International Journal of Biological Macromolecules 223 (2022) 1126–1137

Contents lists available at ScienceDirect

International Journal of Biological Macromolecules

journal homepage: www.elsevier.com/locate/ijbiomac

High-performance carboxymethyl cellulose-based hydrogel film for food

packaging and preservation system
Yali Zhao a, Siying Zhou a, Xiaodong Xia b, Mingqian Tan c, Yanna Lv a, Yi Cheng a, Yehan Tao a,
Jie Lu a, Jian Du a, *, Haisong Wang a, *
a
Liaoning Key Lab of Lignocellulose Chemistry and BioMaterials, Liaoning Collaborative Innovation Center for Lignocellulosic Biorefinery, College of Light Industry and
Chemical Engineering, Dalian Polytechnic University, Dalian 116034, China
b
School of Food Science and Technology, National Engineering Research Center of Seafood, Dalian Polytechnic University, Dalian, Liaoning 116034, China
c
Academy of Food Interdisciplinary Science, Dalian Polytechnic University, Dalian, Liaoning 116034, China

A R T I C L E I N F O A B S T R A C T

Keywords:
Highly stretchable hydrogel film
Food packaging and preservation
Intermolecular interaction
Dynamic reversible non-covalent bonds
Most traditional food packaging and preservation films suffer from limited stretchability and relatively simple
functionality, which severely restricts their practical application. In this study, a highly stretchable and versatile
sodium carboxymethyl cellulose (CMC)/polyvinyl alcohol (PVA)/poly(ethylene imine) (PEI)/tannic acid (TA)
hydrogel film was elaborately designed and demonstrated as an efficient food packaging and preservation sys­
tem. The dynamic reversible non-covalent within three-dimensional (3D) network structures served as sacrificial
bonds to dissipate the loaded energy and endowed the hydrogel film with excellent elongation ~400 %, which is
much larger than that of conventional food packaging films (<50 %). Furthermore, the optimized CMC/PVA/
PEI/TA3 hydrogel film delivers versatile performances, including self-healing, whole UV-blocking (<400 nm),
strong adhesive strength (234.08 KPa), antioxidation virtues, oxygen barrier (32.64 cm3*μm/(m2*d*KPa)) and
water vapor barrier (642.92 g/(m2*24 h)). Notably, the shelf life of fresh strawberries, mangoes, and cherries
was prolonged by at least one week under ambient conditions when the packaging box was covered by the
fabricated CMC/PVA/PEI/TA3 film. Thus, our work not only provides a highly stretchable and versatile hydrogel
film but also boosts the in-depth comprehension and rational design of robust food packaging and preservation
films.

1. Introduction Hydrogels are a type of soft matter with hydrophilic three-

Recently, the substitution of petroleum-based food packaging films
by biopolymers has attracted increasing attention owing to their
renewability, biodegradability, safety, non-toxicity and environmental
friendliness [1,2]. Natural polysaccharides (cellulose, starch, sodium
alginate, pectin, chitosan, etc.) [3,4], proteins (soy protein, animal
protein) [5,6] and lipids (shellac resin, acetyl glycerides, waxes, etc.)
[7,8] are often employed as substrates for the preparation of food
packaging films [9,10]. Sodium carboxymethyl cellulose (CMC) is a
water-soluble cellulose derivative with partial carboxymethyl group
modification. Owing to its biodegradability and excellent film-forming
capacity, CMC has been extensively used in medicine, food, paper,
and packaging [11,12]. However, the small strain, poor mechanical
strength, and relatively low gas barrier properties of CMC-based pack­
aging films limit their further application.
dimensional (3D) network structures that can absorb a large amount
of water without structural damage [13]. Most recently, hydrogel films
have demonstrated significant potential for applications in food pack­
aging systems [14,15]. When packaged by hydrogel films, the removal
of moisture generated by the transpiration effect of fresh food inside the
package slows down the growth of mold, yeast, and spoilage bacteria on
the surface of food, thereby preserving the sensorial characteristics of
packaged foods [16–18]. However, the integrity of the packaged
hydrogel films during transport and storage cannot be well maintained
because of their relatively poor mechanical strength, which reduces the
shelf-life of food. In addition, the commonly reported hydrogel films are
colorless and transparent, displaying no light-shielding performance. UV
light with higher energy penetrates the packaging film and causes rapid
quality loss or spoiling of the packed foods due to vitamin and color loss
and adverse effects on taste [19–21]. Good gas barrier properties of

* Corresponding authors.
E-mail addresses: dujian01@dlpu.edu.cn (J. Du), wanghs@dlpu.edu.cn (H. Wang).

