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Matt Zarek, Michael Layani, Ido Cooperstein, Ela Sachyani, Daniel Cohn,*
and Shlomo Magdassi*
Heat-activated shape memory polymers (SMPs) have enjoyed
a long history of interest and academic development because
of the expectation that they could impart structural responsiveness and, ultimately, autonomous deployment in otherwise
inaccessible places, such as the human body and space.[1,2] The
particular focus on SMPs stems from the broad tunable range
of mechanical, thermal, and optical properties, and from their
low density at low cost, compared to shape memory alloys.[3]
Until now, SMPs were not used in the field of flexible electronics due to the inadequate nature of the present processing
techniques. Here, we show that by using a commercial stereolithography (SLA) 3D digital light processing (DLP) printer, one
can print oligomer melts, rather than liquid resin, to generate
high-resolution 3D shape memory structures, which are further
utilized for constructing flexible electronic devices. The use of a
3D printer enables fabrication of a whole structure with shape
memory properties, in contrast to current methods based on
the assembly of 2D ribbons or extruded tubes. The printable
resin is composed of methacrylated semicrystalline polymer,
a photoinitiator, a dye, and an inhibitor to prevent premature
crosslinking. The ability to fabricate SMP devices in almost any
geometry is important for soft robotics,[4] flexible electronics,[5]
and medical devices.[6]
Additive manufacturing is gaining popularity in a range
of scientific disciplines for reactionware,[7] device fabrication,[8] and tissue engineering.[9] Many thermoplastic-based 3D
printers extrude molten polymer that cools and solidifies to
form a 3D structure. A similar technique was designed to print
low melting point alloys[10] and most recently a combination of
extrusion and in situ photopolymerization was demonstrated to
print a hydrogel that exhibits a cyclical temperature-responsive
volume change.[11] In comparison, common SLA-based printers
use photopolymerization to fabricate objects through a layerby-layer process which is performed within a resin bath containing liquid monomers or oligomers. Our approach is based
on performing the photopolymerization reaction of a melted
solid precursor yielding 3D SMP structures.
Thermally induced shape memory behavior is contingent on
two molecular requirements: chemical or physical crosslinks to

M. Zarek, Dr. M. Layani, I. Cooperstein, E. Sachyani,

Prof. D. Cohn, Prof. S. Magdassi
Casali Center of Applied Chemistry
Institute of Chemistry
The Hebrew University of Jerusalem
Jerusalem 91904, Israel
E-mail: [email protected]; [email protected]

DOI: 10.1002/adma.201503132

Adv. Mater. 2016, 28, 44494454

set the permanent 3D shape, and a melting temperature (Tm) or

a glass transition temperature (Tg), more generally a transition
temperature (Ttrans), to control the molecular switching segments that fix the temporary shape. To set the temporary shape,
the material is deformed while heating above the Ttrans of the
molecular switching segment. The temporary shape is obtained
when T < Ttrans. The material recovers its permanent shape
upon T > Ttrans. Many permutations of molecular switching
segments have been described for a range of different materials and for triggering mechanisms other than temperature.[12]
There have been demonstrations of triple[13] and reversible bidirectional[14] shape memory behavior, where the latter augured
the development of thermally induced monolithic polymer
actuators.[15] However, these structures were reported, fundamentally, as 2D. That is because, to date, unadulterated shape
memory structures are fabricated by casted films or extrusion, where only simple planar or tubular geometries, such
as ribbons, filaments, and cylinders are tenable. The mutually
constrained requirement to cure the material as a liquid, in
the melt or in solution, with a 3D shape is the main reason
shape memory thermoset structures have been confined solely
to spartan geometries. With the approach presented here, the
shape memory structure can be formed in three dimensions.
The ability to fabricate materials into arbitrary 3D structures
with dynamic behavior has been demonstrated with proprietary multimaterial inkjet printers and the prudent choice of
inks (Objet 260 Connex, Stratasys). Tibbits et al. have presented
structures that function by a hygroscopic effect, whereby particular shape transformations are predesigned to the printed
object to induce movements of specific regions by swelling
behavior when placed in water.[16,17] Another implementation
exploits heat as the triggering mechanism. Ge et al. prepared
lamina composites by printing glassy fibers within an elastomeric matrix. Heating the lamina above the Tg of the fibers
activates a shape memory program.[18,19] A more recent study
described a helical structure that was controlled by shape
memory hinges that were triggered at different Tgs.[20] The Tgs
were composed based on the relative proportion of two commercial formulations but with unknown composition. Both
these approaches require expensive hardware, sophisticated
computer modeling, and a closed material palette but above all,
the responsive elements of these printed structures are only a
fraction of the total printed structure and each object tolerates a
single transformation pathway.
Here, we demonstrate that it is possible to fabricate complex
shape memory structures with a viscous melt (30 Pa s) using
a commercial SLA printer (Picoplus39, Asiga) and a customized heated resin bath (Figure 1a; photograph of the system
setup is available in Figure S1, Supporting Information). The

