileyonlinelibrary.com © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
3D mesostructures with a height of up to 1 mm and
micrometer feature size were also fabricated by our group via
DLW.[42] A functional photoresist based on the photoinduced
reaction between thiols and alkynes was employed in this case.
The structures were fabricated by employing yet again the
commercial Nanoscribe set-up containing a femtosecond laser
(780 nm). In order to determine the achievable axial resolution
of the developed photoresist, woodpile photonic crystals were
created and investigated as complex 3D benchmark structures.
The wood piles were fabricated with a writing speed of 1 cm s−1,
a total number of 10 periods (40 layers), a rod distance of 3 µm,
and a layer distance of 1.13 µm as fixed parameters and the
laser power was varied. Subsequently, reflectance spectra of the
fabricated woodpiles powers were recorded in order to investi­
gate the corresponding photonic stop bands. No stop band was
visible for high average laser powers during fabrication, indi­
cating that the corresponding structure were most probably not
resolved, while a stop band could be assigned for lower powers.
Furthermore, by decreasing writing powers, the filling fraction
of the woodpile is also decreased and the corresponding stop
band was shifted to lower wavelengths.
Further, woodpile photonic crystals were fabricated by our
group by employing a photoinduced Diels–Alder reaction
between o-quinodimethanes and maleimides via DLW.[68] In
this case, the DLW experiments were conducted using a home-
built setup that has been previously described in detail[127] and
the laser was tuned to 700 nm center wavelength. The fabri­
cated woodpiles based on the Diels–Alder photoresist consisted
of a total of 20 layers (5 periods) with variable rod spacing
and a 20 µm × 20 µm footprint (Figure 15). The laser power
was varied between 2.7 and 3.6 mW with a writing speed of
100 µm s−1, while the rod spacing was selected between
700 and 500 nm. Transmission and reflection spectra of wood­
pile photonic crystals were also recorded and it was found
that photonic woodpiles with a rod spacing between 700 and
600 nm exhibited a stop band in the visible (Figure 15d). The
photonic stop bands were, as expected, clearly shifted to lower
wavelengths for decreased rod spacing. Furthermore, spatially
resolved surface patterning of covalently bonded functional
molecules on fabricated structures was also demonstrated (see
Section 2.2.3).
Bowman and co-workers also employed DLW for 3D photo­
fixation in Diels–Alder networks.[66] 3D fabrication of non-
continuous structures by employing a negative photoresist
is often challenging. In a normal process, each layer acts as
support for the next layer, and hanging parts can collapse due
the increase of the density during crosslinking. In order to cir­
cumvent this problem, the authors present a novel approach
by using a reversibly crosslinking polymer as a photoresist. A
Diels–Alder network was employed as a temporary solid scaf­
fold which can be permanently crosslinked via a photoinitiated
mediated thiol-ene reaction between the Diels–Alder adduct
itself and embedded thiols in the exposed regions. The unex­
posed region were subsequently converted into a low-viscosity
liquid by heating and removed simply by increasing the tem­
perature of the system. Photo-crosslinking was carried out by
irradiation of the initial Diels–Alder network with a 740 nm
femtosecond laser and depolymerization of the non-irradiated
regions took place at 105 °C. Complex shapes, such as eight
Adv. Mater. 2017, 29, 1604005
www.advancedsciencenews.com
Figure 15. SEM images of a woodpile photonic crystal fabricated via
photoinduced Diels–Alder. a) top view; b) entire fabricated structure;
c) interior of the woodpile after focused ion beam milling. Scale bars are
1 µm, 2 µm, and 200 nm, respectively. d) Light microscope images in
transmission and reflection mode of woodpile photonic crystals. Adapted
with permission.[68] Copyright 2014, Wiley-VCH.
freely rotating interlocked rings and log pile structures, were
written into the polymer network via DLW by employing the
mentioned approach (Figure 16).
4. Conclusions and Outlook
During the last years there has been growing interest in the
fabrication of polymeric networks due to their potential appli­
cations in a wide range of fields. The use of light to generate
polymeric networks allows the fine-tuning of the structure
and properties, particularly with spatiotemporal control. One
large field of applications concerns three-dimensional (3D)
printing, which is a major trend worldwide. It allows for
fabricating structures that were difficult or even impossible
to generate previously. 3D micro-optics are an example.[128]
One specific advantage is that fabricated structures no longer
need to be stored. Critically, products can be individualized
without additional cost. Thus, multi-billion dollar markets
with large growth rates are anticipated. Some foresee that in
ten years’ time, 10% of all manufactured goods will be 3D
printed. Eventually, one would like to 3D print a wide array
of materials, including entire functional devices. Getting there
requires an enormous boost regarding spatial printing reso­
lution, printing speed, multi-material printing as well as the
Adv. Mater. 2017, 29, 1604005 © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advmat.de
Review
Figure 16.  SEM images of variable 3D microstructures fabricated from a
Diels–Alder network as a temporary solid scaffold which were permanent
crosslinked via a photoinitiated thiol−ene reaction by DLW: a) interlocked
rings; b) log pile. Scale bar 200 and 40 µm, respectively. Adapted with
permission.[66a] Copyright 2012, Wiley-VCH.
3D printing of functional structures. Early examples for the
latter have only emerged recently,[129] and photopolymers have
played a key role in this area and will very likely be important
in the future, too.