https://doi.org/10.1016/j.ijbiomac.2022.11.102
Received 27 August 2022; Received in revised form 5 November 2022; Accepted 10 November 2022
Available online 14 November 2022
0141-8130/© 2022 Elsevier B.V. All rights reserved.
Y. Zhao et al.
packaging films can significantly suppress the gas exchange rate and
reduce food contamination by microorganisms [22]. In daily life, fresh
fruits are often placed in different containers, such as glass, carton,
plastic, or wooden tableware. The good adhesion performance of the
packaging film on the headspace of various substrates provides an intact
packaging microenvironment. Furthermore, lipid peroxidation often
occurs in food. The oxidation of unsaturated fatty acids results in sig­
nificant generation of dietary advanced lipid oxidation endproducts
(ALEs) which are in part cytotoxic and genotoxic compounds, posing a
threat to human health [23]. Considering these factors, to maximally
prolong the shelf life of food, an ideal packaging system should simul­
taneously possess good gas barrier, strong mechanical strength, UV-
blocking, self-sealing, and antioxidation properties.
To date, several biopolymer-based hydrogel composites (e.g., agar,
sodium alginate, carrageenan, collagen, bacterial cellulose, and CMC)
have been explored as food packaging and preservation films [24,25]. In
general, to achieve better preservation, antimicrobial compounds or
bioactive ingredients are physically incorporated into films [26]. How­
ever, such a relatively simple function cannot simultaneously meet the
aforementioned requirements for food packaging systems in practical
applications. To the best of our knowledge, the integration of these
multifunctional features into one hydrogel film to establish an effective
food packaging and preservation system remains a significant challenge.
Polyvinyl alcohol (PVA), a water-soluble and new type of eco-
friendly material, has been successfully exploited as a matrix in com­
posite films in recent years. Microorganism tests have verified that PVA
cannot restrain the growth of microorganisms and can be degraded
completely [27]. In addition, amino-rich polyethyleneimine (PEI) mol­
ecules can reinforce the interactions between molecular chains by
forming more hydrogen bonds. Herein, a multifunctional CMC/PVA/
PEI/TA composite film with desirable stretchability, UV-blocking,
antioxidation, self-healing, and adhesion features is proposed as a
food packaging and preservation system. The influence of the underly­
ing dynamic reversible non-covalent bonds, auxochromic effect of –NH2
on PEI, and catechol structure on the overall performance of the
hydrogel films was further analyzed. The practical application of the
resultant hydrogel films for the packaging and preservation of several
fresh fruits (strawberry, cherry, and mango) and the corresponding
shelf-life evaluation were performed. This study established the great
potential of multifunctional hydrogel films as food packaging systems
for food preservation.
2. Experimental section
2.1. Materials
Sodium carboxymethyl cellulose (CMC, viscosity:800–1200 mPa•s),
hydroxyethyl cellulose (HEC, viscosity:1000–1500 mPa⋅s), polyvinyl
alcohol (PVA, Mn:16000 g/mol), tannic acid (TA), and sodium chloride
(NaCl) were obtained from Shanghai Aladdin Biochemical Technology
Co., Ltd. Polyethyleneimine (branched PEI, Mn:1800 g/mol) was pro­
vided by Shanghai Macklin Biochemical Co., Ltd. All chemical reagents
were of analytical grade and used without further purification.
2.2. Preparation of CMC/PVA/PEI/TAx hydrogel film
Briefly, 50 mL of CMC solution (4 wt%), 50 mL of PVA solution (8 wt
%) and 0.6 g of TA were mixed under magnetic stirring at room tem­
perature for 1 h to obtain the homogeneous CMC/PVA/TA solution.
Subsequently, PEI was introduced into the solution and maintained at
60 ◦ C for 12 h. The acquired film-forming solution was cast on a parallel
glass plate (20 cm × 20 cm) with a film-making machine, and the coated
solution was frozen at − 20 ◦ C for 12 h. Thereafter, the frozen samples
were defrosted at room temperature, and the final hydrogel film was
obtained and denoted as CMC/PVAx/PEIy/TA (x and y represent the
mass content (%) of PVA and PEI, respectively). The moisture content of
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International Journal of Biological Macromolecules 223 (2022) 1126–1137
hydrogel films was ~89 %. After optimizing the PVA and PEI contents,
the TA doping amount in the optimized CMC/PVA/PEI/TA hydrogel
films was controlled to 0 wt%, 0.2 wt%, 0.4 wt%, 0.6 wt% and 0.8 wt%
and the resultant films were named as CMC/PVA/PEI/TA0, CMC/PVA/
PEI/TA1, CMC/PVA/PEI/TA2, CMC/PVA/PEI/TA3 and CMC/PVA/PEI/
TA4, respectively.
2.3. Characterizations of the hydrogel film
2.3.1. Morphology
The morphology and microstructures of the prepared hydrogel films
were analyzed using scanning electron microscopy (SEM, JSM-7800F,
JEOL, Japan) at an accelerating voltage of 5 kV after spray coating
with gold. The synthesized PVA/CMC/PEI/TAx hydrogel film was brittle
and broke in liquid nitrogen.
2.3.2. FTIR spectroscopy
The chemical structure was investigated using Fourier transform
infrared spectroscopy (FTIR, Spectrum Two, PerkinElmer, USA) and
infrared spectroscopy scans from 450 cm− 1 to 4000 cm− 1 with a reso­
lution of 1 cm− 1 in transmission mode for 32 scans. The intensity ratios
are presented as the average of the three replicates.
2.3.3. XRD pattern
The crystalline structure was recorded using an X-ray diffractometer
(XRD-6100, SHIMADZU, Japan) from 10◦ to 80◦ at a scanning rate of 2
o
/min at a voltage of 40 kV.
2.3.4. Barrier properties
The oxygen transmission rate (OTR) was measured using a differ­
ential pressure gas permeameter (BASIC201, LABTHINK, China) at 23 ±
0.5 ◦ C and 50 ± 5 % RH. The water vapor transmission rate (WVTR) was
determined using a water vapor permeability tester (PERMEW3/010,
LABTHINK, China) at 38 ± 0.5 ◦ C and 90 ± 5%RH. All samples were
tested at least five times, and the average values were expressed.
2.3.5. Mechanical properties
Mechanical strength was measured using an electronic universal
material test instrument (Instron 5965, Boston Instron Co. Ltd. USA).
The fabricated hydrogel film was cut into strips of dimensions 80 mm ×
20 mm (length × width). The moving distance between the two clamps
and tensile rate were 40 mm and 10 mm/min, respectively. The tensile
stress–strain curves were averaged over five measurements.
2.3.6. Thermal stability analysis
Thermal stability was measured using a thermogravimetric analyzer
(TGA, Q500, TA, USA) at 25–700 ◦ C under a nitrogen atmosphere.
Differential scanning calorimetry (DSC) analysis was performed using a
DSC Q2000 (Q2000, TA, USA) instrument with a nitrogen flow rate of
50 mL/min. The TGA curves were averaged from three measurements.
2.3.7. Optical properties
The optical properties were observed using a dual-beam UV–vis
spectrophotometer (UH5300, HITACHI, Japan). Light transmittance is
the mean value of five measurements.
2.4. Antioxidant property
The DPPH free radical scavenging activity of the hydrogel films was
characterized according to a previously reported method by Norajit
et al. [28] with modifications. The DPPH radical-scavenging activity of
the films was measured using a dual-beam UV–vis spectrophotometer
(UH5300, HITACHI, Japan) at 517 nm. The absorbance (A1) of the
mixture (2 mL of film-forming solution was mixed with 2 mL of DPPH
solution (0.5 mmol/L)) after storage in the dark for 30 min) was
measured. The initial absorbance (A) of the DPPH solution (2 mL of
Y. Zhao et al. International Journal of Biological Macromolecules 223 (2022) 1126–1137