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Figure 1. a) Illustration of the SLA 3D printer. The print platform descends into the heated resin bath. For each layer cycle, the light source projects
a cross-section of the part on a thin layer of resin in contact with the print platform. The platform then exits the photopolymer resin then restarts the
process for another layer. b) Degree of crystallinity of the macromonomer precursor (circles) and the degree of crystallinity of printed objects (diamonds) as a function of the degree of methacrylation. c) Tensile moduli of printed dogbones below (diamonds) and above (circles) the Tm. d) Strain
at break of printed dogbones above the Tm.

3D printing was performed by layer-by-layer UV curing at

the bottom of the reservoir, curtailing the deleterious effect
of molecular oxygen inhibition.[21] The build times were
dependent on the size of the models and the layer thicknesses;
for example, it took 44 min to print a 1 cm3 cube with a 100 m
layer thickness (optimized printing parameters are presented
in Table S1, Supporting Information). The drawback of slow
print speeds in hindering adoption of additive manufacturing
processes is well known but recently a new SLA technique
was reported with print speeds up to two orders of magnitude
faster that is resin agnostic.[22] The XY-axis resolution of the
printer used in this study is 39 m, whereas on the layer thickness (Z-axis), it can be as low as 1 m. In our experiments,
we used layer thickness of 100 m. Specifically, the unreacted
macromonomer was partially removed from the voids of the
printed objects by immersion in warm isopropyl alcohol under
sonication. Final curing was performed by additional UV exposure in the Asiga flash unit for 30 s.
The shape memory thermosets in this study were based
on polycaprolactone (PCL) (number average molecular
weight 10 000), a semicrystalline polymer. We focus on PCL
because it is widely reported in studies on shape memory
materials, particularly with a view of future use in medical devices, but any crosslinkable polymer with a shape
memory switching segment and manageable melt viscosity
will work. PCL is solid at room temperature and has a Tm
between 43 and 60 C depending on the molecular weight.
The PCL in this study has a Tm of 55 C, quantified as the
peak of the melting endotherm by differential scanning calorimetry (DSC). To prepare the resin, methacrylate groups

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were covalently linked to the chain ends of the PCL macrodiol via a simple alcoholisocyanate reaction (see the Experimental Section).
The degree of methacrylation of the macromethacrylates
directly affects the crosslinking density and, therefore, the
degree of crystallinity of the thermosets.[23] Therefore, we prepared a series of macromethacrylates with various degrees of
methacrylation, determined by NMR, to map the mechanical
properties that are influenced by the degree of crystallinity. To
evaluate the mechanical, thermal, and shape memory properties of the printed objects, dogbone specimens were designed
in Google SketchUp and 3D printed. All the specimens were
identical to avoid any bias as a result of different print orientations. Macromethacrylates with a degree of methacrylation less than 40% could not be successfully photocured. The
crosslinking of the macromethacrylates hinders the formation
of crystallites, thus resulting in a lower and broader melting
transition compared to the non-crosslinked thermoplastic
material.[24] Figure 1b shows that the degree of crystallinity of
the macromethacrylates prior to UV radiation is about 45%,
whereas the UV cured polymer has a decreasing crystalline fraction when the degree of methacrylation increases. This is also
reflected in the degree of swelling in a solvent, which decreases
with the increase of the degree of methacrylation, in line with
Florys swelling theory[25] (Figure S2, Supporting Information).
Figure 1c presents the dependence of the tensile moduli of the
printed thermosets below and above the Tm. The SMP thermosets below the Tm have elastic moduli in the range of 110 to
230 MPa, decreasing as the crystalline fraction drops. In comparison to typical low molecular weight resins, the presence of

