International Journal of Biological Macromolecules 172 (2021) 330–340

Contents lists available at ScienceDirect

International Journal of Biological Macromolecules

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

Novel alginate-cellulose nanofiber-poly(vinyl alcohol) hydrogels for

carrying and delivering nitrogen, phosphorus and potassium chemicals
Shiliang Liu a,b,⁎, Qinglin Wu b,⁎⁎, Xiuxuan Sun b, Yiying Yue c, Brenda Tubana d, Rongjie Yang a, Huai N. Cheng e
a
College of Landscape Architecture, Sichuan Agricultural University, Chengdu, Sichuan 611130, China
b
School of Renewable Natural Resources, Louisiana State University Agricultural Center, Baton Rouge, Louisiana 70803, United States
c
College of Biology and the Environment, Nanjing Forestry University, Nanjing 210037, China
d
School of Plant, Environmental, and Soil Sciences, Louisiana State University Agricultural Center, Baton Rouge, LA 70803, United States
e
Southern Regional Research Center, USDA Agriculture Research Service, New Orleans, LA 70124, United States

a r t i c l e i n f o a b s t r a c t

Article history: Novel nanocomposite hydrogels were successfully prepared by blending and crosslinking sodium alginate (SA),
Received 9 October 2020 poly(vinyl alcohol) (PVA) and cellulose nanofibers (CNFs) in the presence of a fertilizer formulation containing
Received in revised form 9 January 2021 nitrogen (N), phosphorus (P) and potassium (K). The hydrogels had a macroporous flexible core and a micropo-
Accepted 11 January 2021
rous semi- interpenetrating polymer network (IPN) shell. The crystalline nature of the NPK chemicals was
Available online 13 January 2021
retained in the hydrogel nanocomposite network. Furthermore, the SA/CNF/PVA-based hydrogels showed a
Keywords:
higher water-retention capacity in both deionized water and mixed soil. The swelling behavior in various phys-
Alginate-cellulose nanofiber-poly(vinyl alco- iological pH, salt and alkali solutions exhibited good sensitivity. The NPK release from SA/CNF/NPK and SA/CNF/
hol) hydrogel PVA/NPK hydrogels was controlled by Fickian diffusion in both water and soil based on the Korsmeyer-Peppas
Slow-release of chemicals release kinetics model (n < 0.5). Therefore, the prepared hydrogels have the potential for applications in
Swelling kinetics drought-prone and/or fertilizer-loss regions for future development of precision agriculture and horticulture.
© 2021 Published by Elsevier B.V.

1. Introduction
Growing global population relies on modern agriculture and quick-
acting fertilizers to satisfy mankind's huge food needs [1]. However, ex-
cessive use of synthetic fertilizers and large amounts of chemical
leaching from fertilized soil have caused serious environmental prob-
lems worldwide [2–4]. For example, overuse of inorganic mineral fertil-
izers containing nitrogen (N), phosphorus (P) and potassium (K) has
led to soil property deterioration (e.g., degradation of soil structure)
and/or water contamination (e.g., eutrophication) in the estuaries and
coastal regions due to their high mobility property [4–6]. One solution
is to reduce fertilizer use, but this action affects crop yields. The reduc-
tion of fertilizer losses through the use of substrates that can control re-
lease and maintain moisture has been considered a promising
alternative in recent years [4,7,8]. In this regard, slow-release fertilizers
(SRFs) are designed to gradually release fertilizers for plant absorption
to meet the plant's nutrient requirements, while reducing fertilizer
⁎ Correspondence to: S. Liu, College of Landscape Architecture, Sichuan Agricultural
University, Chengdu, Sichuan 611130, China.
⁎⁎ Correspondence to: Q. Wu, School of Renewable Natural Resources, Louisiana Forest
Products Development Center, 227 Renewable Natural Resources Building, Baton Rouge,
LA 70803, United States.
E-mail addresses: liushiliang9@163.com (S. Liu), qwu@agcenter.lsu.edu (Q. Wu).
losses [4,9,10]. The SRFs offer more advantages compared with conven-
tional fertilizers, such as reducing environmental pollution, continuous
fertilizer supply, and increasing fertilizer use efficiency by plants
[2,11]. Meanwhile, water resources pose an important limiting factor
for agricultural production; thus, novel nanomaterials capable of high-
efficiency water management have attracted a lot of attention. In
drought-prone regions, in particular, the combination of water-
retaining characteristics and specific SRFs can help improve water and
nutrient retention in sandy soils, enhance soil permeability and micro-
bial activity, and reduce irrigation frequency and environmental pollu-
tion [1,12].
In recent years, hydrogels have been widely studied because of their
abilities in controlling release of active components and improving
water retention [13–15]. Because of their resistance to biofouling, bio-
compatibility and resource-rich properties, hydrogels prepared using
biopolymers (e.g., cellulose, alginate, and other polysaccharides) have
been widely investigated for bioengineering and agricultural purposes
[13,16,17]. Among these, sodium alginate (SA), a linear polymer con-
taining poly(guluronate) (G) and poly(mannuronate) (M) units in M-
M, G-G, and M-G blocks, has been often utilized in many potential fields
due to its gel-forming properties with divalent cations (e.g., Ba2+ and
Ca2+) [10,13,18]. Alginate is also a pH-sensitive biopolymer with pen-
dant carboxylic groups that accept and provide protons with changing
pH values in aqueous solutions [15,18,19]. Moreover, studies have

