pubs.acs.

org/journal/ascecg Research Article

Ultrafast Self-Healing, Reusable, and Conductive Polysaccharide-

Based Hydrogels for Sensitive Ionic Sensors
Yanling Wang, Hailong Huang, Jieli Wu, Lu Han, Zhongli Yang, Zhicheng Jiang, Rui Wang,
Zhijian Huang, and Min Xu*
Cite This: ACS Sustainable Chem. Eng. 2020, 8, 18506−18518 Read Online

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ABSTRACT: The ever-growing demand for wearable electronic

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devices is stimulating the development of novel materials for

fabrication of flexible electronics. Among all promising candidates,
polysaccharide-based hydrogels are constructing a prospective
pattern for achieving flexible electronic functionalities, benefiting
from their ecofriendliness, renewability, biodegradability, and
sustainability. However, one of the most important drawbacks of
these hydrogels is slow self-healing. To address the above-
mentioned issue, we propose a simple method to fabricate a
starch-based (starch/polyvinyl alcohol (PVA)/borax, SPB) con-
ductive hydrogel. Due to the dual reversible interactions of
hydrogen bonding and the boronic ester linkages, the hydrogel
presents enhanced mechanical performance and ultrafast self-
healing ability both in air and underwater. The mechanical properties recover within 10 s in air and within 120 s underwater, and the
electronic functionality recovers within 90 ms in air and within 110 ms underwater. In addition, the abovementioned two
interactions also endow the hydrogel with reversible sol−gel transition properties, which allow the hydrogel to be reused repeatedly.
Due to large amounts of Na+ and free B(OH)4− ions, the hydrogel showed great conductivity and may work as strain sensor with
high sensitivity (GF = 1.02 at 110−200% strains). The ionic hydrogel sensor could rapidly (≤180 ms) perceive human motions,
even very small motions such as swallowing and pronunciation. With the combination of these seductive features, such an
ecofriendly polysaccharide-derived hydrogel prepared through a facile and green preparation process would have great potential
application for sustainable wearable sensors.
KEYWORDS: starch, hydrogel, ultrafast self-healing, underwater, reusability, sensors

■ INTRODUCTION
During the past few years, modern wearable electronic
in ionic sensors. These conductive hydrogels are intrinsically
flexible and stretchable and could largely sustain their bulk
devices with mechanical performance similar to or beyond conductivity in the process of reversible deformations.16,17 In
general, hydrogels are typically susceptible to tearing or other
that of soft biological tissues have been igniting marvelous
severe mechanical deformations, resulting in losses of their
study sparks, particularly in the fields of human−machine
functionalities. Hence, it is significant to endow hydrogels
interfaces,1−3 implantable physiological tracking,4−6 health-
with a self-healing capacity for their further applications.18,19
care monitoring,7−10 and energy storage.11 For these
Motivated by this point, extensive efforts have been
applications, mechanical deformability (e.g., compression,
devoted to designing hydrogels capable of healing damaged
stretching, and bending) and conductivity of the electronic
structures and properties. According to previous studies,
devices are pivotal to realize their fundamental functionalities.
devising self-healing hydrogels focuses mainly on noncovalent
Considering the functionalities of these devices, mimicking
bonds,20−25 such as electrostatic interactions, metal−ligand
the sensory ability of humans is one of the ultimate goals. In
coordination, hydrogen bonding, hydrophobic association,
particular, flexible and stretchable strain sensors, quantita-
tively monitoring the electrical output signals responsive to
diverse external deformations, have drawn tremendous Received: August 28, 2020
interest because of their wide applications in human− Revised: November 5, 2020
machine interfaces, personalized health monitoring/diagnos- Published: December 9, 2020
ing, soft robotics, and electrical interconnects.12−15 In recent
years, a series of ionic hydrogels containing solvated
deliquescent salts (e.g., NaCl and LiCl) have been applied

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18506 ACS Sustainable Chem. Eng. 2020, 8, 18506−18518
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host−guest recognition, π-π stacking, and invertible dynamic-
covalent bonds,26−28 such as acylhydrazone bonds, disulfide
bonds, imine bonds, and boronic ester bonds. In contrast to
some healing processes requiring external stimuli,29,30 such as
mechanical, thermal, photic, electrical, or magnetic stimuli,
the healing process of repairing the damage automatically
without any other external stimuli attracts more attention. In
addition, there are still other daunting dilemmas such as long
self-healing time and specific repair environments for
hydrogels. In particular, the self-healing performance of
hydrogels underwater has rarely been investigated. In general,
it is still a profound challenge to devise automatically ultrafast
self-healable hydrogels that can be utilized both in air and
underwater.
Additionally, electronic wastes (e-wastes) arising from
nondegradable and nonreusable electronic components in
flexible electronic devices will increase the burden on the
global environment. To solve the abovementioned problem,
consideration has been given to the ecofriendliness and
reusability of electronic materials. Recently, some soft
electronics based on sustainable and ecofriendly biomaterials
such as cellulose derivatives,31 silk,32 polylactic acid,33 and
poly(lactic-co-glycolic acid)34 have been found to decompose
under external triggers. However, it is difficult for these soft
electronics to reutilize and recover their functionalities, but
some hydrogels with sol−gel transition behavior have been
applied to the area of recyclable hydrogel electronics. For
instance, poly(vinyl alcohol) (PVA)/glycerol/polyaniline
(PGA) ecofriendly hydrogels have been used to fabricate a
reusable biosensor to detect the conventional motion signals
of the human body.35 Inspired by this application,
incorporating PVA into renewable natural polysaccharides
to develop polysaccharide-derived hydrogels with sol−gel
transition behavior might be a feasible strategy for the
fabrication of sustainable and reusable hydrogel electronics.