Acrylate-based photoresists together with epoxy photo­
resists have dominated the field until today. Nevertheless, new
light-induced modular reactions have emerged as promising
alternatives, offering new prospects for altering the network
structure and, importantly, functionalization. The use of these
recent light-induced approaches has several advantages, for
example better control of the network structures and the pos­
sibility to modulate the final properties. Clearly, photoinduced
thiol-ene reactions possess specific benefits including minimal
oxygen inhibition and lower shrinkage compared to acrylate
photopolymerizations (Section 2.1.1). By adequate chemical
modifications, either in the catalytic system or in the reactive
groups, it is possible to induce photocontrol in classical, effi­
cient and in principle also in thermal reactions, such as thio-
Michael (Section 2.1.2), CuAAC (Section 2.2.1) or Diels–Alder
(Section 2.2.3) cycloadditions and successfully employ them for
the preparation of networks. In addition, the introduction of
new properties such as fluorescence or reversibility is also pos­
sible by employing light-induced processes such as the NITEC
wileyonlinelibrary.com (25 of 29)  1604005
 www.advmat.de
reaction (Section 2.2.2) or dimerization of photochromic groups
Review
(Section 2.3), respectively.
Although the development of these recent light-induced
approaches has led to substantial advances in the fabrication
of networks and their properties, outstanding key challenges
remain. As an example, a large variety of photo-induced reac­
tions still relies almost exclusively on the use of low-wavelength
high-energy (UVB irradiation), which might be an issue in bio­
logical applications. Advances regarding the development of
systems utilizing visible-light-induced chemistry have already
been achieved by us, yet are limited to just above 420 nm
wavelength.[130] Very recently, we demonstrated that the use
of upconversion technology may be a viable alternative to
chromophore based red-shifting,[2d] although this possibility is
currently fully unexplored in photochemically driven network
formation. Thus, the quest for efficient visible-light-induced
systems remains one of the current key goals. Another chal­
lenge, especially in the field of 3D lithography, consists of the
improvement of the spatial resolution in the fabrication of 3D
microstructures via DLW beyond the diffraction limit. One of
the approaches explored is based on the concept of stimulated
emission depletion (STED) known from fluorescence micros­
copy.[131] By employing the STED approach, the lateral and axial
resolutions have been improved.[132] However, further inves­
tigations of new photoinduced systems that can be efficiently
depleted are essential to continue decreasing the current fea­
ture sizes, not only for the encoding of flat substrates but criti­
cally in three dimensions, where feature sizes of down to 5 nm
line width remain out of reach—while such feature sizes have
been shown in STED optical microscopy. Besides sub-diffrac­
tion resolution, the controlled, efficient and ideally spatially
resolved de-polymerization of crosslinked structures (including
those prepared by DLW) is still a major challenge. To remove a
photo-cured resist, generally, harsh conditions—including high
temperature, strong acid or strong base—are necessary, which
cause a global degradation of the network. Moreover, such con­
ditions are often not consistent with other fabrication process
steps that may follow. In order to introduce the crucial spa­
tial control of the degradation process, a combination of both
light-driven network formation and light-driven degradation is
required. Although few examples of networks based on revers­
ible photodimerization of different groups have been reported,
a system relying on efficient and high-resolution formation and
degradation of polymeric networks remains elusive. Finally, the
chemical microstructure of the prefabricated polymer strands
employed to photochemically generate networks are, at present,
poor. The recent advances in the sequence-defined macromo­
lecular construction of polymers via photochemical methods[133]
entail the enticing prospect that sequence-defined polymers
with precision placed functionalities along the lateral polymer
chain may allow the fine tuning of polymer network properties
with today unseen definition and precision, including in combi­
nation with STED-type coding processes.
Acknowledgements
C.B.-K. and M.W. acknowledge funding from the Karlsruhe Institute
of Technology (KIT) via the Helmholtz association (STN program).
C.B.-K additionally acknowledges funding by the German Research
1604005  (26 of 29) wileyonlinelibrary.com © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
Council (DFG) via their large equipment granting scheme and the
Sonderforschungsbereich (1176). E.B. acknowledges the Alexander
von Humboldt Foundation for financial support. C.B.-K. acknowledges
continued support from the Queensland University of Technology (QUT).
Note: The biography section was corrected on April 10, 2017 after initial
publication online.
Received: July 28, 2016
Revised: October 18, 2016
Published online: January 11, 2017
[1] IUPAC, Pure Appl.Chem. 1996, 68, 2287.
[2] a) Y.-Q. Zou, L.-Q. Lu, L. Fu, N.-J. Chang, J. Rong, J.-R. Chen,
W.-J. Xiao, Angew. Chem. Int. Ed. 2011, 50, 7171; b) M. Majek,
A. Jacobi von Wangelin, Angew. Chem. Int. Ed. 2015, 54, 2270;
c) J. O. Mueller, F. G. Schmidt, J. P. Blinco, C. Barner-Kowollik,
Angew. Chem. Int. Ed. 2015, 54, 10284; d) P. Lederhose, Z. Chen,
R. Müller, J. P. Blinco, S. Wu, C. Barner-Kowollik, Angew. Chem.
Int. Ed. 2016, 55, 12195.
[3] a) C. Decker, Acta Polym. 1994, 45, 333; b) C. Decker, Prog.
Polym. Sci. 1996, 21, 593; c) C. Decker, Polym. Int. 1998, 45,
133; d) E. Andrzejewska, Prog. Polym. Sci. 2001, 26, 605;
e) J. P. Fouassier, J. Lalevée, Polymers 2014, 6, 2588.
[4] a) C. E. Hoyle, R. D. Hensel, M. B. Grubb, Polym. Photochem.