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standard triangle language (STL) file types from popular, free,

and open source CAD hosting sites[7] or generated by commercial CAD software (Autodesk Inventor) and modified with
the native printer software. At room temperature, the printed
structures are rigid and have a wax-like surface, while above the
Tm, the structures are pliant and elastomeric. In this state, any
deformation applied to the structure can be fixated by cooling
below the Tm. Reheating the structure leads to a recovery of the
original printed shape. The Tm of the PCL was 55 C and the
shape memory program was triggered by placing the structures
in a water bath at that temperature. In Figure 2a, heat gun was
used with a set temperature of 70 C for presentation purposes.
To test the limit of this technique, we printed various model
thermoset shape memory vascular stents. Vascular stents are
a challenge to print because of the intricate strut design comprising submillimeter thicknesses and the large number of
voids. Figure 2a shows a stent with strut thicknesses about
600 m. Earlier attempts to implement shape memory stents
struggled with the conventional fabrication methods, which
might explain the lack of progress over the last decade.[2628]
In addition, we printed a scaled Eiffel Tower (Figure 2b) and
a bird (Figure 2c), which were repeatedly cycled through different temporary shapes. The figure shows the high resolution
and different type of complex models that can be obtained with
this approach but cannot be achieved by methods previously

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a high-molecular weight non-methacrylated PCL fraction does

not function as a plasticizer but rather as reinforcing filler when
the material is beneath the Tm. Above the Tm, the trend reverses
with increasing modulus as the crystalline fraction climbs,
albeit at magnitudes spanning only 13 MPa. The higher methacrylate content is reflected in the lower strain at break of the
heated specimens (Figure 1d). The implication from these
results is that by modulating the methacrylate content, a spectrum of mechanical properties is obtainable, including stretchability. While combining the shape memory properties with
printed electrodes, we could form responsive moving electrical
structures as will be described below.
The established metrics for shape memory behavior are
the strain fixity rate Rf, which describes the capability of the
switching segment to fix the transient shape, and the strain
recovery rate Rr, which describes the ability of the material to
reclaim its permanent shape.[24] In our case, Rf indicates the
crystallite shape fixing performance and Rr indicates the effectiveness of the crosslinks in driving the return to the permanent shape. For all the materials, Rr was greater than 93% and
Rf was greater than 98%, demonstrating their excellent shape
memory behavior.
To demonstrate the applicability of the 3D SMP process, we
printed several models (Figure 2ac), exhibiting shape memory
behavior. The digital models were downloaded from the web as

Figure 2. SLA with a molten macromethacrylate can impart shape memory to nearly any object. a) A model cardiovascular stent with a length of 3 cm,
strut thicknesses of 600 m, and open cells of 2.5 mm 2.5 mm, reverting to its original shape at 70 C. Printing such a model stent takes 1 h with
the Asiga printer. b) An Eiffel Tower model, 6 cm tall reverting to its original shape at 70 C. c) A bird with a 3 cm wing span reverting to its original
shape at 70 C.

