Article

Cite This: J. Agric. Food Chem. 2019, 67, 3966−3980 pubs.acs.org/JAFC

A Dual Cross-Linked Strategy to Construct Moldable Hydrogels with

High Stretchability, Good Self-Recovery, and Self-Healing Capability
Yang Qin,†,‡,§ Jinpeng Wang,†,‡,§ Chao Qiu,†,‡,§ Xueming Xu,†,‡,§ and Zhengyu Jin*,†,‡,§
†
State Key Laboratory of Food Science and Technology,‡ School of Food Science and Technology, and §Synergetic Innovation
Center of Food Safety and Nutrition, Jiangnan University, Wuxi, Jiangsu 214122, People’s Republic of China
*
S Supporting Information

ABSTRACT: Most conventional synthetic hydrogels suffer from poor mechanical properties; despite recent significant
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progress in fabricating tough hydrogels, it is still a challenge to simultaneously realize high stretchability, self-recovery, and self-
healing capability in a hydrogel. In this work, a new type of starch/PVA/borax hybrid dual cross-linked (DC) hydrogel was
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synthesized by a one-pot method. The as-prepared DC hydrogels exhibited mechanical properties of remarkable extensibility
(ca. 2485%), excellent toughness (ca. 290.5 kJ m−3), high compression strength (ca. 547.8 kPa), rapid recoverability (81.9%
energy recovery after 30 min), and free-shapeable behavior. More impressively, the DC gels sustained approximately 300 times
their own weight and exhibited an outstanding self-healing capability at room temperature both in air and underwater.
Furthermore, the adsorption amount of methylene blue onto the anionic DC gel (144.68 mg/g) was much higher than that of
corn starch gel. Consequently, the eco-friendly, stable, and biodegradable hydrogels will have a great potential application in
removing anionic dyes from the wastewater produced by agriculture and industry.
KEYWORDS: dual cross-linked network, starch matrix, hydrogels, free-shapeable behavior, swelling-resistant, methylene blue

■ INTRODUCTION
One of the most promising soft and hydrophilic materials,
hydrogels have a three-dimensional cross-linked network
structure composed of polymer chains and adjustable physical
and chemical properties.1,2 These smart materials have
received considerable attention from academia and industry
due to their unique applications in a diverse range of fields,
such as tissue-engineered scaffolds,3−5 coating materials,6 water
treatment,7,8 drug delivery,9−11 and biosensors.12,13 Due to the
intrinsic structural heterogeneity and/or lack of an effective
energy dissipation mechanism, most conventional hydrogels
suffer from poor mechanical properties,14−16 which severely
limits their application in industrial and commercial fields.
High mechanical strength, stretchability, and self-healing
capacity are highly desirable but are inversely related properties
of gel materials. Superior mechanical strength and stretch-
ability avert breakage of the materials, while the self-healing
capacity enables the materials to spontaneously recover their
functionality and mesh structure after being damaged.1 The
presence of diverse mechanical properties in hydrogel systems
has recently become a hotspot for the research focused on the
field.11,17,18 However, most hydrogels possess only one of these
properties and very few possess all properties. Therefore, it is
still a challenging task to combine high stretchability and
strength with good self-healing capacity in a single material.19
Great efforts have been made to develop versatile hydrogels
to solve this predicament by introducing new network
structures and/or energy dissipation strategies to strengthen
the mechanical properties of hydrogels,2,11 such as double-
network (DN) hydrogels, nanocomposite hydrogels, ionically
cross-linked hydrogels, hydrogen-bonded hydrogels,20−24 etc.
First proposed by Gong et al.25 in 2003, DN hydrogels are a
promising way to achieve this goal. The DN hydrogel is
composed of two different polymer networks with asymmetric
structures, i.e., a rigid and brittle first network, which provides
a skeleton structure to the hydrogel, and a soft and stretchable
second network, which provides elasticity.26,27 Owing to the
unique dual-network structure, DN hydrogels have exhibited
desirable mechanical properties and energy-dissipating per-
formance. DN hydrogels are considered impressive materials
because they demonstrate excellent mechanical properties.12,19
Although these DN hydrogels demonstrate improved proper-
ties over their corresponding single-network (SN) parent
hydrogels, the mechanical properties do not improve as
significantly as expected.
Recently, dual cross-linked (DC) network hydrogels, as a
special DN gel, have attracted widespread interest from
academia as they optimize and combine different properties
of each network structure, including dual physically cross-
linked hydrogels,2,16 dual chemically cross-linked hydrogels,28
and hybrid cross-linked hydrogels.29 However, chemically
cross-linked points lack the ability to efficiently recover from
damage caused by stretching and compressing, resulting in a
loss of mechanical properties due to the permanent breaking of
chemical bonds.30,31 In contrast, physically cross-linked points
were reversible, which allowed hydrogels to recover or self-heal
after a large deformation or disruption, i.e., the first network
unzips and dissipates energy upon deformation, and thus, the
physical bonds can reform after removal of the stress.
Afterward, many efforts have been made to endow a self-
healing capacity and multifunctional properties to hydrogels.
Received: September 20, 2018
Revised: March 4, 2019
Accepted: March 19, 2019
Published: March 19, 2019

© 2019 American Chemical Society 3966 DOI: 10.1021/acs.jafc.8b05147

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Journal of Agricultural and Food Chemistry
The research works have focused on the construction of DC
network hydrogels by dynamic and reversible physical bonds
(e.g., hydrogen bond, hydrophobic interaction, π−π stacking,
or ionic bond).14−16,24,32 However, there are a number of self-
healing hydrogels that are frequently plagued with problems
such as long self-healing time and stimulus dependence in
application.6,9,11,14,16 Moreover, it is still worth evaluating the
bioactivity of the synthetic hydrogels owing to a number of
vinyl monomers as the building block for the DC network.
Recently, rising needs in the biochemical, medical, and
functional food fields spurred considerable interest in
developing an efficient strategy for the preparation of nontoxic,
environment-friendly, biocompatible, and biodegradable multi-
functional hydrogels as replacements for synthetic materials.