Table 1 2.6. Adhesive performance

Standard for sensory evaluation of strawberries.
Score Appearance Color Gloss The adhesion properties of the hydrogel films were estimated on
different substrates, including glass, metals, wood, and plastic, accord­
5 Full fruit Red Bright
4 Fuller fruit Small area of dark red Bright ing to a previous work [30]. The shear strength was measured using an
3 Slight atrophy Large area deep red Slightly dim electronic universal material test instrument (Instron 5965, Boston
2 More severe atrophy Dark red Darker Instron Co., Ltd. USA). Briefly, the hydrogel films were cut into 20 mm
1 Severe atrophy Small area brown Dim × 20 mm (length × width) pieces, and one piece of hydrogel film was
0 Complete atrophy Brown Dim
attached to the glass. The contact area between the hydrogel film and
glass was maintained at approximately 10 mm × 10 mm. Subsequently,
DPPH mixed with 2 mL of distilled water) and the absorbance (A0) of the the overlapped hydrogel film on the glass was cured at room tempera­
film-forming solution (2 mL of film-forming solution mixed with 2 mL of ture for 10 min. The shear strength of the adhesion area was measured
methanol) were measured using the same method. DPPH radical scav­ using an intelligent electronic stretching machine, and the tensile rate
enging activity was calculated according to Eq. (1). was set to 10 mm/min [31]. All samples were tested at least five times,
[ ] and the average values are expressed.
(A1 − A0 )
Radical scavenging activity (%) = 1 − × 100 (1)
A
2.7. Application of hydrogel films for fresh fruit preservation

2.5. Self-healing property of fabricated hydrogel film
The self-healing performance of the broken hydrogel film was eval­
uated according to a previously reported work [29]. The fabricated
hydrogel films (length × width = 40 mm × 20 mm) were cut into two
pieces with a knife and then placed into the mold after a simple butt
joint. The healing states of the broken hydrogel films were traced using a
digital camera after 1 h at room temperature (25 ◦ C, 25–30 % RH).
The preservation application of fabricated hydrogel films was pre­
served according to previously reported methods [32,33]. Fresh straw­
berries, cherries, and mangoes of uniform sizes and textures were
purchased from a local market. Prior to the experiment, the fruits were
washed several times with deionized water to remove impurities and
then dried at room temperature. Subsequently, each type of washed fruit
was randomly separated into four batches and packaged with no film,
polyethylene film, CMC/PVA/PEI/TA0 hydrogel film, and CMC/PVA/

Fig. 1. (a) Schematic diagram of preparing CMC-based hydrogel film. (b) FTIR and (c) XRD spectra of CMC/PVA, CMC/PVA/PEI and CMC/PVA/PEI/TA3. (d)
Proposed multiple dynamic reversible non-covalent bonds between polymers. (e) Amidation reaction between PEI and protonated CMC.