1984, 4, 69; b) C. E. Hoyle, R. D. Hensel, M. B. Grubb,
J. Polym. Sci., Polym. Chem. Ed. 1984, 22, 1865; c) N. B. Cramer,
C. N. Bowman, J. Polym. Sci., Part A: Polym. Chem. 2001, 39, 3311;
d) N. B. Cramer, J. P. Scott, C. N. Bowman, Macromolecules 2002,
35, 5361; e) C. E. Hoyle, T. Y. Lee, T. Roper, J. Polym. Sci., Part A:
Polym. Chem. 2004, 42, 5301; f) N. B. Cramer, C. N. Bowman,
Thiol-X Chemistries in Polymer and Materials Science,.
(Ed: A. B. Lowe, C. N. Bowman), The Royal Society of Chem-
istry, 2013; g) C. E. Hoyle, C. N. Bowman, Angew. Chem. Int. Ed.
2010, 49, 1540; e) C. E. Hoyle, A. B. Lowe, C. N. Bowman, Chem.
Soc. Rev. 2010, 39, 1355; h) M. J. Kade, D. J. Burke, C. J. Hawker,
J. Polym. Sci., Part A: Polym. Chem. 2010, 48, 743; i) A. B. Lowe,
Polym. Chem. 2010, 1, 17; j) A. B. Lowe, Polym. Chem. 2014, 5, 4820.
[5] N. B. Cramer, T. Davies, A. K. O’Brien, C. N. Bowman,
Macromolecules 2003, 36, 4631.
[6] a) E. C. Hagberg, M. Malkoch, Y. Ling, C. J. Hawker, K. R. Carter,
Nano Lett. 2007, 7, 233; b) Y. W. Yi, V. Khire, C. N. Bowman,
J. E. Maclennan, N. A. Clark, J. Appl. Phys. 2008, 103, 093518.
[7] V.S. Khire, Y. Yi, N.A. Clark, C. N. Bowman, Adv. Mater. 2008, 20,
3308.
[8] A. S. Quick, J. Fischer, B. Richter, T. Pauloehrl, V. Trouillet,
M. Wegener, C. Barner-Kowollik, Macromol. Rapid Commun. 2013,
34, 335.
[9] A. R. Davis, K. R. Carter, Macromolecules 2015, 48, 1711.
[10] a) A. A. Aimetti, A. J. Machen, K. S. Anseth, Biomaterials 2009,
30, 6048; b) B. D. Fairbanks, M. P. Schwartz, A. E. Halevi,
C. R. Nuttelman, C. N. Bowman, K. S. Anseth, Adv. Mater. 2009,
21, 5005; c) D. D. McKinnon, A. M. Kloxin, K. S. Anseth, Biomater.
Sci. 2013, 1, 460.
[11] C. C. Lin, A. Raza, H. Shih, Biomaterials 2011, 32, 9685.
[12] W. M. Gramlich, I. L. Kim, J. A. Burdick, Biomaterials 2013, 38, 9803.
[13] Z. Mu∼noz, H. Shih, C. C. Lin, Biomater. Sci. 2014, 2, 1063.
[14] X. H. Qin, K. Labuda, J. Chen, V. Hruschka, A. Khadem, R. Liska,
H. Redl, P. Slezak, Adv. Funct. Mater. 2015, 25, 6606.
[15] S. Baudis, D. Bomze, M. Markovic, P. Gruber, A. Ovsianikov,
R. Liska, J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 2060.
[16] Z. Li, J. Torgersen, A. Ajami, S. Muhleder, X. Qin, W. Husinsky,
W. Holnthoner, A. Ovsianikov, J. Stampfl, R. Liska, RSC Adv. 2013,
3, 15939.
Adv. Mater. 2017, 29, 1604005
www.advancedsciencenews.com
[17] a) T. F. Scott, A. D. Schneider, W. D. Cook, C. N. Bowman, Science
2005, 308, 1615; b) W. D. Cook, S. Chausson, F. Chen, L. L. Pluart,
C. N. Bowman, T. F. Scott, Polym. Int. 2008, 57, 469.
[18] a) C. Gorsche, T. Koch, N. Moszner, R. Liska, Polym. Chem. 2015,
6, 2038; b) P. Gauss, S. C. Ligon-Auer, M. Griesser, C. Gorsche,
H. Svajdlenkova, T. Koch, N. Moszner, R. Liska, J. Polym. Sci., Part
A: Polym. Chem. 2016, 54, 1417.
[19] S. Clark Ligon, K. Seidler, C. Gorsche, M. Griesser, N. Moszner,
R. Liska, J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 394.
[20] C. Gorsche, K. Seidler, P. Knaack, P. Dorfinger, T. Koch, J. Stampfl,
N. Moszner, R. Liska, Polym. Chem. 2016, 7, 2009.
[21] N. B. Cramer, J. P. Scott, C. N. Bowman, Macromolecules 2002, 35,
5361.
[22] a) N. B. Cramer, C. N. Bowman, J. Polym. Sci., Part A: Polym.
Chem. 2001, 39, 3311; b) A. K. O’Brien, N. B. Cramer,
C. N. Bowman, J. Polym. Sci., Part A: Polym. Chem. 2006, 44,
2007; c) Y. Hao, H. Shih, Z. Muňoz, A. Kemp, C. C. Lin, Acta Bio-
mater. 2014, 10, 104; d) Y. Hao, C. C. Lin, J. Biomed. Mater. Res. A
2014, 102, 3813.
[23] a) A. E. Rydholm, C. N. Bowman, K. S. Anseth, Biomaterials 2005,
26, 4495; b) A. E. Rydholm, S. K. Reddy, K. S. Anseth, C. N. Bowman,
Biomacromolecules 2006, 7, 2827; c) A. E. Rydholm, N. L. Held,
C. N. Bowman, K. S. Anseth, Macromolecules 2006, 39, 7882.
[24] C. N. Salinas, K. S. Anseth, Macromolecules 2008, 41, 6019.