https://doi.org/10.1016/j.ijbiomac.2021.01.063
0141-8130/© 2021 Published by Elsevier B.V.
S. Liu, Q. Wu, X. Sun et al. International Journal of Biological Macromolecules 172 (2021) 330–340

confirmed that alginate-based materials are excellent adsorbents and (>18 M Ω cm; Merck, Darmstadt, Germany) was used to prepare the
are commonly used to remove water contaminants such as metal ions, samples.
enzymes, and fertilizers in recent years [14,20–22]. However, cation ex-
change can lead to decomposition of the alginate-based hydrogel beads.
2.2. Preparation of SA-based hydrogel beads
For example, the exchange of calcium (Ca) ions with monovalent ions
(such as sodium ions) can affect the crosslinking in alginates [13,23].
SA-based hydrogel beads were synthesized by crosslinking SA and
As a solution to this problem, poly(vinyl alcohol) (PVA) has been
CNF with a CaSO4 solution in the presence of PVA and NPK fertilizer
employed in the formation of chemically or physically cross-linked
(equivalent to 20 N, 20 P and 20 K) (Table S1). First, the 1.5% SA solution
hydrogels, taking advantage of PVA's large numbers of hydrophilic hy-
was added to the formed 0.5 wt% CNF suspension. The mixture was then
droxyl groups [23,24]. The outstanding properties of PVA, such as its
stirred at room temperature until a homogeneous suspension was ob-
simple production process, high chemical resistance, and biodegradabil-
tained. Second, 0.5% PVA solution was prepared by adding pure PVA
ity, make it ideal for agricultural and biomedical applications [25]. How-
powder slowly into deionized water and the mixture was then heated
ever, poor mechanical properties of PVA-SA hydrogels still hinder their
to 90 °C for 2 h using a magnetic stirrer hotplate (Corning Corp., Corning,
wide-spread applications [26].
NY, USA). The amount of deionized water lost during the heating pro-
Incorporating clay, metal, carbon nanotubes and other micro/nano
cess was measured after cooling, and additional water was added to
particles can help reinforce the mechanical properties of hydrogels
the PVA solution to maintain its original concentration. The prepared
[27,28]. Compared with inorganic materials, cellulose nanomaterials
0.5% PVA solution and dissolved 1.5 wt% NPK solution were added to
(CNMs) are sustainable and can offer better mechanical properties
the prepared SA/CNF mixture with constant stirring. Third, the
due to their high aspect ratio, large surface area, and potentially reactive
crosslinking method [11] was used to encapsulate NPK fertilizer within
surface [29,30]. As a major type of nanosized cellulose, cellulose nanofi-
the hydrogels. After being stirred with a Teflon-coated magnetic stir bar
bers (CNFs) can help crosslink PVA-SA matrix to form stable gels
at 500 rpm min−1 for 5 h, homogeneous SA/CNF/PVA/NPK suspensions
[14,31], and the gels were reported to show higher mechanical
were obtained. Each prepared homogeneous suspension was loaded in
strengths and storage moduli compared with pure polymers synthe-
two plastic syringes, and a two-channel syringe pump (Chemyx Fusion
sized using irradiation techniques [32]. Previously, Yue et al. [14] dem-
100T, Stafford, TX, USA) was used to push the suspension through two
onstrated that SA/PVA-based hydrogels were significantly reinforced
20-gauge needles at a flow rate of 15 mL min−1 into a beaker containing
by CNFs, presenting higher (about three times) compressive strength
400 mL of 0.1 wt% CaSO4 solution. The CaSO4 solution was made into a
than that of pure polymer hydrogels. In addition, CNFs with a high mod-
homogeneous solution using deionized water and allowed to stand
ulus of elasticity act as a mitigating agent for crack propagation, thereby
overnight before use. The vertical distance between the needle and
inhibiting the destruction of hydrogels during stressing [33]. Currently,
the surface of the CaSO4 solution was approximately 20 cm. During
some published work [14,32–35] dealt with SA/CNF-based hydrogels.
this process, CaSO4 solution in the beaker was gently agitated mechan-
For example, Yue et al. [14] studied the Ca2+-crosslinked PVA/SA sys-
ically to prevent mutual adhesion among the hydrogel beads. The ter-
tem, but the work did not involve the fertilizers' slow-release behavior
polymer hydrogel beads formed were allowed to cure in the same
from the hydrogels. Kumar et al. [36] only evaluated the influences of
CaSO4 solution for 12 h with stirring at room temperature. The
crosslinking functionality on cellulose nanocrystal (CNC) reinforced
hydrogels were then collected and washed three times with deionized
SA/PVA hybrid scaffolds. However, few studies have focused on the ap-
water to remove residual Ca ions. The diameters of 20 hydrogel beads
plication of SA/CNFs-derived hydrogels in the presence of PVA cross-
were measured using an optical microscope system (Carl Zeiss
linked with Ca2+ for the controlled-release of NPK fertilizers. Therefore,
Axioskop 2, Carl Zeiss, Oberkochen, Germany) based on a previous pro-
the objectives of our study were (1) to develop novel composite
tocol [37]. The wet hydrogel samples were rapidly frozen in a freezer at
hydrogels based on natural CNFs and SA with controlled fertilizer
about −30 °C for 12 h, which were then transferred to a freeze-dryer
(i.e., N, P, K) release functionality and efficient water absorption proper-
(Free-Zone plus 2.5 L, Labconco, Kansas, MO, USA) at a temperature of
ties, and (2) to investigate the morphology, chemical structure, water
−50 °C and freeze dried for 5 days. These fully freeze-dried hydrogels
absorbency, and NPK-release behavior in water and soil of the
were further analyzed in the following experiments.
hydrogels. The hydrogel system offers a promising fertilizer carrier
with controlled release functionality for future agricultural and horticul-
tural applications. 2.3. Hydrogel morphology characterization

