Bio-Inspired Polymer Composite Actuator and Generator Driven by

Water Gradients
Mingming Ma et al.
Science 339, 186 (2013);
DOI: 10.1126/science.1230262

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REPORTS
E. Thomas for useful discussions. This work was supported European provisional patent application EP12177741 was filed Figs. S1 to S3
by Teijin Aramid BV, Teijin Techno Products Ltd., Air Force 25 July 2012. Tables S1 to S3
Office of Scientific Research FA9550-09-1-0590, Russell Berrie References (42–52)
Nanotechnology Institute, Air Force Research Laboratory Supplementary Materials
FA8650-07-2-5061, the U.S. Department of Defense National www.sciencemag.org/cgi/content/full/339/6116/182/DC1
Defense Science and Engineering Graduate fellowship, and the Materials and Methods 27 July 2012; accepted 21 November 2012
Welch Foundation (C-1668 and Evans Attwell fellowship). Supplementary Text 10.1126/science.1228061

gels (10–14). Many organisms use water-sorption–

Bio-Inspired Polymer Composite induced swelling for actuation (15). Several types
of water-responsive hydrogels have been devel-
Actuator and Generator Driven by oped for actuator fabrication (10), but they exhibit
slower response, lower stress generation, and mar-
Water Gradients ginal stability than do animal muscle fibers.
Polypyrrole (PPy) is an electroactive polymer
with many desirable properties that could allow it
Mingming Ma,1 Liang Guo,1 Daniel G. Anderson,1,2 Robert Langer1,2* to act as an artificial muscle (16, 17). PPy can
also absorb water and change its shape, which
Here we describe the development of a water-responsive polymer film. Combining both a rigid matrix

Downloaded from www.sciencemag.org on January 11, 2013

allows it to drive motion in a rotary actuator (18).
(polypyrrole) and a dynamic network (polyol-borate), strong and flexible polymer films were developed However, existing PPy rotary actuators only weak-
that can exchange water with the environment to induce film expansion and contraction, resulting in ly output mechanical force or power, in contrast
rapid and continuous locomotion. The film actuator can generate contractile stress up to 27 megapascals, to PPy-based electroactuators (16, 18). Inspired
lift objects 380 times heavier than itself, and transport cargo 10 times heavier than itself. We have by the network structure of animal dermis, in
assembled a generator by associating this actuator with a piezoelectric element. Driven by water which rigid collagen fibers reinforce an elastic
gradients, this generator outputs alternating electricity at ~0.3 hertz, with a peak voltage of ~1.0 volt. The
electrical energy is stored in capacitors that could power micro- and nanoelectronic devices.
1
David H. Koch Institute for Integrative Cancer Research,
olymeric materials that reversibly change chanical purposes (1). Based on their energy Massachusetts Institute of Technology (MIT), Cambridge, MA

P shape, size, or mechanical properties in

response to external stimuli have attracted
considerable interest because of their potential
sources for actuation, responsive polymeric ma-
terials can be divided into three classes: electro-
active polymers (2, 3), light- or thermal-responsive
02139, USA. 2Harvard-MIT Division of Health Sciences and
Technology, and Department of Chemical Engineering, MIT,
Cambridge, MA 02139, USA.
*To whom correspondence should be addressed. E-mail:
applications as actuators for biomedical and me- elastomers (4–9), and pH- or solvent-responsive [email protected]

Fig. 1. Characterization of PEE-

PPy composite films. (A) A PEE-
PPy composite film (black) is
composed of PPy polymer chains
(gray lines) and a PEE-borate
network (red lines). The struc-
ture changes (involving H bonds
and borate ester bonds) in re-
sponse to water (blue dots) sorp-
tion and desorption. (B) PEE-PPy
weight change (red) synchro-
nizes with air humidity change
(black). (C) ATR-IR spectra show-
ing H/D exchange between the
PEE-PPy film and water vapor.
Top to bottom: before D2O ex-
posure and 0, 1, 2, 3, and 4 min
after D2O exposure. Dashed lines
indicate the three pairs of shift-
ing peaks. (D) A PEE-PPy film
maintains its flexibility and mir-
rorlike surface after 6 months of
open storage.