[25] C. R. Langford, D. W. Johnson, N. R. Cameron, Polym. Chem.
2014, 5, 6200.
[26] A. Chiappone, C. Gerbaldi, I. Roppolo, N. Garino, R. Bongiovanni,
Polymer 2015, 75, 6472.
[27] M. Retailleau, A. Ibrahim, C. Croutxé-Barghorn, X. Allonas, Prog.
Org. Coat. 2016, 100, 51.
[28] a) T. Y. Lee, J. Carioscia, Z. Smith, C. N. Bowman, Macromolecules
2007, 40, 1473; b) T. Y. Lee, Z. Smith, S. K. Reddy,
N. B. Cramer, C. N. Bowman, Macromolecules 2007, 40, 1466;
c) N. B. Cramer, C. Couch, K. M. Schreck, J. A. Carioscia,
J. E. Boulden, J. W. Stansbury, C. N. Bowman, Dent. Mater. 2010,
26, 21; d) N. B. Cramer, C. Couch, K. M. Schreck, J. A. Carioscia,
J. E. Boulden, J. W. Stansbury, C. N. Bowman, Dent. Mater. 2010,
26, 799; e) J. E. Boulden, N. B. Cramer, K. M. Schreck, C. L. Couch,
C. Bracho-Troconisa, J. W. Stansbury, C. N. Bowman, Dent. Mater.
2011, 27, 267.
[29] J. Shin, H. Matsushima, C. M. Comer, C. N. Bowman, C. E. Hoyle,
Chem. Mater. 2010, 22, 2616.
[30] a) J. Shin, H. Matsushima, J. W. Chan, C. E. Hoyle, Macromolecules
2009, 42, 3294; b) H. Matsushima, J. Shin, C. N. Bowman,
C. E. Hoyle, J. Polym. Sci., Part A: Polym. Chem. 2010, 48, 3255.
[31] B. J. Sparks, E. F. T. Hoff, L.T. P. Hayes, D. L. Patton, Chem. Mater.
2012, 24, 3633.
[32] a) M. Sangermano, M. Cerrone, G. Colucci, I. Roppolo,
R. A. Ortiz, Polym. Int. 2010, 59, 1046; b) M. Flores, A. M. Tomuta,
X. Fernández-Francos, X. Ramis, M. Sangermano, A. Serra,
Polymer 2013, 54, 5473.
[33] a) A. Mautner, X. Qin, H. Wutzel, S. C. Ligon, B. Kapeller,
D. Moser, G. Russmueller, J. Stampfl, R. Liska, J. Polym. Sci.,
A: Polym. Chem. 2013, 51, 203; b) A. Mautner, B. Steinbauer,
S. Orman, G. Russmueller, K. Macfelda, T. Koch, J. Stampfl,
R. Liska, J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 1987.
[34] W. Xi, H. Peng, A. Aguirre-Soto, C. J. Kloxin, J. W. Stansbury,
C. N. Bowman, Macromolecules 2014, 47, 6159.
[35] X. Zhang, W. Xi, C. Wang, M. Podgórski, C. N. Bowman, ACS
Macro Lett. 2016, 5, 229.
[36] a) A. B. Lowe, C. E. Hoyle, C. N. Bowman, J. Mater. Chem. 2010,
20, 4745; b) R. Hoogenboom, Angew. Chem. Int. Ed. 2010, 49,
3415; c) A. B. Lowe, Polymer 2014, 22, 5517.
[37] B. D. Fairbanks, E. A. Sims, K. S. Anseth, C. N. Bowman,
Macromolecules 2010, 43, 113.
Adv. Mater. 2017, 29, 1604005 © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advmat.de
[38] B. D. Fairbanks, T. F. Scott, C. J. Kloxin, K. S. Anseth,
Review
C. N. Bowman, Macromolecules 2009, 42, 211.
[39] J. W. Chan, H. Zhou, C. E. Hoyle, A. B. Lowe, A. B. Chem. Mater.
2009, 21, 1579.
[40] J. W. Chan, J Shin, C. E. Hoyle, C. N. Bowman, A. B. Lowe, Macro-
molecules 2010, 43, 4937.
[41] M. Lomba, L. Oriol, R. Alcala, C. Sanchez, M. Moros, V. Grazu,
J. L. Serrano, J. M. De la Fuente, Macromol. Biosci. 2011, 11,
1505.
[42] A. S. Quick, A. de los Santos Pereira, M. Bruns, T. Bückmann,
C. Rodriguez-Emmenegger, M. Wegener, C. Barner-Kowollik, Adv.
Funct. Mater. 2015, 25, 3735.
[43] R. Cervera-Procas, C. Sánchez-Somolinos, J. L. Serrano,
A. Omenat, Macromol. Rapid Commun. 2013, 34, 498.
[44] a) A. Oesterreicher, S. Ayalur-Karunakaran, A. Moser,
F. H. Mostegel, M. Edler, P. Karschnitz, G. Pinter, G. Trimmel,
T. Griesser, J. Polym. Sci. Part A: Polym. Chem. 2016, 54, 3484;
b) A. Oesterreicher, J. Wiener, M. Roth, A. Moser, R. Gmeine,
M. Edler, G. Pinter, T. Griesser, Polym. Chem. 2016, 7, 5169.
[45] a) X. Gong, W. Wen, P. Sheng, Langmuir 2009, 25, 7072;
b) R. A. Prasath, M. T. Gokmen, P. Espeel, F. E. Du Prez, Polym.
Chem. 2010, 1, 685; c) E. Lovelady, S. D. Kimmins, J. Wu,
N. R. Cameron, Polym. Chem. 2011, 2, 559.
[46] M. A. Daniele, A. A. Adams, J. Naciri, S. H. North, F. S. Ligler,
Biomaterials 2014, 35, 1845.