In this study, taking starch, one of the most abundant
polysaccharides present in nature, as the main raw material,
we proposed an easily accessible fabrication method for
ecofriendly polysaccharide-derived hydrogels (starch/polyvin-
yl alcohol (PVA)/borax hydrogels, SPB hydrogels). The
presence of abundant free sodium ions (Na+) and borate ions
(B(OH)4−) imparts conductivity to the SPB hydrogels. Based
on synergistic dual reversible interactions including hydrogen
bonding and dynamic boronic ester linkages, the as-fabricated
hydrogel exhibits enhanced mechanical properties and
ultrafast self-healing properties. The self-healing time is
approximately 10 s for mechanical properties and 90 ms for
electrical properties in air. Moreover, the SPB hydrogel not
only self-heals in air but also self-heals underwater, which has
seldom been achieved for the hydrogels reported previously
(Table S1). The reversible sol−gel transition property
endows the SPB hydrogel with reusability, which might
relieve some of the e-waste pollution on earth. Therefore, the
SPB hydrogels developed in this work simultaneously
integrate several desirable features, including ultrafast self-
healability both in air and underwater, stretchability,
conductivity, reusability, and ecofriendliness, which make
the SPB hydrogels extremely suitable for sustainable flexible
strain sensors to distinctly perceive external stimuli via real-
time electrical output signals.
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■
pubs.acs.org/journal/ascecg Research Article
EXPERIMENTAL SECTION
Materials. Starch (soluble, from potato) and borax (Na2B4O7·
10H2O, guaranteed reagent) were purchased from Sinopharm
Chemical Reagent Co., Ltd. (Shanghai, China). Polyvinyl alcohol
(PVA) (degree of hydrolysis is 99% and viscosity is in the range of
27.0−34.0 mPa·s) was obtained from Shanghai Titan Technology
Co., Ltd. (Shanghai, China). All chemicals were used directly as
received. Deionized water was used for all experiments.
Synthesis of Starch/PVA/Borax (SPB) Hydrogels. The SPB
hydrogels were synthesized by a one-step method. The component
ratios in the hydrogel were tunable. In brief, predesigned weight
ratios of starch, PVA, and borax were weighed and dissolved in
deionized water (95 °C) under stirring for 3 h to form a transparent
and viscous solution. Then, the resultant solution was left to stand
at 95 °C for 2 h to remove trapped air bubbles. Finally, the hydrogel
was obtained after natural cooling to room temperature in the mold.
The ionic hydrogels with different compositions were coded as
SPxBy, where x and y represent the mass of PVA and borax, and the
mass of starch was constant at 10.50 g. For example, the hydrogel
containing 10.50 g of starch, 1.50 g of PVA, 1.20 g of borax, and
66.00 g of water was designated as SP1.50B1.20, and the detailed
compositions of SPB hydrogels are shown in Table S2.
Characterization. Fourier transform infrared spectroscopy
(FTIR, Thermo Nicolet Nexus 670, USA), solid 11B nuclear
magnetic resonance spectroscopy (NMR, Bruker 400 MHz,
Germany), and X-ray photoelectron spectroscopy (XPS, Thermo
Scientific Escalab 250XI, USA) were performed to characterize the
chemical structures of the samples. X-ray powder diffractometry
(XRD, Rigaku Ultima IV, Japan) was performed with Cu Kα (λ =
1.5406 Å) radiation to analyze the crystal distribution of samples
operating at 35 kV and 25 mA. The morphology of the freeze-dried
hydrogel was observed using a scanning electron microscope (SEM,
Hitachi S-4800, Japan).
Mechanical Tests. The mechanical tests were carried out using
a tensile testing machine (Instron 5967, USA) with a 100 N load
cell. The hydrogels with a size of 80 × 10 × 3 mm were pulled at
20 mm/min. Then, the strain (ε) was calculated with the ratio of
the elongated length (L) to the initial length (L0) according to eq 1:
ε = (L − L0)/L0 (1)
All the stresses were calculated using eq 2:
σ = F /A 0 (2)
where F is the applied load, and A0 is the starting cross-sectional
area. The elastic modulus was identified as the initial linear slope of
the stress−strain curve. The toughness was calculated by integrating
the area below the stress−strain curve. The average strengths were
obtained from three parallel samples in the same group.
Self-Healing Experiments. One piece of the hydrogel was
stained with alizarin red, and another piece was stained with
rhodamine B. The two stained hydrogels were cut into two pieces
and then the fresh cross sections of the hydrogel dyed with different
colors were brought into contact in the air and underwater. Then,
the mechanical properties of the healed samples were measured to
evaluate the self-healing capacity based on the detailed parameters of
mechanical tests. The healing efficiency was calculated via eq 3:
η = S0 / S h (3)
where S0 and Sh are the fracture stress of the original and healed
hydrogel samples, respectively.
Reusability of SPB Hydrogels. To demonstrate the reusability
of the SPB hydrogel, the hydrogel was cut into fragments to
simulate the breakage of the hydrogel; and the fractured hydrogel
fragments were heated at 95 °C for 30 min to obtain a uniform
viscous solution. The solution was then poured into designed molds
and cooled to room temperature to obtain a reused hydrogel. The
mechanical and electrical properties were studied accordingly.