186 11 JANUARY 2013 VOL 339 SCIENCE www.sciencemag.org

 REPORTS
network of elastin microfibrils to form a sturdy indicated by peak shifts in 11B nuclear magnetic nized with the humidity change (Fig. 1B), indi-
and flexible material (19), we hypothesized that a resonance (NMR) spectra (20) and increased vis- cating the film’s instant response to water vapor.
composite of a soft water-responsive gel within a cosity (21) (figs. S1 and S2). We hypothesized To probe the polymer’s chemical structure change
rigid polymer matrix would yield a better water- that the anionic PEE-borate complex could be elec- in response to water, a PEE-PPy film was im-
responsive actuator. We made a dynamic polymer trically attracted to the cathode and trapped in the mersed in D2O for 10 s, then taken out and
composite of rigid PPy imbedded with a flexible, growing PPy matrix as macromolecular counter- examined by attenuated total reflectance (ATR)–
interpenetrating polyol-borate network (20) that ions. We attempted to reduce the PPy matrix and IR. After D2O exposure, three IR peaks related to
would be responsive to water sorption and de- export small counterions by applying a nega- O-H or N-H bending disappeared and three new
sorption (Fig. 1A). The dynamic polyol-borate net- tive electrical potential to the PEE-PPy film for peaks appeared (fig. S6 and table S2). The peak
work formed within the PPy matrix also serves as 1 hour in an electrolytic solution (22). The treated shifting was due to the hydrogen-deuterium
a macromolecular counterion for PPy. The polyol- PEE-PPy film showed minimal change in weight, (H-D) exchange of active protons in OH and NH.
borate network is sensitive to water by means of conductivity, and mechanical properties, which The isotopic ratio (vH/vD) of the three peaks was
hydrolysis and reforming of the borate ester cross- suggested that the counterion is a polymeric en- smaller than the theoretical value (vH/vD = 1.37)
linking hub upon water sorption and desorption, tity and cannot be electrically transported out of for free O-H or N-H bonds, suggesting that these
which changes the mechanical properties of the the PPy matrix (22). In contrast, when this active protons were involved in H bonding (23).
composite (Fig. 1A). Intermolecular hydrogen reduction-resistant PEE-PPy film was soaked in When this PEE-PPy film was left in ambient air
bonding between the polyol-borate network and 90°C water for 1 hour, its weight, conductivity, [relative humidity (RH) ~20%], the D peaks
PPy also modulates intermolecular packing of the and mechanical properties significantly decreased quickly shifted back to corresponding H peaks

Downloaded from www.sciencemag.org on January 11, 2013

polymer composite to alter its mechanical prop- (fig. S3 and table S1). PEE and boric acid were within 4 min (Fig. 1C), without contacting any
erties in response to water. Therefore, the polymer identified in the soaked water sample by NMR liquid water. This fast H-D exchange demon-
composite exhibits fast, reversible, and dramatic and infrared (IR) spectroscopy (figs. S4 and S5). strated that the PEE-PPy film was continu-
mechanical deformation and recovery in response The average amount of PEE in the initial PEE- ously and rapidly “breathing” water from the
to environmental moisture, visually reminiscent PPy film was ~12% by weight. The leached PEE air, which should manifest in a fast and revers-
of “fast twitch” muscle activity. and boric acid components indicated hydrolysis ible response to environmental water concentra-
The free-standing composite polymer film was of the polymeric counteranion, suggestive of the tion changes. The film was also characterized
synthesized by electropolymerization of pyrrole water-responsive nature of the PEE-borate net- by Raman spectroscopy, conductivity measure-
in the presence of a polyol-borate complex. The work (Fig. 1A) (20). ments, and mechanical analysis (see the supple-
polyol was pentaerythritol ethoxylate (PEE), a Monitored by a quartz crystal microbalance mentary materials for details), which showed a
four-armed ethylene glycol oligomer (molecular with a humidity module, the PEE-PPy film rap- combination of moderate conductivity (30 S/cm),
weight ~800), which can coordinate with boron(III) idly absorbed up to 10% of water by weight from high tensile strength (115 MPa), and good flex-
species to form a dynamic polymer network as humid air. The film’s weight change synchro- ibility (elongation at break = 23%). The film also

Fig. 2. Locomotion of a PEE-PPy film on a moist substrate. (A) Representative PPy (red) and PPy (black) films correlated with saturated water vapor pressure
images and sketches of the film’s multistage locomotion and a schematic at each substrate temperature (n = 5). One flipping cycle refers to a motion
diagram of the film’s elastic potential energy. (B) Flipping frequency of PEE- process starting from stage I through stage V and back to stage I.