[47] a) H. Y. Park, C. J. Kloxin, T. F. Scott, C. N. Bowman, Macromolecules
2010, 43, 10188; b) S. Ye, N. B. Cramer, I. R. Smith, K. R. Voigt,
C. N. Bowman, Macromolecules , 2011, 44, 9084; c) H. Y. Park,
C. J. Kloxin, M. F. Fordney, C. N. Bowman,Macromolecules 2012,
45, 564.
[48] H. C. Kolb, M. G. Finn, K. B. Sharpless, Angew. Chem. Int. Ed.
2001, 40, 2004.
[49] a) J. F. Lutz, Angew. Chem. Int. Ed. 2007, 46, 1018; b) W. H. Binder,
R. Sachsenhofer, Macromol. Rapid Commun. 2007, 28, 15;
c) W. H. Binder, R. Sachsenhofer, Macromol. Rapid Commun. 2008,
29, 952; d) M. Meldal, C. W. Tornøe, Chem. Rev. 2008, 108, 2952;
e) C. Barner-Kowollik, F. E. Du Prez, P. Espeel, C. J. Hawker,
T. Junkers, H. Schlaad, W. Van Camp, Angew. Chem. Int. Ed. 2011,
50, 60.
[50] a) P. A. C. Dasilva, P. G. David, Bull. Chem. Soc. Jpn. 1982, 5,
2673; b) P. G. David, P. A. C. Dasilva, Bull. Chem. Soc. Jpn. 1985,
58, 3566; c) S. C. Ritter, B. Konig, Chem. Commun. 2006, 45, 4694;
d) M. A. Tasdelen, Y. Yagci, Tetrahedron Lett. 2010, 51, 6945.
[51] B. J. Adzima, Y. Tao, C. J. Kloxin, C. A. DeForest, K. S. Anseth,
C. N. Bowman, Nat. Chem. 2011, 3, 256.
[52] T. Gong, B. J. Adzima, N. H. Baker, C. N. Bowman, Adv. Mater.
2013, 25, 2024.
[53] a) A. Baranek, H. B. Song, M. McBride, P. Finnegan,
C. N. Bowman, Macromolecules 2016, 49, 1191; b) A. Baranek,
H. B. Song, M. McBride, P. Finnegan, C. N. Bowman, Polym.
Chem. 2016, 7, 603.
[54] M. K. McBride, T. Gong, D. P. Nair, C. N. Bowman, Polymer 2014,
55, 5880.
[55] A. A. Alzahrani, D. P. Nair, D. J. Smits, M. Saed, C. M. Yakacki,
C. N. Bowman, Chem. Mater. 2014, 26, 5303.
[56] a) Y. Wang, C. I. Rivera Vera, Q. Lin, Org. Lett. 2007, 9, 4155;
b) Y. Wang, W. J. Hu, W. Song, R. K. V. Lim, Q. Lin, Org. Lett.
2008, 10, 3725; c) W. Song, Y. Wang, J. Qu, M. M. Madden, Q. Lin,
Angew. Chem. Int. Ed. 2008, 47, 2832; d) Y. Yu, R. K. V. Lim, Q. Lin,
Chem.–Eur. J. 2010, 16, 13325; e) Y. Wang, W. Song, W. J. Hu,
Q. Lin, Angew. Chem. Int. Ed. 2009, 48, 5330; f) Z. Li, L. Qian,
L. Li, J. C. Bernhammer, H. V. Huynh, J. S. Lee, S. Q. Yao, Angew.
Chem. Int. Ed. 2016, 55, 2002.
[57] J. S. Clovis, A. Eckell, R. Huisgen, R. Sustmann, Chem. Ber. 1967,
100, 60.
wileyonlinelibrary.com (27 of 29)  1604005
 www.advmat.de
Review
[58] H.-P. M. de Hoog, M. Nallani, B. Liedberg, Polym. Chem. 2012, 3,
302.
[59] a) J. Wang, W. Zhang, W. Song, Y. Wang, Z. Yu, J. Li, M. Wu,
L. Wang, J. Zang, Q. Lin, J. Am. Chem. Soc. 2010, 132, 14812;
b) Z. Yu, R. K. V. Lim, Q. Lin, Chem.–Eur. J. 2010, 16, 13325;
c) Z. Yu, L. Y. Ho, Z. Wang, Q. Lin, Bioorg. Med. Chem. 2011, 21,
5033.
[60] a) M. Dietrich, G. Delaittre, J. P. Blinco, A. J. Inglis, M. Bruns,
C. Barner-Kowollik, Adv. Funct. Mater. 2012, 22, 304; b) E. Blasco,
M. Pinol, L. Oriol, B. V. K. J. Schmidt, A. Welle, V. Trouillet,
M. Bruns, C. Barner-Kowollik, Adv. Funct. Mater. 2013, 23,
4011; c) C. Rodriguez-Emmenegger, C. M. Preuss, B. Yameen,
O. Pop-Georgievski, M. Bachmann, J. O. Mueller, M. Bruns,
A. S. Goldmann, M. Bastmeyer, C. Barner-Kowollik, Adv. Mater.
2013, 25, 6123.
[61] J. O. Mueller, N. K. Guimard, K. K. Oehlenschlaeger, F. G. Schmidt,
C. Barner-Kowollik, Polym. Chem. 2014, 5, 1447.
[62] A. Hufendiek, A. Carlmark, M. A. R. Meier, C. Barner-Kowollik, ACS
Macro Lett. 2016, 5, 139.