Electrochemical Measurements. Electrochemical impedance
spectroscopy (EIS) was recorded using an electrochemical instru-
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Figure 1. Schematic of the synthetic process for the SPB hydrogels and the corresponding interactions inside the hydrogel networks.
ment (Autolab M204, Netherlands) with a two-probe method. The
frequency range was from 1 MHz to 1 Hz with an AC signal
amplitude voltage of 10 mV. Briefly, a piece of SPB hydrogel with a
size of 10 mm (length) × 5 mm (width) × 2 mm (thickness) was
sandwiched between copper sheets and then tested. The ionic
conductivity σ was calculated from the impedance curves through eq
4:
σ = l /(R b × S) (4)
where l is the thickness of the hydrogel, Rb is the bulk resistance
obtained from the EIS diagram, and S is the contact area between
the hydrogel and the copper sheets. To further quantitatively
evaluate the self-healing behavior of the SPB hydrogel, after
repeating cut/healing cycles, measurements of EIS were performed
as soon as the incision contacted; and then the ionic conductivity of
the healed hydrogel was calculated.
In addition, a time-dependent current curve for the electrical
signal healing process was measured by connecting the SPB
hydrogel into a direct current circuit, where a voltage of 1 V was
applied to the circuit to prevent water electrolysis or conceivable
electrochemical reactions.36 First, an open-circuit current emerged
when the hydrogel was completely severed. Then, the current
increased and finally reached close to its starting value. Furthermore,
a battery-powered circuit connecting a piece of the SPB hydrogel in
series with an LED indicator was established to visualize the
electrohealing process of the hydrogel.
Assembly of Strain Sensor. Based on the SPB hydrogels, strain
sensors under compression, tension, and bending were assembled.
The real-time electrical current signals of the hydrogel sensors were
recorded using an Autolab M204 electrochemical device, and
corresponding relative resistance changes were calculated according
to Ohm’s Law.
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■ RESULTS AND DISCUSSION
The one-pot synthesis route of the SPB hydrogel is shown in
Figure 1. Hydrogels with different PVA ratios as well as
different borax contents were fabricated via the one-pot
method. Certain amounts of starch, PVA, and borax were
added into deionized water, followed by stirring at 95 °C for
3 h. After natural cooling, starch-based hydrogels were
formed via dual reversible interactions of hydrogen bonding
and boronic ester linkages. The dynamic noncovalent
hydrogen bonds existed in starch and/or PVA chains and
reversible covalent boronic esters formed by complexing
starch/PVA with boron ions. These two interactions were
expected to endow the hydrogel with fast self-healing ability.
In addition, the entanglement between starch chains and PVA
chains might make the network denser and more stable. To
more intuitively observe the effect of the introduction of PVA
and borax on starch-based hydrogels, the mechanical
properties of the starch hydrogel and the SPB hydrogel
were compared by applying the same amount of force to the
two hydrogels and observing their bent and compressed
states. The detailed results in the Supporting Information
showed that the pure starch hydrogel could not withstand
bending (Figure S1a) and compression (Figure S1b) and
broke into several blocks, indicating its poor mechanical
behavior. By contrast, the SPB hydrogel could bear a certain
degree of stretching (Figure S1c), compression, and bending
(Figure S1d), implying an improvement in the mechanical
properties. Undoubtedly, better mechanical performance
broadens the application range of starch-based hydrogels.
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Figure 2. Characterization of the hydrogel. (a) FTIR spectra of starch, PVA, borax, and SPB hydrogel. (b) Partially enlarged FTIR spectra of
starch and SPB hydrogel in the range of 1650−800 cm−1. (c) Solid 11B NMR spectrum of the SPB hydrogel. (d) XRD patterns of starch, PVA,
borax, and SPB hydrogel.

Figure 3. XPS spectra of (a) starch, PVA, and SPB hydrogel. (b) B 1s XPS spectra of the SPB hydrogel. (c) O 1s XPS spectra of starch, PVA,
and SPB hydrogel. Deconvoluted C 1s XPS spectra of (d) starch, (e) PVA, and (f) SPB hydrogel.

Then, Fourier transform infrared spectroscopy (FTIR) and
solid-state 11B NMR spectroscopy were used to identify the
chemical structure of the resultant hydrogel. The FTIR
spectra of borax, PVA, starch, and SPB freeze-dried hydrogel
are shown in Figure 2a. The characteristic peak for the OH
stretching vibration showed a shift from low wavenumber
(3430 for starch and 3413 cm−1 for PVA) to high
wavenumber (3450 cm−1), indicating the formation of strong
hydrogen bonds between starch and PVA.37 In addition, the
FTIR results verified the formation of boronic ester bonds
through the appearance of two new peaks: peaks at 1346 and
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1112 cm−1 (Figure 2b) corresponding to the stretching
vibration of B−O−C bonds.38,39 Solid-state 11B NMR of the
SPB hydrogel was measured, and the spectrum is presented
in Figure 2c. According to previous reports, the peak at 8.8
ppm was attributed to the free boron signal; and the peaks at
−1.25 and − 5.16 ppm were ascribed to the bound boron
signals of the monoesters and diesters.40,41 The fraction of
the two states could be calculated from the peak areas of the
11
B NMR spectra. Detailed multiple peak fitting and
integration of peak areas are shown in the Supporting
Information (Figure S2). The results showed that fractions of
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boron in the free state and bound state were approximately
20.8 and 79.2% of the total boron in the SPB hydrogel,
respectively. In the bound state, the fractions of monoesters
and diesters were calculated to be 14.8 and 64.4%,
respectively.