Fig. 3. Mechanical performance of a 25-mg PEE-PPy film actuator. (A) (top image) buckling and lifting the slides up for ~2 mm (bottom
The contractile stress and force generated in the film upon water sorp- image). The red arrows indicate the position of the 30-mm-thick
tion and desorption. (B) The load-dependent stroke of the actuator actuator. (D) The flipping frequency of the actuator with cargo loading
contraction. (C) Images of the actuator under microscopy glass slides (n = 5).

www.sciencemag.org SCIENCE VOL 339 11 JANUARY 2013 187

REPORTS
showed good stability while exposed to air and am- moist PPy (Young’s modulus = 0.65 GPa versus only needs activation forces in the millinewton
bient humidity for 6 months (Fig. 1D and fig. S7). 1.65 GPa, table S1). This difference could also be level, which can be generated within 0.1 s in the
The PEE-PPy film spontaneously and con- explained by the interpenetrating polymer struc- film upon water sorption or desorption. The load-
tinuously flipped and navigated over a moist ture being broken or weakened upon water sorp- dependent stroke was measured by preloading
nonwoven paper substrate (movie S1). Film tion and recovered upon water desorption (Fig. the moist actuator up to 21 MPa. Upon water
motility required the water gradient, rather than 1A). The cooperative switching of the PEE-PPy desorption, the actuator contracted under a con-
just water: In a closed chamber saturated by water film between the two states with different phys- stant load, and the linear relation between stroke
vapor, the PEE-PPy film folded into a roll and ical properties (swelling/soft versus shrinking/stiff) and load (Fig. 3B) indicated that the actuator
remained static. One locomotive cycle of the film probably contributed to its rapid locomotion. In worked in its elastic range. The maximum work
was generally composed of five stages (Fig. 2A, I addition, we also found that a larger PEE-PPy during contraction was ~73 J/kg, achieved at 9 to
to V). As a PEE-PPy film contacted the moist film (9 cm by 9 cm, fig. S9) performed fast loco- 15 MPa loading, which matched the maximum
substrate, the bottom face absorbed more water motion at a similar frequency as a smaller one (2 cm elastic potential energy (76 J/kg) stored in a film
than the top face, which caused asymmetric swell- by 4 cm) (movie S3), suggesting that this water- roll. These contractions finished in ~80 s (fig.
ing and film curling away from the substrate (I). gradient–driven actuator is potentially scalable. S10), which provided an average power density
Thus, the film/substrate contact area decreased The contractile force and stress generated in of ~0.9 W/kg. Upon water sorption, this 25-mg
and the film’s gravity center rose, which led to a PEE-PPy film actuator were measured on a me- free film could deform and lift a 9.5 g load to a
mechanical instability (II) and eventually caused chanical analyzer. A 25-mg PEE-PPy film cov- height of 2 mm within 3 s (Fig. 3C). The work
the buckled film to topple over (III). Asymmetric ered by a moist paper was clamped and preloaded output was 7.6 J/kg and the power density was