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Fig. 2. Low- and high- magnification cross-sectional SEM images of (a-c) CMC/PVA, (d-f) CMC/PVA/PEI/TA0 and (g-i) CMC/PVA/PEI/TA3 hydrogel films.
PEI/TA3 hydrogel film. Each batch was further randomly divided into
four or six groups, which were employed to evaluate the freshness of
fruits every two days during the storage period. All groups were stored
under ambient conditions (23–26 ◦ C). Photographs of the fruits were
captured using a digital camera. The physicochemical parameters of
packaged fruits in each batch, including weight loss, hardness, decay
rate, titratable acid content, and total soluble solid (TSS) content, were
measured by destroying the fruits according to a previously reported
method [32]. Appearance, color, and gloss were used as sensory eval­
uation indicators, and the specific evaluation criteria are listed in
Table 1.
Browned strawberry pulp, mildew spots on the surface, and juice
outflow were indicators of rotten strawberries. The number of rotten
strawberries was recorded every day, and the rot rate was expressed by
the rot index according to Eq. (2).
Number of rotten strawberries
Decay rate (%) = (2)
Total number of strawberries
The quality of strawberries was tested with an electronic balance
every day, and the rate of weight loss was calculated using formula (3).
( )
m0 − m1
Weight loss rate (%) = × 100 (3)
m0
where m0 is the original weight of fresh strawberries and m1 is the
weight of strawberries after storage.
Firmness was measured using a texture analyzer in which the
strawberry equator was aligned with the texture analyzer probe, and the
average value was obtained from triplicate measurements.
The soluble solid content was determined using a hand-held refrac­
tometer. Strawberries were randomly selected from each group, and the
strawberry juice was filtered through filter paper after grinding in a
mortar. The refractive index of the filtrate was measured using a hand-
held refractometer.
To determine titratable acids, 5 g of strawberry homogenate was
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International Journal of Biological Macromolecules 223 (2022) 1126–1137
placed in a volumetric flask filled with 50 mL of distilled water, and the
diluted strawberry homogenate was incubated in a water bath at 80 ◦ C
for 30 min. Then, 20 mL of diluted strawberry homogenate containing
two drops of phenolphthalein as an indicator was titrated with NaOH
solution (0.1 mol/L) until the pH reached 8.2. The titratable acid content
was calculated using Eq. (4).
Titratable acids (g citric acid/100 g strawberries)
=
VNaOH × 0.1 × 0.064 × V0
(4)
m × V1
where VNaOH is the volume (mL) of NaOH spent for titration, 0.1 is the
concentration of the NaOH solution (mol/L), 0.064 is the conversion
factor of citric acid, V0 is the volume (mL) of the volumetric flask, m is
the mass (g) of strawberry homogenate, and V1 is the volume (mL) of the
filtrate for titration.
2.8. Statistical analysis
All data tested in this experiment were presented as mean ± standard
deviation (SD). The mean differences in the hydrogel films were deter­
mined using analysis of variance (ANOVA) and Origin (Origin 2018,
Origin Laboratories, Inc., USA). Confidence interval was 95 % (p ≤
0.05).
3. Results and discussion
3.1. Fabrication of hydrogel film and structure analysis
Fig. 1a shows a schematic of the multifunctional CMC-based
hydrogel films prepared by the amidation-assisted freeze-thaw
method. Prior to other experiments, the PVA and PEI contents were
optimized using a typical tensile strength test. As shown in Fig. S1, the
largest tensile stress of (375.43 KPa) and elongation at break (395.21 %)
Y. Zhao et al. International Journal of Biological Macromolecules 223 (2022) 1126–1137

Fig. 3. Mechanical performances of hydrogel films. (a) Typical tensile stress-strain curves of various CMC/PVA/PEI/TAx hydrogel films. (b) Stretching stress-strain
cycle curves (at the strain of 100 % for 50 cycles) and (c) successive stretching stress tests (under 100 %, 200 %, and 300 % strains) of CMC/PVA/PEI/TA3 hydrogel
film. (d) Tensile strain-stress curves of CMC/PVA, HEC/PVA/PEI/TA3 and CMC/PVA/PEI/TA3 hydrogel films. (f) OTR and (g) WVTR of CMC/PVA/PEI/TAx hydrogel
films. (h) Comparison of flexibility and resistance to puncture of CMC/PVA/PEI/TA3 prepared by traditional film-casting method and hydrogel film. Error bars
presented standard deviation (n = 5).