To address these concerns, as a scaffold or functional matrix,
biomacromolecules have been used to construct bioactive DC
hydrogels (e.g., gelatin,17 cellulose,33 chitosan,34 carrageenan,31
and protein2,35). Due to its great cross-linking ability in the
presence of abundant hydroxyl groups, starch is known to be a
good precursor material for preparing hydrogels.36 However,
the starch-based hydrogels exhibit poor mechanical properties
and brittleness, which thus hampers the development of
unmodified starch as a stable hydrogel.36,37 Due to the −OH
groups in each of the repeating molecular units, poly(vinyl
alcohol) (PVA) is proven to simultaneously have good gel- and
film-forming capability.38 Thus, the introduction of PVA
improves the mechanical properties and stability of starch-
based gels.39,40 Furthermore, studies have demonstrated that
introducing cross-linking agents (epichlorohydrin) markedly
strengthens the mechanical and thermal properties of starch/
PVA composite films through cross-linking the chains of starch
and PVA.41 Borax (B), as a reversible cross-linker, dissolves
and dissociates into borate ions (B(OH)4−) in water. The PVA
chains and borate ions can easily form a single cross-linked
(SC) network structure. On the basis of the above strategy,
Sreedhar et al. investigated the effect of B concentrations on
the thermal, mechanical, and surface characterizations of the
soluble starch and PVA blend films.42 Moreover, boron
complexes of PVA and starch blend films were also prepared
by Bursali et al., who investigated the effect of the cross-linking
agent (glutaraldehyde) on the antimicrobial activity of the
composite films.43 These studies had prepared PVA matrix
composite film as the starting point and mainly investigated the
effect of the addition of starch and the cross-linking agent on
the physicochemical properties of the films, rather than
investigating the mechanical behaviors and the interaction
mechanisms. Starch, as a poly hydroxyl macromolecule, is
similar to PVA. Inspired by this, we wondered if we could
simultaneously introduce the PVA chains and borate ions to
starch-based gels for constructing a novel DC hydrogel with
excellent mechanical properties, self-recovery, and self-healing
abilities at room temperature. Moreover, it is necessary to
understand whether cross-linked interactions occurred among
the starch and PVA chains and the borate ions. To the best of
our knowledge, the starch-based DC hydrogels with high
stretchability, mechanical strength, and self-healing properties
have never been reported in the literature previously.
In this paper, we report a new type of hybrid (physical and
chemical hybrid) DC starch-based hydrogel through a one-pot
method, i.e., the retrogradation technology combined with
freezing−thawing technology (Scheme 1). The as-prepared
DC hydrogels consist of a hydrogen-bond-associated starch
network and a dynamic borate bond cross-linked network.
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Scheme 1. Schematically Fabrication of the Method and
Formation Mechanism of CS/PVA/B Double Cross-Linked
(DC) Hydrogel (a) and the Single and Double Cross-
Linked Network (SC and DC) Formed by Several Specific
Interactions among Corn Starch (CS), PVA, and Borax (B):
Hydrogen Bond, Borate Bond (Reversible Ionic Crosslink),
and Chain Entanglement (b)
Within the DC gels, the borate ions further assured the
interpenetration, tangling, and cross-linking of corn starch
(CS) and/or PVA chains by covalent bonds (Scheme 1b).
Consequently, the hydrogen bonds and borate ions jointly
promoted the strong interaction between CS chains and PVA
chains, making the interconnection of the CS and PVA
networks denser. Among the networks, CS networks provide a
firm platform to bear stress, and the dynamic PVA/B networks
endow the hydrogels with a self-healing capacity. As a result,
the DC hydrogels achieved high stretchability and toughness as
well as self-recovery and self-healing abilities at the same time.
Additionally, because of the presence of numerous borate ions
(B(OH)4−) in DC gel, the anionic DC gel exhibited an
efficient adsorption of MB from the aqueous environment
through electrostatic attraction. This work provides a new
design strategy to prepare starch-based gels with highly
mechanical, stable, self-healing, and high adsorption properties;
consequently, we hope the renewable, biocompatible, and
biodegradable DC gel will have a promising application in the
fields of agriculture, biomedicine, and pollutant adsorbents.
■
MATERIALS AND METHODS
Materials. Corn starch (CS, 26.9% amylose content) was
purchased from Ingredient China Ltd. (Guangdong, China). Poly-
(vinyl alcohol) (PVA, DS = 1750 ± 50, degree of deacetylation,
99.0%; Mw = 75000−80000 g/mol) and sodium tetraborate
decahydrate (Borax, over 99.5% purity; Mw = 381.37 g/mol) were
supplied by Sinopharm Chemical Reagent Co., Ltd. (Shanghai,
China). Methylene blue (MB) was supplied by Aladdin and was used
as an adsorbate. All reagents were of reagent-grade.
Synthesis of CS/PVA/B DC Hydrogel. CS/PVA/B hydrogels
with corn starch, PVA, and B were prepared via one-pot tandem
reactions as shown in Scheme 1. PVA powders were dispersed in
deionized water and stirred at 95 °C for 30 min to ensure that the
PVA powders dissolved enough. The PVA solution and the
gelatinized starch solution were well mixed in a PVA solution with
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continuous magnetic stirring (300 rpm/min) to form a mixture of
homogeneous solutions of 10 wt % (starch) and 4 wt % (PVA) in
concentration, respectively. Afterward, the mixed solution was heated
at 95 °C in a water bath with magnetic stirring for 1 h. Subsequently,
B powders were slowly added to the CS/PVA mixed solution with the
concentration of 0.026 mol/L, which were stirred vigorously (300
rpm/min for 2 h) until there was a formation of homogeneous sol. In
order to avoid the evaporation of the water, the heating and stirring
process was conducted in a hermetically sealed beaker. Moreover, the
sol underwent ultrasonic treatment for 5 min to remove air bubbles.
Finally, the resultant uniform sol was poured into a cylindrical plastic
mold (45 mL) and first stored at 4 °C for 12 h to form the gel
network of starch. Afterward, to further enhance the network of the
hydrogels, the samples were frozen at −18 °C for 4 h and unfrozen at
25 °C for 8 h, and the freezing−thawing process was performed one
time. In addition, all of the other hydrogels were prepared according
to the conditions processed for the CS/PVA/B hydrogels. The
control sample, starch, PVA, and starch hydrogels with PVA or B were
synthesized by using the same experiment process. The eventual
samples were named CS, PVA, CS/B, PVA/B, and CS/PVA. All
specimens with various compositions were listed in Table 1.
Table 1. Hydrogels with Various Compositions and the
Corresponding Water Contentsa
starch PVA borax water content
sample (wt %) (wt %) (mol/L) (%)
CS 10.0 0.0 0.0 89.14 ± 2.01
PVA 0.0 4.0 0.0 94.99 ± 1.39
CS/B 10.0 0.0 0.026 86.79 ± 0.95
PVA/B 0.0 4.0 0.026 93.35 ± 1.32
CS/PVA 10.0 4.0 0.0 83.97 ± 1.41
CS/PVA/B 10.0 4.0 0.026 79.46 ± 0.79
a
Values represent the mean ± standard deviation of triplicate tests.