[63] Y. Sugawara, N. Jasinski, M. Kaupp, A. Welle, N. Zydziak,
E. Blasco, C. Barner-Kowollik, Chem. Commun. 2015, 51, 13000.
[64] Y. Sugawara, K. Hiltebrandt, E. Blasco, C. Barner-Kowollik,
Macromol. Rapid Commun. 2016, 37, 1466.
[65] Y. Fan, C. Deng, R. Cheng, F. Meng, Z. Zhong, Biomacromolecules
2013, 14, 2814.
[66] a) B. J. Adzima, C. J. Kloxin, C. A. DeForest, K. S. Anseth,
C. N. Bowman, Macromol. Rapid Commun. 2012, 33, 2092;
b) G. J. Berg, T. Gong, C. R. Fenoli, C. N. Bowman, Macromolecules
2014, 47, 3473.
[67] a) T. Gruendling, K. K. Oehlenschlaeger, E. Frick, M. Glassner,
C. Schmid, C. Barner-Kowollik, Macromol. Rapid Commun. 2011,
32, 807; b) M. Glassner, K. Oehlenschlaeger, T. Gruendling,
C. Barner-Kowollik, Macromolecules 2011, 44, 4681; c) M. Winkler,
J. O. Mueller, K. K. Oehlenschlaeger, L. Montero de Espinosa,
M. A. R. Meier, C. Barner-Kowollik, Macromolecules 2012, 45, 5012;
d) K. K. Oehlenschlaeger, J. O. Mueller, N. B. Heine, M. Glassner,
N. K. Guimard, G. Delaittre, F. G. Schmidt, C. Barner-Kowollik, Angew.
Chem. Int. Ed. 2013, 52, 762; e) T. Pauloehrl, G. Delaittre, V. Winkler,
A. Welle, M. Bruns, H. G. Boerner, A. M. Greiner, M. Bastmeyer,
C. Barner-Kowollik, Angew. Chem. Int. Ed. 2012, 51, 1071.
[68] A. S. Quick, H. Rothfuss, A. Welle, B. Richter, J. Fischer,
M. Wegener, C. Barner-Kowollik, Adv. Funct. Mater. 2014, 24, 3571.
[69] a) B. Richter, T. Pauloehrl, J. Kaschke, D. Fichtner, J. Fischer,
A.M. Greiner, D. Wedlich, M. Wegener, G. Delaittre,
C. Barner-Kowollik, M. Bastmeyer, Adv. Mater. 2013, 25, 6117;
b) T. K. Claus, B. Richter, V. Hahn, A. Welle, S. Kayser, M. Wegener,
M. Bastmeyer, G. Delaittre, C. Barner-Kowollik, Angew. Chem. Int. Ed.
2016, 55, 3817.
[70] E. Blasco, B. Yameen, A. S. Quick, P. Krolla-Sidenstein, A. Welle,
M. Wegener, C. Barner-Kowollik, Macromolecules 2015, 48, 8718.
[71] M. Kaupp, K. Hiltebrandt, V. Trouillet, P. Mueller, A. S. Quick,
M. Wegener, C. Barner-Kowollik, Chem. Commun. 2016, 52, 1975.
[72] a) G. P. Bryan-Brown, I. C. Sage, Liq. Cryst. 1996, 20, 825;
b) K. Ichimura, Y. Akita, H. Akiyama, K. Kudo, Y. Hayashi,
Macromolecules 1997, 30, 903; c) N. Kawatsuki, H. Ono,
H. Takatsuka, T. Yamamoto, O. Sangen, Macromolecules 1997, 30,
6680.
[73] Y. Nakama, T. Matsuda, J. Polym. Sci., Part A: Polym. Chem. 1992,
30, 2451.
[74] C. M. Dong, X. Wu, J. Caves, S. S. Rele, B. S. Thomas, E. L. Chaikof,
Biomaterials 2005, 26, 4041.
[75] Y. Chujo, K. Sada, T. Saegusa, Macromolecules 1990, 23, 2693.
[76] Q. Fu, L. Cheng, Y. Zhang, W. Shi, Polymer 2008, 49, 4981.
[77] J. He, L. Tremblay, S. Lacelle, Y. Zhao, Soft Matter 2011, 7, 2380.
1604005  (28 of 29) wileyonlinelibrary.com © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
[78] a) M. V. S. N. Maddipatla, D. Wehrung, C. Tang, W. Fan,
M. O. Oyewumi, T. Miyoshi, A. Joy, Macromolecules 2013, 46, 5133;
b) J. Lee, M. V. S. N. Maddipatla, A. Joy, B. D. Vogt, Macromolecules
2014, 47, 2891.
[79] Y. Zheng, M. Micic, S. V. Mello, M. Mabrouki, F. M. Andreopoulos,
V. Konka, S. M. Pham, R. M. Leblanc, Macromolecules 2002, 35,
5228.
[80] G. W. Preston, A. J. Wilson, Chem. Soc. Rev. 2013, 42, 3289.
[81] A. Ovsianikov, Z. Li, J. Torgersen, J. Stampfl, R. Liska, Adv. Funct.
Mater. 2012, 22, 3429.
[82] Z. Li, E. Stankevicius, A. Ajami, G. Raciukaitis, W. Husinsky,
A. Ovsianikov, J. Stampfl, R. Liska, Chem. Commun. 2013, 49, 7635.
[83] W. Cao, S. Ye, S. Cao, C. Zhao, Macromol. Rapid Comm. 1997, 18,
983.
[84] T. Cao, S. Yang, J. Cao, M. Zhang, C. Huang, W. Cao, J. Phys. Chem.
B 2001, 105, 11941.
[85] a) T. Cao, Z. Gu, X. Zhou, W. Cao, Chem. Lett. 2000, 29, 1370;
b) T. Cao, S. Yang, Y. Yang, C. Huang, W. Cao, Langmuir 2001, 17,
6034.