were achieved at the concentrations of 8 % PVA and 1 % PEI. Without
special instructions, the optimized CMC/PVA8%/PEI1% was employed as
the matrix in the following hydrogel films. To reveal the chemical in­
teractions between the polymers, Fourier transform infrared spectros­
copy (FTIR) was performed. As shown in Fig. 1b, compared to the CMC/
PVA and CMC/PVA/PEI spectra, a new peak was observed at 1090 cm− 1
in the CMC/PVA/PEI/TA3 spectrum, which could be attributed to the
amide bond formed between –COOH on CMC and –NH2 on PEI [34].
This result indicated that the amidation reaction only occurred between
protonated CMC and PEI in the presence of TA, which provided
hydrogen ions [35,36]. Apart from this peak, no peaks associated with
newly formed chemical bonds were detected, implying physical in­
teractions with the other polymers. The crystalline structures of the
hydrogel films were investigated using XRD, and the measured patterns
are shown in Fig. 1c. The broad characteristic peaks located at 2θ =
21.6o indicate the semi-crystalline structure of the CMC material.
Notably, the diffraction intensity of this peak decreased gradually upon
the successive incorporation of PEI and TA molecules. The reduced
crystallinity of the hydrogel film was attributed to the newly formed
intermolecular bonds between CMC, PVA, PEI, and TA, inhibiting the
movement of CMC/PVA molecular chains and thus reducing the crys­
tallinity and increasing the flexibility [37]. Following this in line, the
proposed molecular interaction diagram and amidation reaction within
hydrogel film was depicted in Fig. 1d and e, respectively.
The microstructures of the hydrogel films were characterized using
SEM, and the corresponding results are shown in Fig. 2. All the hydrogel
films presented a close thickness of 550–600 μm and obvious
honeycomb-like internal structures, implying the typical porous feature
of hydrogel materials (Fig. 2a, d, g). Upon closer observation (Fig. 2b, c
and e, f), CMC/PVA/PEI/TA0 possesses shaggier network structures than
the pristine CMC/PVA hydrogel film because of the restrained CMC/
PVA chain interactions and the reduced proportion of crystal regions
influenced by PEI molecules [38]. Such microscopic morphological
differences matched well with the XRD results shown in Fig. 1c.
Furthermore, the incorporation of TA into CMC/PVA/PEI/TA0 increased
the number of cross-linking sites and reinforced intermolecular in­
teractions such as hydrogen bonds, coordination bonds, and cation-π
interactions [39,40], thereby densifying the 3D network structures of
CMC/PVA/PEI/TA3. Such structures are favorable for improving the
mechanical strength and stretchability of the designed hydrogel films,
which can effectively dissipate the loaded energy [41]. However, the
CMC/PVA/PEI/TA3 film prepared by the traditional casting method
possessed dense structures without 3D network structures, as shown in
Fig. S2, further emphasizing the feasibility of the fabricated hydrogel
film.