Characterization. FTIR spectra of the hydrogels were obtained
on a Nicolet IS10 spectrometer (Thermo Nicolet, Inc., Waltham, MA,
U.S.A.) equipped with an attenuated total reflection (ATR) accessory
over the wavenumber range of 4000−400 cm−1. XRD diffraction
results for the hydrogels were obtained using an XRD diffractometer
(D2 PHASER, Bruker AXS, Inc., Germany) equipped with Cu Kα
radiation in the range of 4−40° at a scan rate of 0.02°/min. All
samples were freeze-dried prior to analysis. The morphology of the
specimens was taken with a scanning electron microscope (SEM,
7500F, JEOL, Japan) at an accelerating voltage of 5 kV. The hydrogels
were frozen in liquid nitrogen, snapped immediately, and further dried
for 24 h in vacuum. Afterward, the cross sections of the specimens
were coated with gold vapor, observed, and photographed. Water
content and degree of swelling of the hydrogel were determined by
the gravimetric method. The weight of the cylindrical hydrogel (25
mm × 16 mm) was determined (W1). Then, the samples were dried
at −80 °C for 48 h to obtain the dry mass (Wd). The water content is
defined as (W1 − Wd)/W1. The gels were continuously retrieved from
the deionized water at room temperature. The swelling ratio of the
hydrogel was measured gravimetrically as a function of time (0−96 h)
after excess water was removed on the surface of the gels with dry
paper. The swelling ratio of the hydrogels can be calculated as (Wt −
Wd)/Wd, where Wt is the weight of the swollen gel. The zeta potential
of the swollen DC gel solution was determined by a dynamic light
scattering instrument (Zetasizer Nano ZS, Malvern, U.K.) under
different pH conditions adjusted by using NaOH and HCl solutions.
MB Adsorption Test. The adsorption of MB from aqueous
solution onto gel adsorbent was systematically evaluated. A certain
amount of gel adsorbent was added into 100 mL of MB solution (150
mg L−1), and the mixture was placed in an isothermal water bath
shaker (25 °C) at 250 rpm. After a period of time, the supernatant
was centrifuged and the concentration was measured with a UV−vis
spectrophotometer (UV-1800, Shimadzu Corporation, Japan) at 663
nm as λmax of MB. Effects of contact time (0−48 h), pH level (2−10),
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hydrogel dosage (25−250 mg), initial MB concentration (50−250
mg/L), and temperature (25, 37, 50, and 55 °C) have been explored
to evaluate the performance of sorbents. Then, the adsorption
capacity was calculated using the following equation:
qt = (C0 − Ct )V /m
where qt (mg/g) is the adsorbed amount after time t, C0 and Ct (mg/
L) are the initial concentration and remaining concentration after
time t, respectively. V (mL) is the volume of MB solution, and m
(mg) is the weight of gels.
Mechanical Property Measurement. Compressive Tests. The
compressive properties of the hydrogels were analyzed using a texture
analyzer (TA-XTplus, Stable Micro Systems, Surrey, U.K.). Both
uniaxial and cyclic compressive tests were all conducted on a
cylindrical sample (25 mm in diameter and 16 mm in height).
Afterward, it was placed on the lower plate of the instrument and
compressed with a P36R probe at a strain rate of 0.2 mm s−1 at room
temperature (25 °C) in air. The compressive modulus was calculated
by fitting the initial slope of the stress−strain curves.44 Compression
strain and stress data were recorded during the experiments.
Hysteresis Tests. The cylindrical hydrogel specimens were first
compressed by a loading cycle to a maximum strain of 70% with a
speed of 0.2 mm s−1 and then unloaded at the same rate. As for the
recovery experiments, the gel samples were relaxed at 25 °C for a
certain waiting time (0 min, 30 min, and 5 h) before the next loading
process, during which time the specimens were coated with a silicon
oil surface and then encased in a plastic wrap to avoid and minimize
water evaporation. The energy dissipation was calculated from the
area between the loading−unloading curves.45 The residual strain
ratio was calculated by the ratio of height change along the direction
of stress after removal of stress with respect to the original height of
the specimen.46
Tensile Tests. The hydrogels were cut into a dumbbell shape with a
gauge length of 20 mm, a width of 10 mm, and a thickness of 5 mm.
Subsequently, the samples were elongated to breakage at a rate of 100
mm min−1. The tensile strain was determined as the elongation
divided by the initial length. The tensile stress was defined as the load
force divided by the original specimen cross-sectional area. The elastic
modulus of the gels was calculated by fitting the initial linear regime of
the stress−strain curve.47 For the self-healing experiments, the strip
hydrogels were cut into halves, and then the two parts were placed in
contact with each other at room temperature in air. Moreover, there
was no other outside stimulus applied during the healing process.
After self-healing, the tensile test was carried out again to calculate the
healing efficiency. In addition, the hardness of the hydrogel was
analyzed using a texture analyzer fitted with a P 0.5 probe. The test
speed was 0.5 mm s−1, and the hydrogels were compressed twice to a
strain of 70%.
■
RESULTS AND DISCUSSION
Fabrication Process and Formation Mechanism.
Scheme 1 schematically indicates the fabrication process and
formation mechanism of the CS/PVA/B DC hydrogel. When
the gelatinized starch solution was well mixed in a PVA
solution completely, PVA chains transferred into the interstitial
water phases of the starch gels. Afterward, the resulting pastes
were stored at 4 °C, and the amylose and/or amylopectin
chains in starch cross-linked via numerous hydrogen bonds and
formed a strong physical cross-linking framework in the
gel.48,49 Neighboring PVA chains formed crystallites through
the freezing−thawing method,50 and the crystallites served as
linked points for the PVA chains to fabricate another soft
network. Borate ions further assured the interpenetration,
tangling, and cross-linking of CS and/or PVA chains by
covalent bonds and hydrogen bonds (Scheme 1b). Due to the
high affinity toward hydroxyl groups, the borate ions formed
complexes rapidly and reversibly in aqueous media with the
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Figure 1. (a) FTIR spectra and (b) X-ray diffraction patterns of CS, CS/B, PVA, PVA/B, CS/PVA, and CS/PVA/B hydrogels. SEM images
exhibiting the microstructure of (c) CS, (d) CS/B, (e) PVA, (f) PVA/B, (g) CS/PVA, and (h) CS/PVA/B hydrogels.
poly hydroxyl polymers,51,52 and then the borate ions acted as
an ionic cross-linker between the CS and/or PVA chains.