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Figure 3. Fabrication of shape memory-based electrical devices. a) A 3D printed construct (top) programmed into its temporary state to enable inkjet
printing on a 2D surface (bottom). b) Conductive ink printed (OmniJet100 inkjet printer) on the shape memory construct. c) Fabricated temperature
sensor in its off state (top) and on state (bottom). d) The SMP object was printed as a flat sheet followed by deposition of a CNT layer and was fixated
in a curved state (left image). When a voltage was applied, the crystalline fraction melted leading the structure to return to its original flat state (right
image). e) The SMP object is used as a shape memory connector, which upon applying the voltage closes the electrical circuit.

reported on shape memory thermosets from casted films or

simple molds. All the constructs ultimately recovered their permanent shape upon heating (Movie S1S4, Supporting Information). Transparency is another mutable property of these
printed structures. At room temperature the printed structures
are opaque due to the presence of crystallites; when the crystallites melt, the object becomes transparent to a level dependent
on the thickness of the printed part (see Figure S3 in the Supporting Information).
The printed shape memory objects can be applied in flexible electronics by integrating the SMPs with conductive materials, and we demonstrate possible applications in two types of
responsive electrical devices. In one device, we fabricated an
electrical temperature sensor. The device is composed of a 3D
shape memory polymer printed object (Figure 3a) onto which
electrical contacts were inkjet printed with silver nanoparticle
ink (Figure 3b).[29] This silver ink is unique due to its ability
to undergo a sintering process at room temperature, thus it is
suitable for printing on the temperature sensitive polymers utilized in this study. Figure 3c (and Movie S5, Supporting Information) illustrates the function of the device: the temporary
shape is an open electrical circuit, and when heated above the
Tm, the circuit closes and lights an LED. It should be noted that
the use of a shape memory material has an additional advantage to printable flexible electronics since a 3D object can be
temporarily turned into a flat surface onto which other materials can be deposited by simple printers, eliminating the need
for highly complicated and costly printers that enable five-axis
movement.[30]

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The second device is based on depositing a layer of carbon

nanotubes (CNTs) on top of the printed SMP objects to form
an electrical heater that enables thermal transformation from
a temporary shape into the original shape of the object. Similar
types of architecture, with materials having different thermal
expansion coefficients were recently reported to form electrical
actuators.[31,32] In these reports, the movements of the actuator
were strictly limited to shapes based on 2D flat films. Here,
we show the deposition of the CNT layer (horse shoe pattern)
on printed SMP objects, which enable a complex movement
depending on the 3D printed structure. The CNT layer acts as
an electrical heater (100 C), and the direction of movement
is determined by the SMP structure. Figure 3d,e shows two
temporary shapes of the printed structures, where these fixated shapes cannot be obtained using standard planar actuators. While applying a voltage of 50 V, the temperature of
the printed SMP increases above the Tm, causing the structure
to return to its original printed shape (Figure 3d). We further
show how this movement can close a circuit to turn on an LED
lamp (Figure 3e). It should be noted that once the SMP returns
to its original shape, to initiate another cycle it must be manually fixated into another temporary shape. This can be solved by
combining the SMP with another polymer having a different
thermal expansion coefficient. To demonstrate this, we fabricated a sandwich structure, in which a Kapton film is coated
on one side with a CNT layer and on the other side an SMP
layer, thus, enabling a reversible movement of the actuator. This
resulted in a movement at a larger deflection angle (180) due
to the presence of the SMP, compared to typical CNT deposited

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Fabrication of Electronic Devices: The inkjet printing of the conductive
silver electrode was performed with the ink reported by Magdassi
et al.[29] The silver electrodes were prepared by inkjet printing (OmniJet
100, Unijet Korea) with a 30 pL piezoelectric printhead (Dimatix, Fujifilm
USA) and then sintered by exposure to HCl vapor at room temperature.
The CNT ink was composed of MWCNT (NC7000, Nanocyl). The ink
and deposition was performed as described by Azoubel et al.[34] The
silver lines were printed after the programing of the temporary shapes
and the conductivity remained constant for at least 20 cycles.