[86] B. Yu, H. L. Cong, H. W. Liu, C. H. Lu, F. Wei, W. X. Cao, Anal.
Bioanal. Chem. 2006, 384, 385.
[87] M. Lomba, L. Oriol, C. Sánchez, Eur. Polym. J. 2009, 45, 1785.
[88] M. Lomba, L. Oriol, C. Sánchez, V. Grazú, B. Sáez Gutiérrez,
J. L. Serrano, J. Martínez De la Fuente, Carbohydr. Polym. 2012, 90, 419.
[89] M. A. Azagarsamy, I. A. Marozas, S. Spaans, K. S. Anseth, ACS
Macro Lett. 2016, 5, 19.
[90] K. S. Anseth, S. M. Newman, C. N. Bowman, Adv. Polym. Sci.
1995, 122, 177.
[91] a) H. Lu, J. A. Carioscia, J. W. Stansbury, C. N. Bowman, Dent.
Mater. 2005, 21, 1129; b) J. A. Carioscia, H. Lu, J. W. Stanbury,
C. N. Bowman, Dent. Mater. 2005, 21, 1137.
[92] a) M. Podgórski, E. Becka, M. Claudino, A. Flores, P. K. Shaha,
J. W. Stansbury, C. N. Bowman, Dent. Mater. 2015, 31, 1255;
b) M. Podgórski, E. Becka, M. Claudino, A. Flores, P. K. Shaha,
J. W. Stansbury, C. N. Bowman, Dent. Mater. 2015, 31, 1263.
[93] S. Reinelt, M. Tabatabai, U. K. Fischer, N. Moszner, A. Utterodt,
H. Ritter, Beilstein J. Org. Chem. 2014, 10, 1733.
[94] S. Reinelt, M. Tabatabai, N. Moszner, U. K. Fischer, A. Utterodt,
H. Ritter, Macromol. Chem. Phys 2014, 215, 1415.
[95] a) K. Nguyen, J. L. West, Biomaterials 2002, 23, 4307; b) D. Seliktar,
Science 2012, 336, 1124; c) J. Torgersen, X. H. Qin, Z. Li,
A. Ovsianikov, R. Liska, J. Stampfl, Adv. Funct. Mater. 2013, 23,
4542; d) J. F. Xing, M. L. Zheng, X. M. Duan, Chem. Soc. Rev 2015,
44, 5031; e) C. C. Lin, C. S. Ki, H. Shih, J. Appl. Polym. Sci. 2015,
132, 41563; f) J. C. Grim, I. A. Marozas, K. S. Anseth, J. Controlled
Release 2015, 219, 95.
[96] K. A. Kyburz, K. S. Anseth, Acta Biomater. 2013, 9, 6381.
[97] J. D. McCall, K. S. Anseth, Biomacromolecules 2012, 13, 2410.
[98] H. Shih, C. C Lin, Macromol. Rapid Comm. 2013, 34, 269.
[99] A. K. Fraser, C. S. Ki, C. C. Lin, Macromol. Chem. Phys. 2014, 215,
507.
[100] J. J. Roberts, S. J Bryant, Biomaterials 2013, 34, 9969.
[101] X. H. Qin, K. Labuda, J. Chen, V. Hruschka, A. Khadem, R. Liska,
H. Redl, P. Slezak, Adv. Funct. Mater. 2015, 25, 6606.
[102] S. Rothemund, T. B. Aigner, A. Iturmendi, M. Rigau, B. Husár,
F. Hildner, E. Oberbauer, M. Prambauer, G. Olawale, R. Forstner,
R. Liska, K. R. Schröder, O. Brüggemann, I. Teasdale, Macromol.
Biosci. 2015, 15, 351.
[103] L. Wu, J. Baghdachi. Functional Polymer Coatings: Principles,
Methods, and Applications, John Wiley & Sons, Inc., Hoboken, NJ,
USA 2015.
[104] a) M. Sangermano, S. Gross, A. Priola, G. Rizza, C. Sada,
Macromol. Chem. Phys. 2007, 208, 2560; b) M. Sangermano,
G. Colucci, M. Fragale, G. Rizza, React. Funct. Polym. 2009, 69, 719.
Adv. Mater. 2017, 29, 1604005
www.advancedsciencenews.com
[105] T. M. Roper, T. Kwee, T. Y. Lee, C. A. Guymon, C. E. Hoyle, Polymer
2004, 45, 2921.
[106] M. Black, J. W. Rawlins, Eur. Polym. J. 2009, 45, 1433.
[107] Z. Chen, B. J. Chisholm, R. Patani, J. F. Wu, S. Fernando,
K. Jogodzinski, D. C. Webster, J. Coat. Technol. Res. 2010, 7, 603.
[108] G. Colucci, A. Aluigi, C. Tonin, R. Bongiovanni. Prog. Org. Coat.
2014, 77, 1104.
[109] Z. Yang, D. A. Wicks, C. E. Hoyle, H. Pu, J. Yuan, D. Wan, Y. Liu,
Polymer 2009, 50, 1717.
[110] E. Çakmakç, Y. Mülazim, M.V. Kahraman, N. K. Apohan, React.
Funct. Polym. 2011, 71, 36.
[111] P. Lundberg, A. Bruin, J. W. Klijnstra, A. M. Nyström,
M. Johansson, M. Malkoch, A. Hult, ACS Appl. Mater. Interfaces
2010, 2, 903.
[112] J. T. Wu, C. H. Huang, W. C. Liang, Y.L. Wu, J. Yu, H.Y. Chen,
Macromol. Rapid Comm. 2012, 33, 922.