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Fig. 4. (a) UV-blocking, (b) scavenging activities on DPPH free radicals and (c) self-healing performance of CMC/PVA/PEI/TAx hydrogel films. (d) Self-healing
capacity of hydrogel film. (e) Adhesive property of hydrogel film to metal, plastic, wood and glass and (f) the adhesive strength of CMC/PVA/PEI/TA hydrogel
films on glass. (g) The adhesion mechanism.
3.2. Mechanical and gas barrier properties
In practice, the application scenarios and lifespan of food packaging
films are highly determined by their mechanical properties [42]. From
the typical tensile stress–strain curves in Fig. 3a, pristine CMC/PVA/PEI
hydrogel film delivered a tensile strength of 202.74 kPa and elongation
at a break of 208.97 %. Under low TA concentrations (<0.8 %), both the
tensile stress and strain were elevated by increasing the TA doping
amount, and a maximum tensile stress of 502.12 kPa and strain of
397.65 % can be achieved at 0.6 % TA. This is because highly concen­
trated TA molecules provided more cross-linking sites (e.g., hydrogen
bonds, electrostatic interactions, amide bonds, coordination bonds, and
cation-π interactions) and were beneficial for forming a denser network
structure in the hydrogel film, which could effectively dissipate the
loaded energy. Upon further increasing the TA content, the reinforced
interaction with polymer chains endowed the hydrogel film with a
higher tensile stress of 645.93 kPa. However, the strain was reduced to
311.29 % owing to the rigid nature of agglomerated TA (graphene-like
structure) under π–π stacking and hydrogen bonds [43].
As shown in Fig. 3b, when the CMC/PVA/PEI/TA3 hydrogel film was
repeatedly stretched 50 times, the hysteresis loop did not change
significantly, except for the 1st cycle, indicating that the network
structure of the hydrogel film could quickly recover to its initial state.
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International Journal of Biological Macromolecules 223 (2022) 1126–1137
The underlying mechanism is the fast breaking and repair of dynamic
reversible non-covalent bonds, accompanied by energy dissipation [44].
Such network changes and energy dissipation in the hydrogel film under
repetitive stretching suggest satisfactory resilience to elastic deforma­
tion and fatigue of the hydrogel films.
Furthermore, as shown in Fig. 3c, the cyclic tensile loading-
unloading tests of hydrogel films with varying strains (100 %, 200 %,
and 300 %) demonstrated that hysteresis loops were observed under
different strains. However, hydrogel films cross-linked by physical
structure were not easily destroyed, even at high strain of 300 %,
implying the relatively stable mechanical performance. When the
carboxyl sodium was replaced by HEC free of Na+, both the tensile
strength and strain of the HEC/PVA/PEI/TA3 hydrogel film were
significantly reduced (Fig. 3d), which further verified the key role of
cation–π interactions (between Na+ and the benzene ring in TA) in
reinforcing the mechanical strength of the hydrogel film [45]. Impres­
sively, the fabricated CMC/PVA/PEI/TA3 hydrogel film displayed
excellent extensibility and the strain reached as high as up to 400 %
without disintegration, as shown in Fig. 3e. The stretched CMC/PVA/
PEI/TA3 hydrogel film also visually presented deformation resistance (e.
g., stretching and curving) and anti-puncture characteristics (Fig. 3h).
Overall, all of the above-mentioned merits, including mechanical
strength, elongation at break, fatigue, and puncture resistance, meet the
Y. Zhao et al.
Fig. 5. Comparison of overall performances of previously reported hydrogel-based food packaging and preservation films with CMC/PVA/PEI/TA3 in this work.
basic mechanical performance demands and give rise to significant ap­
plications in packaging films. In addition, the TGA and DSC curves in
Fig. S3, the slightly enhanced onset decomposition temperature (To) of
the CMC/PVA/PEI/TAx hydrogel films upon incorporation of TA sug­
gested the salutary influence of TA on thermal stability.
Most of the decay mechanisms of fruits and vegetables are correlated
with the presence of gaseous molecules inside packaging, which regulate
their physiological metabolism [46,47]. The ideal gas environment
(relatively low concentration of oxygen and high concentration of car­
bon dioxide) slowed the respiratory effect of fruits and vegetables and
inhibited the growth of microorganisms [48]. Fig. 3f and g present the
oxygen transmission rate (OTR) and water vapor transmission rate
(WVTR) of CMC/PVA/PEI/TAx hydrogel films as a function of the TA
doping amount. Typically, the largest OTR value of 60.61 cm3*μm/
(m2*d*kPa) and WVTR value of 813.81 g/m2*24 h were obtained for
CMC/PVA/PEI/TA0. With increasing TA content, the OTR and WVTR
values were decreased to 32.64 cm3*μm/(m2*d*kPa) and 642.92 g/
m2*24 h, respectively, at TA concentration of 0.6 % (CMC/PVA/PEI/
TA3). The enhanced gas barrier properties of the hydrogel films were
ascribed to the formation of denser network structures, in which the
motion of the matrix (polymer) correlated with the gaseous-diffusion
coefficient was suppressed [49]. However, the WVTR and OTR of the
hydrogel films were reduced by 0.8 % TA. The permeability of the films
also depends on the crystallinity and hydrophobicity of the matrix [50].
As shown in Fig. 1c, the incorporation of TA into the hydrogel film
decreased the crystallinity of the CMC/PVA/PEI. In this manner, the
crystallinity would be further reduced at higher TA doping dosages
(Fig. S4), which deteriorated the gas-barrier properties of the hydrogel
films. In addition, the hydrophilicity of the hydrogel film was improved
by increasing the amount of water-soluble tannic acid, which is
conducive to the penetration and diffusion of water molecules, reducing
the gas barrier performance [51]. Moreover, at higher TA concentra­
tions in CMC/PVA/PEI/TA4, agglomerated TA under π–π stacking and
hydrogen bonds caused the non-uniformity of TA in the matrix. These
factors resulted in relatively improved OTR and WVTR values [52].
3.3. UV-shielding, antioxidants activity, self-healing and adhesiveness
performances
The UV-blocking performance of the fabricated hydrogel films was
characterized, and the corresponding UV–vis transmittance spectra are
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International Journal of Biological Macromolecules 223 (2022) 1126–1137
shown in Fig. 4a. Clearly, the light transmittance was sensitive to the
film composition. The CMC/PVA/PEI/TA0 film displayed the highest
transmittance within the UV region, indicating a poor UV-blocking
performance. However, when 0.6 % TA was doped into hydrogel film
(89 % moisture content), the almost 0 % transmittance of CMC/PVA/
PEI/TA3 in whole UV region suggested the excellent UV-shielding abil­
ity. This phenomenon could be explained from two aspects: (I) the ar­
omatic ring structure on TA effectively reduced the penetration of UV
light; (II) the auxochromic group of -NH2 on PEI boosted the UV-
shielding capacity of TA, which was further confirmed by the
increased transmittance of CMC/PVA/PEI0/TA3 at 400 nm. Moreover,
the reduced transmittance and darkened color of the CMC/PVA/PEI/
TA3 film-forming solution as the PEI content in the hydrogel gradually
increased and confirmed the validity of this conclusion, as shown in
Fig. S5.
The structural degradation and nutritional quality loss of food are
often caused by the oxidative deterioration of food between atmospheric
oxygen and nutritional ingredients [53]. The DPPH radical scavenging
assay is based on the ability of antioxidants to quench the DPPH radicals.
As well known, tannic acid (TA), plant-derived polyphenols rich in
catechol groups, has been widely used as a natural antioxidant to pre­
vent the food from being oxidized [54]. It can be seen from Fig. 4b, the
DPPH free radical scavenging rate of CMC/PVA/PEI/TAx hydrogel films
was observably increased from 2.3 % to 78.7 % as the TA content
increased gradually. TA pyrogallol with a large number of ortho-
phenolic hydroxyl groups provided a hydrogen donor. DPPH is a rela­
tively stable nitrogen-centered free radical that has three aromatic ring
structures and belongs to the aromatic class of free radicals [55].
Consequently, TA can directly capture or combine with DPPH free
radicals, thereby endowing the films with desirable antioxidant activity.
Fig. 4c reveals that the two disconnected hydrogel films can be self-
healed at room temperature without any external stimuli, and the healed
hydrogels can still withstand mechanical deformations, such as a 500 g
weight. Such excellent self-healing characteristics can be attributed to
the abundant dynamic reversible physical bonds (e.g., hydrogen bonds,
coordination bonds, and cation–π interactions) within the network
structures [56]. The broken physical bonds on the fracture surface on
hydrogel films would connect with each other when the two surfaces
were jointed together and the proposed self-healing mechanism was
drawn in Fig. 4d. In addition, the hydrogel film exhibited excellent
adhesion performance to various materials (Fig. 4e), including metals,
Y. Zhao et al. International Journal of Biological Macromolecules 223 (2022) 1126–1137