Downloaded from www.sciencemag.org on January 11, 2013

water sorption was repeated at the film/substrate with a force of 0.05 N to keep the film tight and 2.5 W/kg. In addition, we found that a load of sil-
interface, which cooperated with water release straight. When the film was uncovered, a con- ver wires weighing up to 260 mg attached to the
from the raised part of the film to generate hori- tractile force of up to 14 N was generated by the film perimeter was efficiently transported along a
zontal movement (IV). Finally, most of the con- film’s shrinking and stiffening caused by water substrate-derived water gradient (Fig. 3D, movie
tact area curled up, and the film fell back to the desorption (Fig. 3A). The maximum stress was S4, and fig. S11).
substrate with a new face down (V) to start a new 27 MPa, which was about 80 times higher than To probe the capability of the PEE-PPy ac-
cycle (I). During the flipping process (stages I to that of mammalian skeletal muscle (~0.35 MPa) tuator, we did a theoretical thermodynamic anal-
V), both faces of the film were equilibrating with (17) and comparable to the maximum stress elec- ysis of its water-induced expansion/contraction
water in the substrate and in the lower-humidity trochemically generated in other PPy-based ac- cycle and came up with the following two equa-
air above. Thus, the water gradient between sub- tuators (22 to 34 MPa) (24, 25). When the film tions (see the supplementary materials for detailed
strate and air was reflected in the asymmetric was again covered by a moist paper, the contract- analysis)
film deformation that drove the film locomotion, ile force and stress decreased to zero as a result
E
d ð−DGcycle
rÞ
with the cooperation of film gravity and friction of the water-induced film swelling and softening. < ð1Þ
with the substrate. Analysis of the frequency of The expansion/contraction cycle could be repeated R M
film flipping motion as a function of the satu- hundreds of times. One full expansion/contraction
E
d3
rated water vapor pressure Ps (proportional to the cycle needed ~5 min at room temperature and > fad ð2Þ
water evaporation rate, eq. S1) at each substrate 20% RH, possibly due to slow water diffusion in 2R2
temperature indicated a roughly linear correla- the film (18). This does not conflict with the E, d, and R are the elastic modulus, thick-
tion (Fig. 2B), suggesting that the film locomo- film’s fast locomotion, because the locomotion ness, and curvature of the buckled actuator, re-
tion could be regulated by controlling the water
evaporation rate. If the air close to the substrate
was water-saturated, the PEE-PPy film would
fold into a roll (VI), which possessed high elastic
energy of 21 to 76 J/kg and could partially release
the energy in a sudden and quick leap (Fig. 2A
energy diagram, movie S2, and eqs. S2 and S3).
Water gradients were most effective in driving
PEE-PPy film locomotion. Volatile polar organic
solvents (such as alcohols, ketones, and esters)
also caused the PEE-PPy film to swell and buckle,
but its translational motion was significantly
weaker or unable to be completed. This can be
explained by the interpenetrating polymer struc-
ture (the PEE-borate network and its H-bond in-
teraction with the polypyrrole matrix) being more
sensitive to water than to other organic solvents
(20). We also found that PPy films without an
interpenetrating PEE-borate network (18) ex-
hibited marginal film buckling on a moist sub-
strate, with no translational motion, in contrast to
a PEE-PPy film that navigated on the same sub-
strate. The different behaviors could be attributed Fig. 4. Design and performance of a water-gradient–driven generator. (A) The assembly of a piezo-
to the observation that water sorption had a bigger electric PVDF element with a PEE-PPy actuator to form the generator. (B) The connection of the generator
softening effect on a PEE-PPy film than on a with a 10-megohm resistor as load. (C) The configuration of the rectifying circuit and charge storage
PPy film (fig. S8). Although dry PPy and PEE- capacitor. (D) The generator’s output voltage onto the 10-megohm resistor. (E) Voltage across a capacitor
PPy films had similar tensile moduli of ~2.3 GPa, when being charged by the generator. The inset shows a stepwise increase in the capacitor voltage
the moist PEE-PPy was much softer than the accompanying each cycle of the energy conversion process.