In the X-ray diffraction analysis (XRD) patterns of the SPB
hydrogel, shown in Figure 2d, PVA itself exhibited a main
diffraction peak at 2θ of 20°, corresponding to the
crystallinity of PVA. Starch itself showed typical B-type
diffraction peaks at 2θ of 17.5° and the 2θ region of 22−24°.
The SPB hydrogel mainly showed crystallinity similar to that
of starch without the diffraction peak of PVA, indicating that
the formation process of the hydrogel might hamper the
recrystallization of PVA. Briefly, FTIR, 11B NMR spectra, and
XRD confirmed the existence of dual reversible interactions,
including hydrogen bonding and boronic esters. The presence
of abundant free borate ions (B(OH)4−) endowed the SPB
hydrogel with great ionic conductivity, which provided the
possibility for the hydrogel to be applied in the field of
flexible wearable electronic devices.
X-ray photoelectron spectroscopy (XPS) was performed to
further analyze the physical and chemical structure of the
SPB hydrogel. As shown in Figure 3a,b, the SPB hydrogel
exhibited a B 1s peak at 191.5 eV (Figure 3b), arising from
B-complexed compounds. Figure 3c shows that the binding
energy of O 1s in the SPB hydrogel (531.10 eV) was lower
than that of starch and PVA, indicating the formation of
boronic esters. In addition, the high-resolution C 1s XPS
peaks of starch, PVA, and SPB hydrogel were deconvoluted.
For starch, there were three typical peaks at 284.3, 285.8, and
287.4 eV, which were ascribed to C−C/C−H, C−O, and O−
C−O groups, respectively (Figure 3d). For PVA, there were
two main peaks at 284.4 and 285.8 eV, assigned to the C−C/
C−H and C−O groups (Figure 3e). For the SPB hydrogel,
deconvoluted peaks for C 1s were observed at 284.3, 285.7,
and 287.2 eV, attributed to C−C/C−H, C−O, and O−C−
O/C−O−B bonds, respectively (Figure 3f). With XPS
spectra, we could clearly observe the carbon atoms in
different chemical environments in starch, PVA, and SPB
hydrogels.
To investigate the morphology and microstructure of the
samples, scanning electron microscopy (SEM) was per-
formed. Freeze-dried starch hydrogel exhibited a porous
structure with an aperture of approximately 30 μm (Figure
4a), and the freeze-dried PVA hydrogel presented an uneven
porous structure (Figure 4b). Compared with starch and
PVA hydrogel, freeze-dried SPB hydrogel in Figure 4c,d
Figure 4. SEM images of the freeze-dried (a) starch hydrogel, (b)
PVA hydrogel, and (c,d) SPB hydrogel.
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exhibited a three-dimensional and interconnected multilevel-
pore architecture, which might play an important role in ion
transportation and the mechanical properties. To further
study the effect of borax and PVA on the gel morphology,
SEM images of a series of samples with different components
were obtained as shown in Figure S3. The results showed
that as the borax content increased, the pore size of the
freeze-dried hydrogel decreased. With PVA content increas-
ing, pore size of the freeze-dried hydrogel decreased, and the
pore walls became thinner. As the PVA content increased
further, the pore distribution became uneven, and porous
areas were separated by nonporous areas.
The effect of borax and PVA concentrations on the
mechanical behavior of the SPB hydrogel has been
demonstrated through the stress−strain curves. Figure 5a
shows digital photographs of the original SPB hydrogel and
the stretched hydrogel using an Instron universal testing
machine. First, the mechanical performance of SPB hydrogels
with different contents of borax was tested (Figure 5b).
Obviously, the mechanical performance of the hydrogel was
effectively enhanced by adding borax, which connected the
hydroxyl groups on starch and PVA to form boronic esters.
Specifically, as the mass of borax increased from 0 to 1.35 g,
the fracture stress of the hydrogel increased from 0.26 to 1.84
kPa (Figure 5b and Figure S4a), while the toughness
increased from 6.8 to 50.5 kJ/m3 (Figure 5c). However,
the corresponding rupture strain of the hydrogel presented a
tendency to increase first and then decrease with increasing
borax mass from 0 to 1.35 g (Figure 5c). The explanation of
this phenomenon could be that as the mass of borax
increased, the elastic modulus of the SPB hydrogel increased,
which reflected the increase of the cross-link densities.42 Also,
enhanced cross-link densities would restrict the macro-
molecular chain mobility.
In addition, the influence of PVA on the mechanical
behavior of the hydrogel was also discussed. The incorpo-
ration of PVA evidently enhanced the mechanical perform-
ance of the SPB hydrogels according to the tensile stress−
strain curves (Figure 5d). The tensile fracture stress and
toughness of the SP0.75B1.20 hydrogel were approximately 0.24
kPa and 6.8 kJ/m3, which was significantly improved
compared with the tensile fracture stress and toughness of
the SP0B1.20 hydrogel (0.17 kPa and 1.8 kJ/m3) (Figure 5e
and Figure S4b), and the corresponding fracture strain was
approximately 688%, almost eight times longer than the
fracture strain of the SP0B1.20 hydrogel (120%) (Figure 5e).