Moreover, hydrogen bonds and borate ions jointly promoted
the strong interactions between CS and PVA chains, and then,
the two networks were connected more closely. The two
networks become entangled and sustain each other via
hydrogen bonds and ionic interactions, resulting in the strong
DC hydrogel.25,27
Structures and Morphologies of the Hydrogels. To
confirm whether there were ionic interactions between CS and
PVA chains in the presence of the cross-linking agent (B),
FTIR was carried out to gain insight into the vibration of
molecules. As shown in Figure 1a, a large peak attributed to
O−H stretching was observed and located at 3100−3700 cm−1
in all spectra. The C−O−C bond of starch showed discernible
absorption peaks at 1160 and 1080 cm−1.53,54 In the pure
spectrum of PVA, the absorption peak at 1100 cm−1 was
related to the C−O in stretching mode for PVA.55 Compared
with the CS/PVA gel, the −OH stretching peak of the CS/
PVA/B DC hydrogel shifted to a lower wavenumber (blue-
shift). Stronger H-bonding leads to a more significant shift in
vibrational frequency.50 Because borate ions are probably
attached to the −OH groups of PVA, amylose, and/or
amylopectin chains via H-bonds, the interactions of H-bonds
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were enhanced. Therefore, the broad band from 3100 to 3700
cm−1 may be assigned to the −OH groups of starch and PVA,
as well as the complexes that formed among starch and/or
PVA with borate ions. A similar result was reported by Manna
and Patil (2009).56 After the addition of B molecules within
the hydrogels, they displayed several distinct peaks character-
istic of B and borate, i.e., 661 cm−1 (bending of B−O−B
linkages within borate networks), 833 cm−1 (B−O stretching
from residual B), and 1330 and 1420 cm−1 (asymmetric
stretching of B−O−C from the complexes).57 When borate
ions were introduced into the networks of CS, PVA, and CS/
PVA gels, separately, there were two new vibrational
absorption peaks observed at 1330 and 1420 cm−1. The CS/
PVA/B DC hydrogel spectra showed the characteristic
absorption peaks of starch, PVA, and B. This confirmed not
only the occurrence of complexes between borate ions and CS
or PVA chains but also the presence of cross-linking networks
among CS chains and PVA chains with borate ions within the
hydrogels.
The XRD profiles of SN (CS and PVA), SC (CS/B and
PVA/B), DN (CS/PVA), and DC (CS/PVA/B) gels are
presented in Figure 1b. The retrograded CS SN gel at low
temperature exhibited a B-type with diffraction peaks at 2θ of
17.1° and 22.2°.58 With the addition of B, the typical peaks of
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Figure 2. Photographs showing the processes of the compressing and loosening behaviors of shapeable CS-based hydrogels: (a) CS single network
hydrogel, (b) CS/PVA double network hydrogel, (c) CS/B single cross-linked hydrogel, and (d) CS/PVA/B double cross-linked hydrogel.
Schematic illustration of the possible mechanisms of the CS-based gel network compression and loosening process.
CS crystallites disappeared, with only a blunt amorphous peak
centered at 2θ = 22.2°. These results revealed that the strong
interaction between CS chains and borate irons inhibited the
retrogradation of the amylose and/or amylopectin in starch
and led to the decrease of CS crystallites. The PVA gel showed
two typical peaks at 2θ of 19.4° and 22.9°.59 Borate ions
destroyed the organized configuration of PVA, and thus the
diffraction peaks of PVA/B gel became weaker.51 The intensity
of the diffraction peak at 17.1° of CS/PVA gel decreased
significantly, indicating that the hydrogen bonding interactions
between CS and PVA chains were disadvantageous to
improving the ordering arrangement of the amylose and/or
amylopectin chains. However, the CS/PVA/B DC gel
displayed very low crystallinity, even lower than those of the
CS/PVA gels. The result indicates that borate ions could
weaken the self-hydrogen bonding of the DC gel to a
considerable degree by forming new cross-linking bonds with
CS and/or PVA chains and thus further restrains the
crystallization of CS/PVA gels. It was thus concluded that
the presence of borate ions and PVA chains would inhibit the
retrogradation of amylose and amylopectin in starch, and in
turn affected the starch crystal structure of DC hydrogels.
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Morphology of the Hydrogels. SEM images of the inner
morphologies of freeze-dried hydrogels are shown in Figure
1(c−h). The pure CS gels showed a lamellar and loose
microstructure. After borate ions were introduced, the CS/B
hydrogel structure became dense in the pore wall. The fracture
surface of the PVA gel was rather flat and smooth without
holes, while the addition of B to the hydrogel resulted in a fine,
micrometer-porous network structure. The phenomenon may
be caused by the formation of densely cross-linked complexes
among starch (amylose and/or amylopectin) or PVA chains
with borate ions. Moreover, CS/PVA gel exhibited a
comparatively coarse and porous surface, which combined
the characteristics of both CS and PVA. Compared with two
different cross-linked gels (CS/B and PVA/B), the surface
image of the CS/PVA/B DC gel in Figure 1h formed an
enhanced microstructure with a large number of small, regular
cellular nests. From the micromorphology, the internal
skeleton of the DC gel was more orderly and compact,
which could lead to its better mechanical properties.
Steadiness of the Hydrogels. The cylindrical shaped
samples were kept at room temperature for 60 s, and a shape
change was observed (Figure S1). In particular, the shape of
the PVA/B SC hydrogel showed significant changes, proving
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Figure 3. Mechanical properties of hydrogels at room temperature: (a) compressive stress−strain curves, (b) compressive loading−unloading
curves, and (c) compression modulus and hysteresis energy of CS, CS/B, PVA/B, CS/PVA, and CS/PVA/B hydrogels. (d) Photographs revealing
the notable compression resistance of CS/PVA/B DC hydrogel.
that the bonds of borate ions and PVA hydroxyls are
dynamic.32 The prepared pure PVA specimen was in the sol
state and exhibited good fluidity. Compared with the PVA/B
SC hydrogel, the shape of the DC hydrogel remained the same.
The reason for the higher stability of the hydrogel is the greater
number of hydrogen bonds and the stronger cross-linked
interactions obstructing the motion of the PVA chains.60,61
Moreover, the first starch network also provided an additional
platform to firm the structure, thus improving the stability of
the second network. Although all of the CS-based hydrogels
(CS, CS/B, CS/PVA, and CS/PVA/B) could remain at the
same initial shape, significant differences in the mechanical
strengths were exhibited.
Mechanical Properties. Then, we initially compared the
compression behavior of CS-based hydrogels. While the
hydrogels were compressed, the cylindrical CS SN and CS/
PVA DC gels exhibited different degrees of damage (Figure 2a,
b). Because the polysaccharide-based hydrogels exhibited poor
mechanical strength and a brittle network structure,62,63 we
speculated that the breakage of the SN and DN hydrogels were
related to the first starch networks formed through hydrogen
bonds of amylose and/or amylopectin chains (Figure 2e, f). As
the borate ions were introduced into the hydrogels, the CS/B
SC and CS/PVA/B DC hydrogels could be compressed using
high strain without breaking (Figure 2c, d), indicating that
introducing borate ions markedly strengthens the networks of
the two hydrogels and endows extraordinary mechanical
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properties. In spite of withstanding high-level deformation
compression (over 50%), the CS/B and CS/PVA/B gels
exhibited only deformation behavior, while no stiff CS network
or flexible PVA network destruction was observed. The
mechanical strength and toughness of the SC and DC gels
was an enhanced result owing to the cross-linked interactions
of CS and/or PVA chains with borate ions. More importantly,
upon removal of the deformation force, the compressed DC
gels could recover their initial height and shape (after five
repetitions), while the CS/B SC hydrogels partly returned to
their initial height (approximately 60%). CS supported many
hydroxyl groups on their surfaces that formed hydrogen bonds
with PVA chains, forming a cross-linked network with chain
entanglement. The borate ions cross-linked the chain
entanglement of CS and PVA and further reinforced the
networks, which enhanced the ductility of the DC gels (Figure
5k, l). The cyclic compression and stress relaxation processes
revealed that SC and DC gels exhibited excellent shape-
recovery properties.30,64 To further evaluate whether CS-based
hydrogels could withstand continuous compression stress,
optical photographs of the mechanical performance of the
hydrogels were taken, as shown in Figure S2. The CS, CS/B,
and CS/PVA hydrogels break down directly when the gels
were subjected to weight (∼1 kg) for 5, 60, and 15 s,
respectively. By contrast, the DC hydrogel with a slight
deformation sustained a loading weight of ∼1 kg (approx-
imately 300 times its own weight) for more than 5 min. Upon
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Figure 4. Self-recovery of CS/PVA/B DC hydrogels at room temperature: (a) compressive curves, (b) loading−unloading curves, and (c) time-
dependent hysteresis recovery and hysteresis energy histogram of DC hydrogels and the corresponding recovery photographs (inserted image). (d)
The consecutive compression curves with gradient increased in maximum strain on CS/PVA/B DC hydrogels; the DC hydrogel withstand the
compressive strain of 99% without breakage.