Fig. 6. The evolution of (a) weight loss rate, (b) hardness, (c) decay rate, (d) titratable acid content, (e) TSS content and (f) sensory evaluation score of strawberries
packaged by different films during storage period under ambient conditions for 7 days.

plastics, wood, and glass, owing to the abundant catechol functional
groups in TA [43]. To quantify the adhesion strength of the hydrogel
films with different TA doping concentrations, detailed adhesive
strength measurements were conducted. As shown in Fig. 4f, it is
obvious that the adhesive strength is directly proportional to the TA
doping amount, and the maximum adhesive strength of 234.08 KPa can
be reached for CMC/PVA/PEI/TA4, which is mainly attributed to the
increased number of catechol groups associated with adhesion sites in
the hydrogel film (Fig. 4g).
Based on the above results and analysis, it can be clearly concluded
that the fabricated CMC/PVA/PEI/TAx hydrogel films simultaneously
possess excellent mechanical strength, gas barrier, UV-blocking, self-
healing, and adhesion performance compared to previously reported
hydrogel-based packaging films (Fig. 5). These merits satisfy the

Fig. 7. Visual appearance change of strawberries during storage period.

1133
Y. Zhao et al. International Journal of Biological Macromolecules 223 (2022) 1126–1137

Fig. 8. Visual appearance change of cherries during storage period.

practical application requirements of food packaging and preservation
films [57–59].
3.4. Application of hydrogel films for fruits packaging and preservation
Strawberries are beautiful in shape, sweet in taste, and deeply loved.
However, they are susceptible to mechanical damage during harvesting
and storage processes, resulting in microbial infection and a high rot rate
[60]. Thus, safe and efficient packaging and preservation technologies
are highly desired to prolong the shelf life. In this study, potential ap­
plications of the prepared hydrogel films as packaging and preservation
systems were evaluated (Fig. S6). Under ambient conditions, fresh
strawberries were packaged in different films for 7 days, and changes in
weight loss rate, hardness, decay rate, TA content, TSS content, sensory
evaluation score, and visual appearance were periodically monitored.
Water loss from fruits inevitably promotes the hydrolysis of enzymes

Fig. 9. Visual appearance change of mangos during storage period.