As the PVA mass increased from 0.75 to 1.50 g, the tensile
fracture stress, toughness, and rupture strain simultaneously
increased (Figure 5e and Figure S4b). The results illustrated
that the incorporation of PVA chains substantially enhanced
the mechanical properties of starch-based hydrogels. We
speculate that the improvement of mechanical performance
due to PVA could be attributed to two reasons: on the one
hand, PVA chains with many hydroxyl groups on their
surfaces form intra- and intermolecular hydrogen bonds with
starch chains and dynamic boronic esters with borate ions,
which would act as noncovalent sacrificial bonds43 and
dynamic-covalent sacrificial bonds44 efficiently dissipating
large amounts of energy. On the other hand, PVA chains
and starch chains would form a cross-linked network with
chain entanglements to further reinforce the mechanical
properties of the SPB hydrogel,45 which endows the
hydrogels with the ability to withstand large deformations
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Figure 5. Mechanical measurements of the hydrogels. (a) Digital photograph of the original SPB hydrogel and the stretched hydrogel using an
Instron universal testing machine. (b) Tensile stress−strain curves, and (c) toughness and fracture strain of SPB hydrogels with a fixed mass of
PVA (1.50 g) and different masses of borax (0, 1.05, 1.20, and 1.35 g). (d) Tensile stress−strain curves, and (e) toughness and fracture strain of
SPB hydrogels with a fixed mass of borax (1.20 g) and different masses of PVA (0, 0.75, 1.13, and 1.50 g).
and thereby satisfies the potential applications in real life.
After comprehensively evaluating the mechanical properties of
the samples, we chose SP1.50B1.20 hydrogel for further studies
unless otherwise stated.
The self-healing capacity of the hydrogel was evaluated. As
shown in Figure 6a(i, ii), when we cut the dyed SPB
hydrogels into two pieces and then placed the two parts with
different colors in contact in the air, they rapidly and
automatically rejoined within 10 s without any external
stimuli. In the meantime, the resultant hydrogels could
withstand a certain stretch (Movie S1). The severed blocks
with different colors could self-heal and support their own
weight after 10 s (Figure 6a(iv)) in the air. The hydrogel
debris was placed into a heart-shaped mold and gradually
healed into a whole in 5 h, which could bear stretching, as
presented in Figure 6b. In addition, the SPB hydrogels also
have the ability to repair themselves underwater, which
addresses the issue that hydrophilic polymers cannot heal
themselves underwater and hence broaden the practical
applications of the SPB hydrogels. As Figure 6a(iii) shows,
the two pieces with different colors were brought together
immediately underwater. Be sure to make the two pieces of
hydrogel fully contacted. After 120 s, the self-healed hydrogel
could withstand a certain stretch underwater (Movie S2).
The above experiments demonstrated that the SPB hydrogel
possessed excellent self-healing properties in different
environments and had broader application prospects.
To quantitatively assess the self-healing performance, we
carried out mechanical and ionic conductivity tests of the
hydrogel after self-healing in air and underwater to investigate
their healing efficiencies. As shown in Figure 6c(i−iv), after
being nipped by a mechanical testing machine, the original
SPB hydrogel was cut into two pieces and then made to self-
heal. After 10 s, the self-healed hydrogel was stretched to
measure its mechanical properties. As seen from Figure 6d,
the stress−strain curve of the healed hydrogel was almost
consistent with that of original hydrogel, and the self-healing
efficiency could reach to 94.3%, indicating outstanding self-
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healing ability of the hydrogel. We deemed that the
synergistic effect of dynamic-covalent boronic esters and
noncovalent intra- and intermolecular hydrogen bonds among
PVA chains and starch chains conduced to excellent self-
healing performance, which coincided with previous studies
on the ultrafast self-healing performance of boronic
esters.46−49 However, the general recovery of self-healed
materials requires several minutes or even dozens of
hours.50,51 Figure 6e shows the tensile fracture stress versus
time of the healed SPB hydrogel underwater, and the tensile
fracture stress of the healed hydrogel obviously increased
with healing time. The tensile stress of the SPB hydrogel after
recovery for 120 s was up to 93.5%, implying the ultrafast
self-healing capacity of the hydrogel underwater. This process
may occur because borate ions can move freely in the water
environment, reforming new dynamic boronic esters between
borate ions and hydroxyl groups at the hydrogel section, and
starch/PVA chains in the presence of hydrogen bonds are
still tangled. Hence, the SPB hydrogels can self-heal and
address the issue that hydrophilic polymers are difficult to
repair in water or wet environments because water on the
fracture surface of a hydrophilic polymer hydrogel can reduce
the van der Waals attraction and the electrostatic interactions,
and it is easier to form a certain interface with macro-
molecules with polar groups, thus preventing the diffusion
and collision of polymer chains.
In addition, to further quantitatively evaluate the self-
healing behavior of the SPB hydrogel, after repeating cut/
healing cycles, measurements of electrochemical impedance
spectroscopy (EIS) were performed as soon as the incision
contacted, and then the ionic conductivity of the healed
hydrogel was calculated. As shown in EIS curves (Figure 7a),
the healed hydrogel exhibited the bulk resistances similar to
its pristine counterpart, and the corresponding ionic
conductivity after the first and fifth cut/healing cycles showed
no dramatic decrease (remaining approximately 80% of the
original value) (Figure 7b), indicating excellent self-healing
performance of the SPB hydrogel for the electrical properties.
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Figure 6. Self-healing tests and photographs of the original and self-healed SPB hydrogel. (a) Two SPB hydrogels dyed in different colors were
cut into two pieces (i), hydrogel could autonomously self-heal without external stimuli in air after being in contact for 10 s (ii), and underwater
after healing for 120 s (iii); and the severed hydrogel that healed for 10 s could support its own weight (iv). (b) Hydrogel debris was put into a
heart-shaped mold and gradually healed to withstand a certain stretch. (c) Strip-shaped SPB hydrogel was cut into two pieces and stretched
after being in contact for 10 s without external stimuli. (d) Tensile stress−strain curve of the SPB hydrogel and the curve of the SPB hydrogel
healed in the air. (e) Fracture stress vs time of the SPB hydrogel healed underwater.