removal of the load, the DC hydrogel rapidly recovered its
original shape within 15 s. These results determined that
introducing PVA chains and borate ions reinforced DC
hydrogels and made the DC gels able to withstand continuous
compression and, consequently, possess higher stiffness and
compression strength, which far exceed those of the parent gels
(CS, CS/B, and CS/PVA).
To better understand how the second PVA/B network
compositions affect the mechanical properties of DC gels, we
conducted a series of compressive tests to investigate the effect
of PVA chains or borate ions on the mechanical properties of
DC hydrogels (Figures S3 and S4). When the PVA
concentrations were increased from 2 to 4 wt %, the DC
gels exhibited a monotonically enhanced compression stress,
compression modulus, and hysteresis energy. The result was
possibly due to more CS chains cross-linked with PVA chains
via borate ions, thus leading to an enhancement in the
mechanical properties of the DC hydrogel. However, a further
increase in the PVA content resulted in the decrease of
mechanical strength in the DC gel, which might be attributed
to the inhibited formation of the first starch networks by
residual PVA chains. Similar to the PVA concentration effect,
when the DC gels contained 0.026 mol/L of B, both
compression stress and hysteresis energy achieved maximal
values of 219.6 ± 15.7 kPa and 5790 ± 450 J m−3, respectively
(Figure S4bd). However, at the high B concentration (0.039
mol/L), the mechanical behavior of the DC gels exhibited a
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decreasing trend. Previous studies reported that excessive
cross-linking could cause the first and second networks to
become brittle and lose ductility.17 Therefore, the CS/PVA/B
DC gels prepared under optimal conditions were used in the
subsequent experiments.
Favorable mechanical properties are of great significance for
hydrogels in practical applications. The pure CS SN and CS/
PVA DN hydrogels exhibited brittle behavior (Figure 3a) and
fractured at a strain of 32.3 and 29.4% (Figure S5a),
respectively, which meant the cross-linked networks of the
hydrogen bonds were not able to withstand large deformations.
The load force changed the orientation and relative position of
amylose and amylopectin chains in the CS gel. Meanwhile, the
interstitial waters were squeezed out, and thus, the
compression stress of the CS increased with the increasing
strain. However, the interspace for chain movement
determined the increase of the compression strain. Once the
compressive deformation reached its limit, a further increase in
the load resulted in much more breakage of the gel networks.
By contrast, the reinforced CS/B and PVA/B SC hydrogels did
not break at strains as high as 70%, suggesting a soft yet tough
behavior. Moreover, incorporation of borate ions and PVA
chains to form the PVA/B SC gel also conquered the low
modulus of the PVA SN gel. It can be clearly seen that when
the second PVA/B network was combined with the CS
network, the mechanical strength of the DC gel increased
dramatically. For instance, the compression stress reached up
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Figure 5. CS/PVA/B DC hydrogels exhibiting an excellent free-shapeable property to form any complex shape with very fine structures, including
starfish (a), shell (b), conch (c), and cherry blossom (d, e). DC gels are highly strong and flexible to withstand stretch winding (f), convolving (g),
knotting (h), knot stretching (i), and stretching (j) without breakage. Tensile stress−strain curves of DC hydrogel: the DC gel achieved the highest
strain of 2485% (k). The image of stretched hydrogel (l) and the schematic diagram of original and stretched DC gel network structure (m).

to 209.8 ± 16.8 kPa for the DC gel, which was 1090%, 1200%,
and 1410% higher than those of the corresponding CS SN
(19.2 ± 2.3 kPa), CS/B SC (17.4 ± 1.6 kPa), and CS/PVA
DN (14.7 ± 1.3 kPa) hydrogels, respectively (Figure S5b).
Moreover, the compression modulus was 13.54 kPa for the DC
hydrogel, 8.61 kPa for the CS SN hydrogel, and 7.21 kPa for
the CS/PVA DN hydrogel (Figure 3c), indicating the
mechanical strength of the DC gel exceeded those of either
of its parent gels. Furthermore, the photographs of the DC
hydrogel for the presentation of mechanical properties have
been recorded as well. As shown in Figure 3d, the DC gels can
partly return to their initial shapes after compression with a
strain of 70%−80%, showing a much improved toughness than
conventional hydrogels.65 Cyclic compressive assays were
performed to evaluate the energy dissipation capacity of the
hydrogels (Figure 3b, c). The CS/PVA/B DC hydrogel had a
larger hysteresis loop than the CS-based and PVA/B SC
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hydrogels, confirming the more efficient energy dissipation of
the DC gels. Moreover, the energy dissipation of the DC gels
reached as high as 5750 ± 450 J/m−3, which was 4.5, 8.0, and
11.5 times higher than the CS, CS/B, and CS/PVA gels,
respectively (Figure 3c). Intriguingly, the values of the
cumulative energy dissipation of all the control specimen gels
(CS, CS/B, CS/PVA, and PVA/B) were approximately two
times lower than that of the DC hydrogel. The results further
illustrated that incorporating PVA chains and borate ions
improved the mechanical properties of the starch hydrogels.
We speculated that the reason for the notable hysteresis loop
could stem from the much more reversible dissociation−
association of CS and PVA chains cross-linked by the ionic
bridge of the borate ions upon compression. Meanwhile, the
reversible dissociation−association process enabled an efficient
stress transfer and energy dissipation,46 contributing more
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significant viscous dissipation and shock absorbing capacity
than those of H-bonds in the SN gels.