188 11 JANUARY 2013 VOL 339 SCIENCE www.sciencemag.org

 REPORTS
spectively. r and M are the density and molecular generated alternating electrical pulses by the gen- 12. G. H. Chen, A. S. Hoffman, Nature 373, 49 (1995).
weight of water, respectively. ∆Gcycle is the molar erator were rectified using a commercial full-wave 13. J. M. Benns, J. S. Choi, R. I. Mahato, J. S. Park, S. W. Kim,
Bioconjug. Chem. 11, 637 (2000).
Gibbs free-energy change of absorbed water dur- bridge rectifier, then stored in a 2.2 mF capacitor 14. M. E. Caldorera-Moore, W. B. Liechty, N. A. Peppas,
ing one expansion/contraction cycle. fad is the (Fig. 4C). Within 7 min of charging, the voltage of Acc. Chem. Res. 44, 1061 (2011).
adhesive force coefficient between PEE-PPy films the capacitor was saturated to ~0.66 V (Fig. 4E). 15. P. Fratzl, F. G. Barth, Nature 462, 442 (2009).
and moist substrates. Given a certain E, R, and This was lower than the peak output voltage of the 16. E. Smela, Adv. Mater. 15, 481 (2003).
17. R. H. Baughman, Science 308, 63 (2005).
fad, Eqs. 1 and 2 roughly define a theoretical max- generator, possibly due to voltage drop across 18. H. Okuzaki, T. Kuwabara, T. Kunugi, J. Polym. Sci. B
imum and minimum limit on the required thick- the rectifying diodes and/or current leakage of Polym. Phys. 36, 2237 (1998).
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In practice, we found that the optimal thickness This PEE-PPy polymer composite system fea- 20. M. Shibayama, M. Sato, Y. Kimura, H. Fujiwara,
S. Nomura, Polymer (Guildf.) 29, 336 (1988).
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roughly 15 to 40 mm. Actuators thinner than 15 mm mer with a soft, hydrolytically sensitive polymer (2006).
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tuators thicker than 40 mm showed significantly ment, converting the chemical potential energy in 23. M. Szafran, Z. Degaszafran, J. Mol. Struct. 321, 57 (1994).
24. S. Hara, T. Zama, W. Takashima, K. Kaneto, Polym. J. 36,
slower locomotion. water gradients to mechanical work. Besides me-
151 (2004).
Because this PEE-PPy actuator could contin- chanical vibration energy, the generator based 25. J. D. Madden, P. G. Madden, P. A. Anquetil, I. W. Hunter,
uously extract chemical potential energy out of on this powerful actuator can use ubiquitous low- in Electroactive Polymers and Rapid Prototyping
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work, it should be able to drive a piezoelectric in contrast to state-of-the-art piezoelectric energy vol. 698, p. 137.
26. Y. Qin, X. Wang, Z. L. Wang, Nature 451, 809 (2008).
element to convert the mechanical energy into scavengers that rely solely on mechanical vibration
electrical energy. A 9-mm-thick piezoelectric poly- energy (26). Thus, the water-gradient–driven actu- Acknowledgments: M.M. and R.L. conceived the idea and
vinylidene difluoride (PVDF) film was metallized, ator and generator demonstrated potential applica- designed the experiments. M.M. and L.G. performed the
wired, and insulated on both faces (Fig. 4A). A tions as sensors, switches, and power sources for experiments. M.M., L.G., D.G.A., and R.L. contributed materials
and/or tools, analyzed the data, and wrote the paper.
27-mm-thick PEE-PPy actuator was attached to ultralow-power devices. This research was supported in part by a National Heart, Lung,
one face of the PVDF element. When placed on a and Blood Institute Program of Excellence in Nanotechnology
moist substrate with the actuator facing down, the References and Notes:
(PEN) Award, contract no. HHSN268201000045C; National
actuator bent and stretched the PVDF element Cancer Institute grant CA151884; and Armed Forces Institute
1. S. Minko, Responsive Polymer Materials: Design and
of Regenerative Medicine Award no. W81XWH-08-2-0034.
repeatedly (movie S5), generating an open-circuit Applications (Blackwell, Ames, IA, 2006).
Experimental procedures, additional data for materials
voltage up to 3 V. A 10-megohm resistor was 2. E. W. H. Jager, E. Smela, O. Inganäs, Science 290, 1540
characterization, and the device test are presented in the
(2000).
loaded onto this generator (Fig. 4B), and the peak supplementary materials. We thank D. Bong for thoughtful
3. Y. Osada, H. Okuzaki, H. Hori, Nature 355, 242 (1992).
output reached ~1.0 V (Fig. 4D). Analysis indi- discussion and N. Zhang for help in the preparation of figures.
4. A. Lendlein, H. Y. Jiang, O. Jünger, R. Langer, Nature
cated that the frequency of the alternating voltage 434, 879 (2005). Supplementary Materials
signal was ~0.3 Hz (fig. S12), which matched the 5. A. Lendlein, R. Langer, Science 296, 1673 (2002). www.sciencemag.org/cgi/content/full/339/6116/186/DC1
motion frequency of the generator (movie S5). The 6. M. Camacho-Lopez, H. Finkelmann, P. Palffy-Muhoray, Materials and Methods
M. Shelley, Nat. Mater. 3, 307 (2004). Supplementary Text
average power output was 5.6 nW (fig. S13), which 7. C. L. van Oosten, C. W. M. Bastiaansen, D. J. Broer, Figs. S1 to S16
corresponded to a power density of 56 mW/kg for Nat. Mater. 8, 677 (2009). Tables S1 and S2
the 100-mg generator. In contrast, the same PVDF 8. Y. Yu, M. Nakano, T. Ikeda, Nature 425, 145 (2003). Eqs. S1 to S3
element did not move on the moist substrate, and 9. J. Kim, J. A. Hanna, M. Byun, C. D. Santangelo, Movies S1 to S5
R. C. Hayward, Science 335, 1201 (2012). References (27–32)
the recording showed only noise (fig. S14), with 10. A. Sidorenko, T. Krupenkin, A. Taylor, P. Fratzl,
analysis of this background noise giving an av- J. Aizenberg, Science 315, 487 (2007). 17 September 2012; accepted 9 November 2012
erage power output of 0.015 nW (fig. S15). The 11. D. J. Beebe et al., Nature 404, 588 (2000). 10.1126/science.1230262