[113] C. D. Donahoe, T. L. Cohen, W. Li, P. K. Nguyen, J. D. Fortner,
R. D. Mitra, D. L. Elbert, Langmuir 2013, 29, 4128.
[114] L. J. Guo, Adv. Mater. 2007, 19, 495.
[115] a) Y. Xia, G. M. Whitesides, Polym. Mater. Sci. Eng. 1997, 77, 596;
b) Y. Xia, G. M. Whitesides, Angew. Chem. Int. Ed. 1998, 37, 550.
[116] A. N. Broers, A. C. F. Hoole, J. M. Ryan, Microelectron. Eng. 1996,
32, 131.
[117] R. D. Piner, J. Zhu, F. Xu, S. Hong, C. A. Mirkin, Science 1999, 283, 661.
[118] a) M. Deubel, G. von Freymann, M. Wegener, S. Pereira, K. Busch,
C. M. Soukoulis, Nat. Mater. 2004, 3, 444; b) G. Freymann,
A. Ledermann, M. Thiel, I. Staude, S. Essig, Sabine, K. Busch,
M. Wegener, Adv. Funct. Mater. 2010, 20, 1038.
[119] J. Kettle, P. Coppo, G. Lalev, C. Tattershall, S. Dimov, M. L. Turner.
Microelectron. Eng. 2008, 85, 850.
[120] L. M. Campos, I. Meinel, R. G. Guino, M. Schierhorn, N. Gupta,
G. D. Stucky, C. J. Hawker, Adv. Mater. 2008, 20, 3728.
[121] L. M. Campos, T. T. Truong, D. E. Shim, M. D. Dimitriou, D. Shir,
I. Meinel, J. A. Gerbec, H. T. Hahn, J. A. Rogers, C. J. Hawker,
Chem. Mater. 2009, 21, 5319.
[122] H. Lin, X. Wan, X. Jiang, Q. Wang, J. Yin, Adv. Funct. Mater. 2011,
21, 2960.
[123] H. Lin, X. Wan, X. Jiang, Q. Wang, J. Yin, J. Mater. Chem. 2012, 22, 2616.
Adv. Mater. 2017, 29, 1604005 © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advmat.de
[124] C. J. Kloxin, T. F. Scott, H. Y. Park, C. N. Bowman, Adv. Mater.
Review
2011, 23, 1977.
[125] a) A. Wolfberger, B. Rupp, W. Kern, T. Griesser, C. Slugovc,
Macromol. Rapid Comm. 2011, 32, 518; b) T. Griesser,
A. Wolfberger, U. Daschiel, V. Schmidt, A. Fian, A. Jerrar,
C. Teicherte, W. Kernac, Polym. Chem. 2013, 4, 1708.
[126] J. Kumpfmueller, K. Stadlmann, Z. Li, V. Satzinger, J. Stampfl,
R. Liska, Des. Monomers Polym. 2014, 17, 390.
[127] J. Fischer, J. B. Mueller, J. Kaschke, T. J. A. Wolf, A. N. Unterreiner,
M. Wegener, Opt. Express 2013, 21, 26244.
[128] a) M. Schumann, S. Wiesendanger, J.-C. Goldschmidt, B. Bläsi,
K. Bittkau, U.W. Paetzold, A. Sprafke, R. Wehrspohn, C. Rockstuhl,
M. Wegener, Optica 2015, 2, 850; b) T. Gissibl, S. Thiele,
A. Herkommer, H. Giessen, Nat. Photonics 2016, 10, 554;
c) T. Gissibl, S. Thiele, A. Herkommer, H. Giessen, Nat. Commun.
2016, 7, 11763; d) S. Paul, V. S. Lyubopytov, M. F. Schumann,
J. Cesar, A. Chipouline, M. Wegener, F. Küppers, Opt. Lett. 2016,
41, 3249.
[129] Q. Shi, B. Sontheimer, N. Nikolay, A. Schell, A. Naber, O. Benson,
M. Wegener, Sci. Rep. 2016, 6, 31135.
[130] a) P. Lederhose, K. N. R. Wuest, C. Barner-Kowollik, J. P. Blinco.
Chem. Commun. 2016, 52, 5928; b) J. O. Mueller, F. G. Schmidt,
J. P. Blinco, C. Barner-Kowollik, Angew. Chem. Int. Ed. 2015, 54,
10284.
[131] S. W. Hell, Nat. Methods 2009, 6, 24.
[132] a) L. Li, R. R. Gattass, E. Gershgoren, H. Hwang, J. P. Fourkas,
Science 2009, 324, 910; b) J. Fischer, M. Wegener, Opt. Mater.
Express 2011, 1, 614; c) Y. Cao, Z. Gan, B. Jia, R. A. Evans, M. Gu,
Opt. Express 2011, 19, 19486; d) R. Wollhofen, J. Katzmann,
C. Hrelescu, J. Jacak, T. A. Klar, Opt. Express 2013, 21, 10831;
e) B. Buchegger, J. Kreutzer, B. Plochberger, R. Wollhofen,
D. Sivun, J. Jacak, G. J. Schütz, U. Schubert, T. A. Klar, ACS
Nano 2016, 10, 1954; f) C. Barner-Kowollik, A. S. Goldmann,
F. H. Schacher, Macromolecules 2016, 49, 5001.
[133] a) N. Zydziak, F. Feist, B. Huber, J. O. Mueller, C. Barner-Kowollik,
Chem. Commun. 2015, 51, 1799; b) N. Zydziak, W. Konrad,
F. Feist, S. Afonin, S. Weidner, C. Barner-Kowollik, Nat. Commun.
2016, 7, 13672.
wileyonlinelibrary.com (29 of 29)  1604005