Self-Recovery Behaviors of DC Hydrogels. In addition
to the reinforcement of mechanical strength, another advanta-
geous feature of the DC network structure is the ability to
undergo repeated association to endow excellent self-recovery
behaviors of gels (Figure 2d). To evaluate the self-recovery
efficiency of DC hydrogels, the recovery performance of the
gels at a strain of 70% with different interval times (0−5 h) was
tested. The compression strength and hysteresis loop of the
DC hydrogels gradually increased with the extension of the
resting time (Figure 4a, b). Moreover, we used the hysteresis
energy to calculate the recovery efficiency of the DC hydrogel,
and the recovery efficiency of DC gel exceeded 81.9% and
93.5% after 30 min and 5 h, respectively. As the resting time
was prolonged from 0 min to 5 h, the hysteresis energy
increased from 3970 ± 190 to 5360 ± 310 J m−3. Owing to the
dynamic nature of the coordination interactions (hydrogen
bonds, borate ion cross-link interactions, etc.) within the DC
hydrogel, they can be rapidly reestablished when the external
load is removed. Therefore, the gels could recover all or part of
the original mechanical properties if the second load was
delayed for a longer time, highlighting their efficiency as an
energy dissipating mechanism. The morphology of the DC gels
after recuperating for 30 min and 5 h is shown in Figure 4c.
The consecutive compression curves with gradient increases in
the maximum strain on DC hydrogels are shown in Figure 4d.
Upon increasing the strain (70%−99%), the compressive
strength of the gels increased from 211.7 to 547.8 kPa. The
result suggested that the DC gels mentioned above could
sustain the high-level compressive deformation (strain up to
99%), and the breakage surface of the gel was not observed
after the load was removed.
Free-Shapeable Properties and Stretchability of DC
Hydrogels. Figure 5 shows that the DC hydrogels displayed a
milky white color as well as strong and free-shapeable
properties. As shown in Figure 5a−e, DC gels were highly
free-shapeable to form different fine structures, such as a
starfish, shell, conch, and cherry blossom shapes. This is
important to extend the starch-based hydrogel’s application,
especially in the bioengineering field where artificial tissues
with specific geometrical shapes are used to achieve their
biologically mimicking functions.13,28 Additionally, DC gels are
highly ductile and flexible to withstand stretch winding (Figure
5f), convolving (Figure 5g), knotting (Figure 5h), knot
stretching (Figure 5i), and stretching (Figure 5j). Moreover,
an intact DC gel was easily stretched to approximately 4-fold
its original length (Figure 5j). Particularly upon removal of the
deformation force, the convolving hydrogels could recover
their initial shapes, which further confirmed that the gels
exhibit excellent shape-recovery properties. Afterward, the
recuperative DC gel was knotted again, which also bore a large
deformation of 350% without breakage (Figure 5i). As a proof-
of-concept, Figure 5k and l shows the tensile stress−strain
properties of the DC hydrogel. The pure starch matrix
hydrogels were too brittle to be tested for mechanical tensile
properties, while the obtained DC hydrogel exhibited much
better tensile properties. The fracture strain of the DC gel
reached up to 2480% with a tensile strength of ∼12500 Pa,
which are the top values ever reported in starch hydrogel
systems. In addition, the visual inspection of the stretching
demonstrated that the DC hydrogels had excellent mechanical
tensile properties (Figure 5i). The enhanced stretchability of
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the DC gels was due to the chain entanglement of amylose
and/or amylopectin chains and PVA chains through ionic
interaction of the borate ions (Figure 5m). The fantastic
integration of good ductility, flexibility, and free-shapeability
would broaden the scope of application for the fabricated
composite hydrogels.33
Self-Healing Capacity of DC Hydrogels. The novelty of
this DC hydrogel is not only reflected in its excellent
mechanical and free-shapeable properties but also in its
outstanding automatic self-healing capacity. We conducted a
macro self-healing experiment where the cylindrical DC gel
was cut into three pieces, and the pieces were kept in close
proximity, as represented in Figure 6a. After contact for 15 s, it
Figure 6. Visual evidence of self-healing of a CS/PVA/B DC
hydrogel. A cubic DC hydrogel is cut into three pieces (a1); two or
three parts of the hydrogels are then placed in contact with each other
for 15 s (a2, a3), and the whole hydrogel is lifted without any of the
pieces falling. (a4) The self-healed hydrogel on a bridge support which
can withstand 50 g of weight (approximately 5-fold its own weight).
After the pieces were in contact for 30 s, the self-healed hydrogel
could withstand 1000 g of weight (approximately 100-fold its own
weight) without breakage. Conch shaped hydrogel: the cut sample of
the conch hydrogel (b1). The self-healed gel can bear its own weight
(b2) and sustain bending without breaking (b3, reverse; b4, lateral).
Shell shaped hydrogel: strip shaped hydrogel (c1); the self-healed shell
hydrogel also can withstand its weight (c2) and bend in a U shape
without breaking (c3, up−down; c4, left−right). The shell hydrogel is
cut into small pieces (c5); the pieces are put in the shell- or crab-
shaped mold, and are molded in air or water for 5 h. The gel pieces
heal as integral shell- and crab-shaped hydrogels (c6, c7). The points
of contact are encircled by a red circle.
should be noted that the pieces of hydrogel joined together to
form a single entity without a visible joint interface, and then
the integrated gel could be lifted without falling (Figure 6a2,
a3), supported its own weight by placing it on a bridge (Figure
6a4), and withstood an ∼50 g weight (approximately 5-fold its
own weight). If the contact time of the pieces was delayed for
30 s, we found that the self-healed DC hydrogels did not break
under a static load of ∼1 kg (more than 100-fold its own
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Figure 7. Schematic illustration of the mechanism of CS/PVA/B DC hydrogel self-healing process in air at room temperature (a).The tensile
stress−strain curves of the self-healed DC hydrogels with various healing time at room temperature (b), the corresponding fracture stress and
fracture strain (c), and the elastic modulus and toughness (d) of self-healed DC hydrogels for the indicated times. Numbers denote the healing
efficiency of DC gels.
weight). Moreover, the self-healing property of the conch- and
shell-shaped DC hydrogel was also proven by lifting it with
fingers, standing it upright on a table, and by bending the gel in
a U shape (conch-shaped, reverse and lateral; shell-shaped,
up−down and left−right) as shown in Figure 6b and c (b1−b4
and c1−c4) where the self-healed pieces are intact. The point of
self-healing can be noted from the remaining scar (red circle).
Afterward, we further challenged our DC gels to inspect their
self-healing properties. As shown in Figure 6c, the self-healed
shell-shaped DC hydrogels were cut into multiple fragments
again (c5) and put into a shell- and crab-shaped mold,
respectively. It is noteworthy that the fragments could also be
remolded and could form an unabridged shell- and crab-
shaped hydrogel both in air and underwater after contact for 5
h (c6, c7), which suggested excellent self-healing performance
of the DC hydrogels. The dynamic cross-linking of CS and/or
PVA chains with borate ions was possibly still carried out, with
these chains intertwining with each other, and thus the
hydrogels could heal. With the rapid self-healing capacity both
in air and underwater, the DC gels will have huge potential
applications, especially in fields that require a fast response or
fast working behaviors.