For the purpose of more intuitively observing the self-healing
process of electrical properties, Figure 7c,d presents time-
dependent current curves for the healing process of electrical
function in the air and underwater, respectively. One piece of
the SPB hydrogel was cut into halves, and then the fresh
surfaces of the two pieces were brought together. At this
point, the current increased and was close to its initial value.
The entire electrical healing process lasted only approximately
90 ms in the air and 110 ms underwater. Moreover, a
battery-powered direct current circuit linking an SPB
hydrogel and an LED indicator in series was established to
visualize the electrohealing process of the hydrogel shown in
Figure S5 and Movie S3. The illuminated LED indicator was
extinguished after the hydrogel was completely cut off, and
then the LED indicator was momentarily lit up when the two
pieces were brought into contact, suggesting that the SPB
hydrogel possessed excellent self-healing capacity for the
electrical function.
To better understand the self-healing mechanism of the
SPB hydrogel, we treated fresh-cut sections with urea and
glycol before contact to heal. Figure 7e shows the stress−
strain diagram of the original, urea-treated, and glycol-treated
hydrogel pieces after healing for 2 min. The tensile fracture
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stress of glycol-treated hydrogel dramatically decreased to
0.49 kPa, which was only approximately 31.0% of the tensile
fracture stress tested for the original hydrogel (Figure 7f).
The main reason for the decrease in strength is that borate
ions are more easily complexed with diol groups of small
polyols, meaning that in this case, glycol hinders the
complexation of borate ions and adjacent hydroxyls on starch
or PVA.52,53 By comparison, the tensile fracture stress of
urea-treated hydrogel piece was 1.10 kPa, approximately
69.0% of the tensile fracture stress measured for the original
hydrogel (Figure 7f), although urea could largely destroy the
hydrogen bond interaction at the cut sections. These
outcomes revealed that reversible dynamic-covalent boronic
esters mainly contributed to the excellent self-healing
performance of the SPB hydrogel. The possible mechanism
of the self-healing behavior of SPB hydrogel is illustrated in
Figure 7g.
For most previously reported hydrogel electronics, the
rupture of hydrogels would lead to the functional failure of
the device, generating large amounts of e-waste and
increasing manufacturing costs.54 The reusable hydrogel
electronics might offer a significant opportunity to address
this issue. In this study, our designed SPB hydrogel is fully
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Figure 7. Self-healing tests of the electrical properties of the SPB hydrogel. (a) Electrochemical impedance spectroscopy (EIS) of the hydrogel
after different cut/healing cycles. The inset is a model for EIS measurement of the hydrogel. (b) Ionic conductivity of the SPB hydrogel after
different cut/healing cycles. (c) Time evolution of the electrical healing process for 90 ms in the air using current measurements at room
temperature. (d) Time evolution of the electrical healing process for 110 ms underwater using current measurements at room temperature. (e)
Effect of urea and glycol treatments on the mechanical performance of the healed pieces using tensile stress−strain curves. (f) Tensile fracture
stress of original healed piece, urea-treated, and glycol-treated healed pieces. (g) Illustration of the self-healing mechanism of the SPB hydrogel.

cross-linked by two interactions, hydrogen bonds and boronic
esters. These reversible interactions endow the hydrogel with
a temperature-dependent sol−gel transition behavior (Figure
S6). The SPB hydrogel remained unstable and turned into a
viscous solution under high temperature (95 °C) and was
easily remolded into the needed shape. With decreasing
temperature, the hydrogel network gradually reformed and
remained stable. Based on this amazing property, a cylindrical
SPB hydrogel was remolded into diverse three-dimensional
geometrical shapes with intricately detailed structures (Figure
8a). Similarly, the hydrogel fragments mimicking the damage
of the hydrogel electronics could also be transformed into
whole pieces of hydrogel by heating and cooling processes
(Figure 8b).
The reused SPB hydrogel could almost recover its
mechanical and electrical functions. As exhibited in Figure
8c, the recycled hydrogel was still able to withstand stretching
and recovered its original size after the stretching was
released. Simultaneously, the LED indicator could be lit when
the reused hydrogel was connected in a circuit. Similar to the
original hydrogel, the luminance of the LED indicator
changed periodically with the stretching and release of the
hydrogel. The above results indicate that the reused SPB
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hydrogel was conductive and strain-sensitive. To further
prove the reusability of the hydrogel, mechanical and
electrochemical measurements were performed after one
cycle and five cycles. Figure 8d,e shows the tensile stress−
strain curves and corresponding toughness and elastic
modulus of the hydrogel before and after recycling one and
five times, respectively. The recycled hydrogel obviously had
a stress−strain behavior similar to the original hydrogel. The
toughness and elastic modulus showed a small increase. In
addition, EIS curves (Figure 8f) and ionic conductivity
(Figure 8g) of the hydrogels after one cycle and five cycles
exhibited only a slight decrease. The increase in toughness
and elastic modulus and the decrease in ionic conductivity
might be attributed to water evaporation during the repeated
heating processes. The results demonstrate the feasibility of
the reusable strain sensor prepared using the SPB hydrogel.