(bacterial) to ~ 4.3-MD (eukaryotic) molecular

Sequence-Specific Peptide Synthesis by machine found in all living cells that assembles
amino acids from tRNA building blocks into a
an Artificial Small-Molecule Machine peptide chain with an order defined by the
sequence of the mRNA strand that it moves
Bartosz Lewandowski,1 Guillaume De Bo,1 John W. Ward,1 Marcus Papmeyer,1 Sonja Kuschel,1 along. Artificial small-molecule machines (5)
María J. Aldegunde,2 Philipp M. E. Gramlich,2 Dominik Heckmann,2 Stephen M. Goldup,2 have previously been used to store information
Daniel M. D’Souza,2 Antony E. Fernandes,2 David A. Leigh1,2* (6, 7) and do mechanical work (8–11); others
have been employed in synthesis to processive-
The ribosome builds proteins by joining together amino acids in an order determined by messenger ly epoxidize an unsaturated polymer (12, 13),
RNA. Here, we report on the design, synthesis, and operation of an artificial small-molecule switch “on” and “off” catalytic activity (14–17),
machine that travels along a molecular strand, picking up amino acids that block its path, to and change the handedness of a reaction product
synthesize a peptide in a sequence-specific manner. The chemical structure is based on a rotaxane, (18). Large synthetic DNA molecules have been
a molecular ring threaded onto a molecular axle. The ring carries a thiolate group that iteratively used to guide the formation of bonds between
removes amino acids in order from the strand and transfers them to a peptide-elongation site unnatural building blocks (19–22) and assemble
through native chemical ligation. The synthesis is demonstrated with ~1018 molecular machines
acting in parallel; this process generates milligram quantities of a peptide with a single sequence 1
confirmed by tandem mass spectrometry. School of Chemistry, University of Manchester, Oxford Road,
Manchester M13 9PL, UK. 2School of Chemistry, University of
Edinburgh, The King’s Buildings, West Mains Road, Edinburgh
ells achieve the sequence-specific synthe- molecular machines that transcribe information

C
EH9 3JJ, UK.
sis of information-rich oligomers and poly- from the genetic code (1). The most extraordi- *To whom correspondence should be addressed. E-mail:
mers through the operation of complex nary of these is the ribosome (2–4), a ~2.6-MD [email protected]

www.sciencemag.org SCIENCE VOL 339 11 JANUARY 2013 189