Healing efficiency is an important parameter to characterize
the degree of self-healing; therefore, tensile tests were
conducted on the original and self-healed samples.66,67
Fracture strain and stress recovery percentages of the self-
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healed gels were defined as the self-healing efficiency.68 The
fractured parts were put back together, in contact, for different
lengths of time (15, 30, 60, and 600 s) in the air at room
temperature. The healed hydrogel was stretched to test the
tensile strength (Figure 7). In the case of 15 s healing time, the
cut gels were partially self-healed; the healed gel could sustain a
tensile stress of 6300 Pa with elongation strain of 985% before
fracture. Moreover, the elastic modulus, fracture strain, and
healing efficiencies significantly increased (p < 0.05) with an
increased healing time. When the healing time exceeding 600 s,
the fracture energy of the healed gel was 199.1 ± 21.1 kJ m−3
with a strain over 2000% (the fracture energy and fracture
strain of the initial gel were 290.5 ± 19.4 kJ m−3 and 2485%,
respectively). The healing efficiency was 68.5% based on stress
or 81.2% based on strain. The tensile strain recovered to more
than 80%, and thus, we speculated that the CS network could
be responsible for the healing process. Therefore, we also
investigated the self-healing behaviors of the parents of the DC
hydrogel. Although the CS SN and CS/PVA DN hydrogels did
not exhibit self-healing (Figure S6), the introduced borate ions
cross-linked CS/B hydrogel possessed a self-healing behavior
(Figure S7). As shown in Figure S7, the two pieces of CS/B
SC hydrogel formed an integrated gel which was lifted and
could withstand its weight (b, c3). Afterward, the two broken
starfish-shaped SC hydrogels healed completely without a
visible joint interface after 12 h at 25 °C. The healed gel could
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Figure 8. Swelling properties of hydrogels. Photos of the shapeable CS, CS/B, CS/PVA, and CS/PVA/B aerogels before (a) and after (b) swelling
in deionized water. Light-weight CS/PVA/B DC aerogel could be supported by a tender leaf (c). Swelling kinetics of CS, CS/B, PVA, PVA/B, CS/
PVA, and CS/PVA/B aerogels in the deionized water at room temperature. The PVA, CS/B, and PVA/B aerogels reach equilibrium within 9 h,
while the CS, CS/PVA DN, and CS/PVA/B DC aerogels can reach equilibrium at approximately 36, 30, and 60 h, respectively (d). Compression
stress−strain curves of the CS, CS/B, CS/PVA, and CS/PVA/B gels in the swollen state (e).

withstand gentle stretching (c4). These results further
confirmed the occurrence of cross-linking networks between
CS chains with borate ions within the CS/B SC hydrogels. In
addition, we predicted the healing mechanisms of the DC gel
(Figure 7a). When the two fracture surfaces were put in
contact at room temperature, the borate bonds within the
network were able to recross-link the broken CS and/or PVA
chains by forming new complexes. The CS chains were
dragged by PVA chains and tangled with each other via
hydrogen bonds to form a new network. Self-healing
capabilities were demonstrated by uniting the two pieces
into one.69 Once they were repaired with the reversible ionic
cross-link and hydrogen bond mechanism, the hydrogel
samples could regain their mechanical properties. Overall,
the fast self-healing of the DC gels resulted from the
reestablishment of the network structure.
Swelling Properties of Hydrogels. Figure 8d shows the
time dependence of the water absorbency of the hydrogels.
Due to the loose network structure of the hydrogel, the SN
(CS and PVA) and SC (CS/B and PVA/B) aerogels exhibited
fast initial swelling. Compared with the SN and SC gels, the
CS/PVA DN and CS/PVA/B DC gels were capable of
absorbing fewer quality water molecules. Moreover, the
equilibrium water content (EWC) of DC and DN was only
4.52 and 3.15 g/g, respectively (Figure 8a). These results
suggested that the DC hydrogel exhibited good swelling
resistance as compared with those of either of its parent gels.
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This phenomenon is possible due to the stronger double cross-
linked structure and more chain entanglements via hydrogen
bonds, making the network closer and hindering the water
molecules from accessing the hydrogel cage, which results in
lower EWC. When borate ions are introduced into the
network, we noticed the EWC of the cross-linked network gels
(CS/B, PVA/B, and CS/PVA/B) was larger than the
corresponding control (CS, PVA, and CS/PVA). The borate
ions may influence the formation of the crystallinity of the
starch and PVA networks and result in an increased
amorphous region of the hydrogels; thus, their water-holding
abilities increased. This observation was also noted in the X-ray
results (Figure 1b). At the same time, Figure 8b exhibits the
dried and swollen CS, CS/B, CS/PVA, and CS/PVA/B gels,
which nearly hold their initial shapes in a swollen state.
However, the swollen PVA and PVA/B gels were collapsed and
could not retain their shapes, and thus, the PVA and PVA/B
were not shown in the figure.
Then, we further inspected the compressive properties and
textural hardness of the pillar-shaped hydrogels in their swollen
states (Figures 8c and S5). The mechanical properties of the
swollen CS and CS/B gels were slightly decreased compared
with the original levels. This result was due to the destruction
of the network structure during the freeze-drying process,
causing the SN and SC gels to exhibit a weaker mechanical
property. As listed in Table 1, the water content of the gels
remained at a high level (70−95%) owing to the strong H-
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Figure 9. Effects of contact time, pH, temperature, hydrogel dosage, and initial MB concentration on the adsorption amount of MB onto gels. (a)
Contact time (t = 0−48 h, C0 = 150 mg/L, V = 100 mL, T = 25 °C, pH = 6.45, dos. = 100 mg), (b) temperature (CS/PVA/B DC gel, C0 = 150
mg/L, V = 100 mL, t = 24 h, pH = 6.45, dos. = 100 mg), pH (CS/PVA/B DC gel, C0 = 150 mg/L, V = 100 mL, t = 24 h, T = 25 °C, dos. = 100
mg), (c) initial concentration (CS/PVA/B DC gel, t = 24 h, V = 100 mL, T = 25 °C, dos. = 100 mg), and hydrogel dosage (CS/PVA/B DC gel, C0
= 150 mg/L, t = 24 h, V = 100 mL, T = 25 °C, pH = 6.45). Here, qe represents the adsorption amount of MB onto gels at equilibrium.

bonds and sufficient interaction between the hydroxyl groups
of adjacent polymer strands.70 Therefore, we speculated that
the reason for the decreased strain was more water molecules
were introduced into the CS network from the swelling,
thereby leading to decreased interactions between the CS
strands. The freeze-drying process enhanced the crystalline and
cross-linking density of PVA within the hydrogel, and
consequently, the mechanical strength of the CS/PVA gel
increased. It is noteworthy that although the strength of the
swollen DC hydrogels was lower than that of the initial DC
gels upon addition of borate ions, the swollen DC hydrogels
still exhibited excellent mechanical properties. Figure 8c shows
the compression stress−strain curves of the swollen hydrogels,
and one can see the DC hydrogel demonstrated high
mechanical performance with 166.2 kPa compression stress,
70% compressive strain, and 1610.7 g of hardness (Figure S5).