In addition, as shown in Table S1, although some flexible
hydrogel electronics exhibited stretchability, self-healability,
and adhesiveness, the ecofriendly, self-healable both in air
and underwater, fully reusable, and stretchable hydrogel
electronics developed in our work are rarely realized in these
reported hydrogel electronics.
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Figure 8. (a) Reshapeability of the dyed SPB hydrogel. (b) Demonstration of the recycling process. When mechanically broken, the dyed SPB
hydrogel could be recycled by using the hydrogel fragments at 95 °C and remolding at room temperature. (c) Images showing that the reused
hydrogel was stretchable and ionically conductive under large deformation. (d) Stress−strain curves and (e) corresponding toughness and elastic
modulus of the SPB hydrogel before and after reuse. (f) Electrochemical impedance spectroscopy (EIS) and (g) corresponding ionic
conductivity of the SPB hydrogel after different recycling cycles.

Owing to many appealing features including ultrafast self-
healing capacity, reusability, conductivity, and flexibility of
SPB hydrogels, we explored the feasibility of their potential
application as strain sensors for detecting real-time human
motions. The relative resistance changes of SPB hydrogel
resembled those of conventional ion sensors, increasing with
enhanced tensile strain due to the simultaneous shrinkage of
the cross-sectional area and enhancement of the path length
during the tensile testing process.17,37 The luminance of the
LED indicator gradually darkened as the hydrogel was
stretched, indicating that the SPB hydrogel had good
responsiveness to mechanical deformation. Besides, strain
sensitivity is a basic performance indicator of a strain sensor,
and strain sensitivity is defined as the gauge factor (GF)
according to eq 5:
GF = (R − R 0)/εR 0 (5)
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where ε is the strain, and R0 and R are the resistance at 0%
strain and the tensile strain, respectively. Under stretching,
the resistance of the hydrogel sensor increases, and the
relative resistance change ratio (R − R0)/R0 increases linearly
with increasing strain. The GF for the strain (0 < ε < 110%)
was 0.73, then increased to 1.02 at a large strain (110 < ε <
200%) (Figure 9a). This high sensitivity and quasi-linear
response might occur because the well-distributed porous
networks provided large space for the migration of large
numbers of free Na+ and B(OH)4− ions in the hydrogel.
Under tensile deformation, free ions could rapidly disperse
and rearrange via an interconnected porous structure, leading
to a rapid decrease in the ion concentration per unit volume
and eventually a fast increase in resistance (Figure 9b).
To validate the suitability of the SPB hydrogel for use in
cutting-edge wearable electronic devices, we assembled a
strain sensor based on the SPB hydrogel to detect diverse
deformations including stretching, compressing, and bending.
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Figure 9. Application demonstration of strain sensors based on SPB hydrogel. (a) Relative resistance changes of the hydrogel sensor under
tension. The inset pictures are the luminance variations of the LED indicator as the tension loading increases. (b) Schematic for ionic
concentration change per unit volume before and after hydrogel sensor stretching. Relative resistance changes in the hydrogel sensor in response
to (c) different degrees of stretching (30, 50, and 100%), (d) gentle and brutal finger presses, and (e) bending of the forefinger at different
angles (0, 30, 60, and 90°). (f) Relative resistance changes of the strain sensor at selected frequencies under a 30% strain. (g) Quick response of
the hydrogel sensor to bending. (h) Durability test under a 20% strain for 5000 cycles. (i) Schematic for signature sensing. Relative resistance
changes of the hydrogel sensor in response to (j) swallow action, (k) different pronunciation of letters: E, C, N, and U, and (l) pronunciation of
“love” with low voice and loud voice.

Figure 9c illustrates that the strain sensor was stretched and
responded rapidly to increased strains (30, 50, and 100%),
revealing the validity of the SPB hydrogel sensor under large
deformation. The variations in relative resistance presented a
positive correlation with the applied strain, matching the
results shown in Figure 9a. The hydrogel strain sensor under
compression also displayed excellent ability to distinguish
gentle pressure and brutal pressure immediately (Figure 9d),
which is a typical phenomenon for ionic hydrogels.55−57 The
restraint of ion transport was weakened, and the resistance of
the hydrogel decreased when pressure was imposed on it.
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After the pressure was withdrawn, the resistance recovered to
its original value. In addition, we attached the prepared strain
sensor to the forefinger to detect its repeated bending (Movie
S4) and bending with a stepwise increase (decrease) in angles
(0, 30, 60, and 90°). As shown in Figure 9e, the relative
resistance changes of the strain sensor increased to different
levels with the increase in the degree of the bending of the
forefinger and remained unchanged. Then, the relative
resistance changes rapidly recovered to their original levels
once the forefinger was straightened stepwise, implying a high
sensitivity of the hydrogel strain sensor (Movie S5). In
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ACS Sustainable Chemistry & Engineering
addition, the bending of other human joints (wrist, elbow,
and knee) could also be detected in real-time using an SPB
hydrogel sensor (Figure S7). Figure 9f shows the frequency
response of the SPB hydrogel strain sensor at a frequency of
0.2−1 Hz under a strain of 30%, which confirmed the
potency of the SPB hydrogel sensor in high-frequency motion
identification. The response time of the SPB hydrogel sensor
was determined by a real-time current−time curve as the
strain sensor was bent (Figure 9g). Obviously, the response
time was 150 ms for bending and 180 ms for recovering,
which is sufficient to monitor fast and transient human
motions. Stability and durability are of great importance for
the applications of strain sensors. To evaluate the stability
and durability of the SPB hydrogel sensor, loading/unloading
tensile test at a strain of 20% was performed. As shown in
Figure 9h, the relative resistance changes of the strain sensor
presented good stability over 5000 cycles except a slight
increase, and the insets exhibited the excellent repeatability of
the relative resistance changes throughout the entire stability
test, indicating a remarkable electrical stability of the SPB
hydrogel sensor.