1134
Y. Zhao et al.
and cell aging, deactivating the nutritional component in strawberries
[61]. The average water content of strawberries is approximately 90 %,
and the moisture loss can be attributed to two factors. The transpiration
effect of strawberries resulted in water loss owing to the lack of radiating
wax and cuticle structure. However, relatively strong respiratory
metabolism consumes part of the water [62]. As shown in Fig. 6a, the
mass loss rate of all the strawberry samples gradually increased during
storage. Clearly, strawberries free of packaging lost the most moisture as
there was no packaging material to block the loss of water into the air.
The lowest mass loss rate was realized when the strawberries were
packaged with commercial PE film because of the densest structure of
the petroleum-based PE film. Compared with CMC/PVA/PEI/TA0, the
CMC/PVA/PEI/TA3 hydrogel film with a higher gas barrier ability
exhibited a lower mass loss rate, which is beneficial for preserving
nutritional ingredients.
The appearance and taste of strawberries is largely related to their
hardness. Originating from the degradation of the cell wall by cellulase
and pectin lyase [63], the firmness of strawberries gradually decreased
over storage time, as shown in Fig. 6b. Typically, strawberries packaged
by CMC/PVA/PEI/TA3 hydrogel films had the highest hardness, which
may be attributed to the anti-oxidation effect and the suppressed
metabolic rate, thereby prolonging the shelf life of strawberries.
As shown in Fig. 6c, the rot rate of strawberries free of packaging,
packaged by CMC/PVA/PEITA0 and commercial PE film almost reached
100 %, 100 %, and 75 %, respectively, after 7 days. Exhilaratingly, the
lowest decay rate of 50 % was achieved for the CMC/PVA/PEI/TA3
hydrogel film. The good self-sealing property of the fabricated hydrogel
film inhibited the invasion of bacteria, and the presence of TA restrained
the growth of microorganisms [64].
The titratable acid content is related to the strawberry flavor. Owing
to the post-ripeness of the picked strawberries, the titratable acid con­
tent in all groups increased rapidly within 4 days, as shown in Fig. 6d.
Subsequently, the titratable acid concentration was further enhanced,
which could be attributed to the acid produced by infected microor­
ganisms. This phenomenon is consistent with the appearance of a white
spot on the surface of strawberries (Fig. 7). In particular, CMC/PVA/
PEI/TA3 delivered the lowest titratable acid concentration, owing to the
excellent antioxidant and antibacterial effects of the hydrogel film.
Moreover, the TSS content first increased and then decreased gradually
as a function of storage time in all the groups (Fig. 6e). The increased
TSS content is ascribed to the post-ripeness of strawberries, and the
decreased TSS content is attributed to the aging or decay of strawberries
[65]. The comparable TSS content in the commercial PE, CMC/PVA/
PEI/TA0, and CMC/PVA/PEI/TA3 groups suggested that the packaging
film could delay the degradation of soluble solids.
Sensory evaluation is the most intuitive manifestation of fruit quality
and a decisive factor in customers' purchases. Usually, the appearance,
color, and glossiness together contribute to the sensory evaluation of
strawberries, and the corresponding evaluation results are displayed in
Fig. 6f. Among all the groups, CMC/PVA/PEI/TA3 delivered the highest
scores after storage for 7 days, which is a crucial parameter for deter­
mining the best preservation effect. Surprisingly, the strawberries stored
in the CMC/PVA/PEI/TA3 hydrogel film remained relatively intact after
seven days, as shown in Fig. 7, whereas the strawberries in the control
groups were completely rotten. In summary, the prepared CMC/PVA/
PEI/TA3 hydrogel film could effectively extend the shelf life of straw­
berries for at least 7 days under ambient conditions.
The fabricated CMC/PVA/PEI/TA3 hydrogel film was demonstrated
to have a significant packaging and preservation effect on prolonging
the shelf life of strawberries; therefore, such films were also employed to
preserve fresh cherries and mangos. As shown in Figs. 8 and 9, both the
cherries and mangos packaged by the CMC/PVA/PEI/TA3 hydrogel film
remained in a fresh state after storage for one week under ambient
conditions, whereas the corruption phenomenon could be observed in
the control groups. This result indicates that the multifunctional
hydrogel film is suitable for packaging and preserving various fresh
1135
International Journal of Biological Macromolecules 223 (2022) 1126–1137
fruits.
4. Conclusion
In summary, a CMC/PVA/PEI/TA hydrogel film based on natural
biodegradable polysaccharides was successfully prepared by integrating
excellent stretchability, adhesion, self-healing, UV shielding, and gas
barrier performance, which has been employed in food packaging and
preservation. Such multifunctional packaging materials based on
hydrogel films overcome the limitations of poor tensile strain and rela­
tively simple function in traditional food packaging films. In addition,
the incorporation of bioactive TA endowed hydrogel films with desir­
able antioxidant and antimicrobial properties. When the fabricated
hydrogel film was employed as a food packaging and preservation film
in practical applications, the shelf lives of fresh strawberries, mangoes,
and cherries were effectively prolonged. This work boosted the blos­
soming of hydrogel films in the area of fruit packaging and preservation.
CRediT authorship contribution statement
Yali Zhao: Investigation, Conceptualization, Methodology, Data
Curation, Writing-Original draft preparation.
Siying Zhou: Investigation, Conceptualization, Methodology.
Xiaodong Xia: Conceptualization, Investigation, Writing-Review &
Editing.
Mingqian Tan: Conceptualization, Data Curation.
Yanna Lv: Conceptualization, Methodology.
Yi Cheng: Data Curation, Investigation.
Yehan Tao: Conceptualization, Methodology.
Jie Lu: Formal analysis, Data Curation, Writing-Reviewing and
Editing.
Jian Du: Supervision, Methodology, Writing-Review & Editing.
Haisong Wang: Funding acquisition, Supervision, Writing-Review &
Editing.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
This work was supported by the National Key Research and Devel­
opment Program of China (SQ2022YFD2100005), the National Natural
Science Foundation of China (No. 21978029, No. 22278047, No.
22208038, No. 22208040 and No. 32201501) and Liaoning Revitaliza­
tion Talents Program (No. XLYC2002024).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.ijbiomac.2022.11.102.
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