The mechanical strength recovered to a great extent, i.e., the
recovery efficiency of swollen DC gel reached as high as 79.2%
and 100% based on the compression stress and strain,
respectively. In addition, the CS/PVA/B DC aerogel was
lightweight and could be supported by a tender leaf (Figure
8c).
Absorption of MB. Contact time is an important factor
that indicates whether the adsorbent removes the target
contaminant to reach the equilibrium. It is apparent that the
adsorption amount rapidly increased initially and then
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gradually slowed until equilibrium was reached (Figure 9a).
This may be ascribed to the higher MB concentration, faster
diffusion, and more adsorptive sites at the initial adsorption
phase.71 With increasing adsorption time, the vacant adsorptive
sites of the DC gel decreased, which lowered the probability of
interactions between MB and the adsorptive site, and
consequently, the adsorption gradually slowed and eventually
tended to balance. When the adsorption of the hydrogels
achieved equilibrium, the MB adsorption capacities of CS/B,
PVA/B, and CS/PVA/B respectively reached 80.32, 65.26, and
144.68 mg/g, which were higher than those of the
corresponding CS (16.43 mg/g), PVA (38.29 mg/g), and
CS/PVA (26.41 mg/g) gels. Considering the anionic
characteristic of the hydrogels, we hypothesized that a possible
reason for the increase of the adsorbed ionic dyes might be
attributed to the electrostatic interactions.71 Furthermore, the
porous cross-linked structure would be beneficial for the
adsorption process since it increased surface area and
facilitated diffusion of dyes into the adsorbent.72 Thus, a
significant increase in the adsorption capacity of CS/PVA/B
was observed. Moreover, the color of the solution with CS/
PVA/B DC gel turned significantly transparent (Figure S8),
especially in comparison with CS, indicating the beneficial
effects of borate ions and PVA on MB adsorption.
The effects of temperature and pH on the removal amount
are important factors to evaluate dye adsorption in agricultural
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and industrial wastewater at different temperatures and pH
values. When the temperature increased, the adsorption
capacity of MB on DC gel decreased; however, it was still
higher than that of the gels (CS, CS/B, PVA, PVA/B, and CS/
PVA) at 25 °C. As the solution pH was changed from acidic to
basic, the zeta potential of the swollen DC gel solution
decreased from −0.24 to −25.60 mV (Figure S9). It can be
speculated that the isoelectric point (pI) for the DC gel was
less than pH 1.0. When the solution pH > pI, the DC gel is
negatively charged, which was favorable for adsorbing MB
owing to the electrostatic attraction. It can be seen that the MB
adsorption of DC hydrogels was highly pH dependent. Close
to neutrality or under alkaline conditions, an obvious increase
in the adsorption amount was observed. Moreover, the
adsorption amount of MB on DC gel markedly increased
from 56.33 to 144.29 mg/g as the solution pH increase from
2.0 to 8.0 (Figure 9b). Under acidic conditions (pH of 1.0−
5.0), the protonation of boric acid (B(OH)3) groups was
unfavorable for the adsorption process due to the fewer
hydrogen bonds between the DC gel and MB. At basic
conditions, the deprotonation of B(OH)4− resulted in the
destruction of hydrogen bonding interactions and the “charge
screening effect” of excess Na+ ions also prevented effective
electrostatic interactions between the borate ions of gel and
MB. Under neutral conditions, the moderate residual B(OH)4−
and B(OH)3 groups may be conducive to the formation of
electrostatic interactions and hydrogen bonds between DC gel
and MB, leading to the optimal adsorption capacity of DC gel
for MB. As depicted in Figure 9c, because the initial MB
concentration is fixed, when the gel dosage increased, the total
adsorption amount of MB on the hydrogel increased, but the
adsorption amount per unit mass of DC gel was decreased and
the utilization of adsorbent would be greatly reduced. In
addition, the adsorption amount was significantly affected by
the initial concentrations of dye solution. With increasing the
MB concentrations, the adsorption amount exhibited an
initially increasing and then an equilibrium trend (Figure
9c). The removal amount was 143.66 mg/g at 150 mg/L MB
dye initial concentration, which increased to 170.29 mg/g at
200 mg/L initial concentration.
In summary, we have designed and fabricated a one-pot
method, which is a simple, time-saving, and easily controlled
process to prepare hybrid DC hydrogels. Within the DC gel,
hydrogen bonds cross-linked to CS chains created the rigid and
brittle first network, and dynamic borate bonds cross-linked to
PVA chains formed the second network. The first network
provides reversible sacrificial bonds and dissipates energy,
whereas the second network provides elasticity to the DC
hydrogel. Because of the distinct hybrid physically and
chemically cross-linked structure, the DC hydrogels showed
notably improved mechanical properties over the single
physically cross-linked starch-based hydrogels. The tensile
fracture strains and toughness of the DC hydrogels could be as
high as 2485% and 290.5 kJ m−3, respectively. Moreover, the
compression strength of the DC gels reached 547.8 kPa at a
compression strain of 99%, which was significantly higher than
those of the starch matrix hydrogels previously reported in the
literature. They retained their original shapes after continuous
loading−unloading compressive cyclic tests, demonstrating
their superior self-recovery ability. Furthermore, the DC gels
exhibited remarkable self-healing properties both in air and
underwater at room temperature. Especially, the healed DC
hydrogel specimens still showed ∼20 times elongation at their
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break. What’s more, because of its unique reversible network
structures, the gel system is able to form any complex shape.
The combination of good mechanical properties, self-recovery
of strength and toughness, and free-shapeable ability, along
with an easy synthesis method, allow the materials to have
many potential applications in the fields of biomaterials and
load-bearing artificial soft tissues. In addition, the introduction
of borate ions and PVA play an important role in the
adsorption of MB by DC hydrogel, whose maximum removal
amount reaches 144.68 mg/g, which is much higher than that
of CS gel. Consequently, the prepared DC gels could serve as
eco-friendly, stable, and efficient adsorbents for cationic dyes
from agricultural and industrial effluents.
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.jafc.8b05147.
Compressive stress−strain curves, compression stress
and modulus, compressive loading−unloading curves,
and corresponding hysteresis energy of hydrogels with
different PVA and B concentrations; hydrogel steadiness
images; photographs of the mechanical performance of
CS-based hydrogels; self-healing properties of CS, CS/
PVA, and CS/B hydrogels; compressive strain, stress,
and textural hardness of hydrogels in the initial and
swollen states; and images of the MB dye solution
adsorption on different hydrogels (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: fpcenter@jiangnan.edu.cn.
ORCID
Zhengyu Jin: 0000-0001-6880-9955
Funding
This work was supported by the National First-Class Discipline
Program of Food Science and Technology
(JUFSTR20180203).
Notes
The authors declare no competing financial interest.
■
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3980 DOI: 10.1021/acs.jafc.8b05147

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