Furthermore, through a hydrogel sensor attached to the
throat, subtle motions were also precisely detected, including
swallowing and pronunciation of letters and words. The
signature sensing model is exhibited in Figure 9i. The relative
resistance change of the hydrogel detecting swallow action
was below 30% (Figure 9j). The pronunciation of different
letters “E, C, N, and U” could be clearly distinguished on the
basis of real-time resistance changes showing different line
types (Figure 9k). This result indicated that our flexible
hydrogel strain sensor had high sensitivity and could
accurately monitor and distinguish the tiny signals, including
different degrees of vibration of the vocal cords when
pronouncing different letters. In addition, pronunciation of
“love” with a low voice and a loud voice presented a similar
line type with different relative resistance changes (the higher
the voice, the greater the relative resistance changes) (Figure
9l). Consequently, our SPB hydrogel sensor with high
sensitivity, ultrafast self-healing ability, reusability, and
environmental friendliness was suitable for applications in
flexible electronics fields.
■
CONCLUSIONS
In summary, inspired by the naturally occurring self-healing
phenomena, we have presented a facile one-step method to
construct an ecofriendly polysaccharide-derived SPB hydrogel,
integrating several appealing characteristics such as automatic
ultrafast self-healability, conductivity, ecofriendliness, and
reusability. For this hydrogel system, soluble potato starch,
a cheap, abundant, and renewable natural polysaccharide, was
selected to serve as the main network, and PVA was
introduced to enhance the mechanical performance. Dual
dynamic reversible destruction and reconstruction of hydro-
gen bonds and boronic esters in the hydrogels endowed them
with ultrafast self-healing capacity both in mechanical (94.3%
restoration after 10 s in the air and 93.5% restoration after
120 s underwater) and electrical functionalities (approx-
imately 100% restoration after 90 ms in the air and 110 ms
underwater), which enhanced the working stability and
service life of these hydrogel sensors. Additionally, the sol−
gel transition behavior provided hydrogel electronics with the
possibility for reusability, which would address the collection/
reprocessing issue and realize the sustainability of hydrogel
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pubs.acs.org/journal/ascecg Research Article
electronics. Benefiting from the aforementioned desirable
features, the SPB hydrogels were assembled into strain
sensors, which could distinctly perceive both large and tiny
human motions rapidly (≤180 ms) through electrical output
signals. Consequently, these ecofriendly polysaccharide-
derived hydrogels fabricated through a facile and green
preparation process with desirable self-healability, mechanical
properties, conductivity, and reusability further uncovered
prospective candidates for polysaccharide-based hydrogel
sensors to serve as the cutting-edge flexible wearable
electronic devices.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acssuschemeng.0c06258.
The images of the comparison of mechanical proper-
ties, solid 11B NMR spectrum, SEM images, fracture
stress of SPB hydrogels with different contents of borax
and PVA, self-healing process shown via an LED
indicator, images of sol−gel transition, strain sensor to
detect the human bending motions, comparison of
reported flexible strain sensors with this work in
properties, and the detailed compositions of SPB
hydrogels (PDF)
Self-healing process in the air (MP4)
Self-healing process underwater (MP4)
Self-healing process showed via an LED indicator
(MP4)
Strain sensor to detect the bend of a finger (MP4)
Strain sensor to detect different bend angles of a finger
(MP4)
■
AUTHOR INFORMATION
Corresponding Author
Min Xu − School of Physics and Electronic Science, Shanghai
Key Laboratory of Magnetic Resonance, East China Normal
University, Shanghai 200062, China; orcid.org/0000-
0002-3761-1396; Email: xumin@phy.ecnu.edu.cn
Authors
Yanling Wang − School of Physics and Electronic Science,
Shanghai Key Laboratory of Magnetic Resonance, East
China Normal University, Shanghai 200062, China
Hailong Huang − School of Physics and Electronic Science,
Shanghai Key Laboratory of Magnetic Resonance, East
China Normal University, Shanghai 200062, China
Jieli Wu − Instrumental Analysis Center, Shanghai Jiao Tong
University, Shanghai 200240, China
Lu Han − School of Physics and Electronic Science, Shanghai
Key Laboratory of Magnetic Resonance, East China Normal
University, Shanghai 200062, China
Zhongli Yang − School of Physics and Electronic Science,
Shanghai Key Laboratory of Magnetic Resonance, East
China Normal University, Shanghai 200062, China
Zhicheng Jiang − School of Physics and Electronic Science,
Shanghai Key Laboratory of Magnetic Resonance, East
China Normal University, Shanghai 200062, China
Rui Wang − School of Physics and Electronic Science,
Shanghai Key Laboratory of Magnetic Resonance, East
China Normal University, Shanghai 200062, China
https://dx.doi.org/10.1021/acssuschemeng.0c06258
ACS Sustainable Chem. Eng. 2020, 8, 18506−18518
ACS Sustainable Chemistry & Engineering
Zhijian Huang − School of Physics and Electronic Science,
Shanghai Key Laboratory of Magnetic Resonance, East
China Normal University, Shanghai 200062, China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acssuschemeng.0c06258
Author Contributions
The manuscript was written through contributions of all
authors. All authors have given approval to the final version
of the manuscript.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was funded by the National Natural Science
Foundation of China (grant no. 21875068).
■
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