Experimental Section

Acknowledgements

Synthesis of PCL Macromonomer: PCL10K (SigmaAldrich) was

charged to a round bottom flask and dried under vacuum at 120 C
for 2 h. Isocyanatoethyl methacrylate (Tokyo Chemical Industry) was
added under nitrogen and reacted for 2 h at 85 C in dioxane (Bio-Lab
Israel), which was previously dried over molecular sieves (Merck). The
macromonomer was precipitated with cold petroleum ether (Bio-Lab
Israel). The macromonomer was dried in a fumehood overnight.
Determination of the Degree of Methacrylation: 1H-NMR spectroscopy
was conducted on a Bruker 500 MHz spectrometer using deuterated
chloroform as the solvent and TMS as an internal standard. Scans
were performed at 500 MHz resonance frequency with the spectral
width of 10 KHz. To determine the degree of methacrylation, the signal
intensities of the methyl protons in the methacrylate group were taken
relative to protons on the ethylene glycol initiator, with a correction to
remove the contribution of two methacrylate protons that overlap with
the initiator. The following signals were used: CCH3 (methyl protons
in the methacrylate group, = 1.9 ppm, MC3), CH2CH2 (protons
in the initiator, = 4.2 ppm, MC4), and CH2 (methylene protons in
the methacrylate group, = 5.6 ppm and = 6.1 ppm, MP1 and MP2,
respectively). The degree of methacrylation was calculated as follows,
with the coefficient present to normalize the result:

M.Z. and M.L. contributed equally to this work. This research was
partially supported by the Singapore National Research Foundation
under the CREATE program: Nanomaterials for Energy and Water
Management, and by the Israel National Nanotechnology Initiative FTA
project on functional coatings and printing.

D=

IMC3
4
6 IMC4 IMP1 IMP2

(1)

Resin Additives: The PCL formulations contained 4 wt%

2,4,6-trimethylbenzoyl-diphenyl-phosphineoxide as photoinitiator (BASF,
Germany), 0.1 wt% of vitamin E (Ahava, Israel) to prevent premature
crosslinking, and 0.01 wt% Orasol Orange G dye (BASF, Germany).
3D Printing Process: The shape memory resin was prepared for
printing by first heating the PCL macromethacrylate above its melting
temperature (60 C) followed by adding the photoinitiator, inhibitor
and dye to the melt. Once the melt is homogenous, it is poured into
the custom printer monomer bath, where it is maintained at 90 C
during the printing process. The print parameters are listed in Table S1
(Supporting Information).
Mechanical Testing and Shape Memory Testing: The mechanical tests
and shape memory testing was conducted on the printed dogbones
with an Instron 4500 Universal Testing Machine with a custom heating
apparatus according to the protocols described by Lendlein et al.[33]
Thermal Characterization: The precursor macromethacrylates and
photocured printed samples were evaluated by DSC on a MettlerToledo
TA-400 DSC calorimeter from 10 to 80 C with history erase. The initial
heating rate was 10 K min1, followed by a cooling rate at 2 K min1 and
a heating rate of 4 K min1.
Network Characterization: The printed thermoset networks where
characterized by determining the gel content and the degree of swelling
as described elsewhere.[33]

Adv. Mater. 2016, 28, 44494454

Supporting Information

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on Kapton (90). It should be noted that preliminary experiments indicate that the same material and printing method
enable forming stretchable conductive patterns. Stretching of at
least 30% can be obtained with a resistivity change of less than
5%, as will be presented in a future study.
In summary, we describe a general and facile method based
on 3D printing methacrylated macromonomers to fabricate
shape memory objects that can be used in flexible and responsive electrical circuits. Such responsive objects can be used in
fabrication of soft robotics, minimal invasive medical devices,
sensors, and wearable electronics. The use of 3D printing overcomes the poor processing characteristics of thermosets and
enables complex geometries that are not easily accessible by
other techniques.

Supporting Information is available from the Wiley Online Library or

from the author.

Received: June 29, 2015

Revised: July 24, 2015
Published online: September 24, 2015

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