2. Experimental 2.3.1. Transmission electron microscopy (TEM)

2.1. Materials and sample preparation
Poly(vinyl alcohol) (Mw 89,000; 99% hydrolyzed) and NPK fertilizer
(potassium chloride, KCl, and ammonium dihydrogen phosphate,
NH4H2PO4) were obtained from Sigma-Aldrich Corp. (St. Louis, MO,
USA). Sodium alginate (Protanal® RF 6650 with Mw ~ 270,000, G/M
ratio = 2:1, and pH = 6.0–8.0) was purchased from the FMC Corp.
(Philadelphia, PA, USA). Calcium sulfate (CaSO4) and Dulbecco's phos-
phate buffer saline (PBS) (without Ca2+ and Mg2+) were purchased
from Thermo Fisher Scientific (Waltham, MA, USA) and Invitrogen
Corp. (Carlsbad, CA, USA), respectively. The original CNF suspension
(2.0 wt%) was extracted from bamboo fibers. The suspension was first
diluted to the 0.5 wt% concentration. The diluted material was proc-
essed using an M-110EH-30 Microfluidizer® (Microfluidics Interna-
tional Corp., Newton, MA, USA) at an operating pressure of 202 MPa
for ten passes. The treatment with the microfluidizer helped breakup
CNF bundles in the suspension, which improved CNF dispersion in
water. Millipore deionized water from Millipore Milli-Q® system
The 0.1 wt% CNF suspension was prepared and sonicated for 1 h for
the TEM study of fiber morphology. A droplet (5 μL) of the diluted CNF
suspension (0.1 wt%) was deposited onto a 300-mesh Lacey carbon film
grid (LC300-CU-100, Agar Scientific, Stansted, UK), which was nega-
tively stained with a 2 wt% uranyl acetate solution for 2 min. The pre-
pared samples were analyzed using a model JEM-1400 TEM (JEOL Ltd.,
Tokyo, Japan) at a 120 kV acceleration voltage. The average width of
CNF samples was measured using the ImageJ software (NIH, Bethesda,
MD, USA) from the collected TEM images following our previous proto-
col [30].
2.3.2. Field emission-scanning electron microscopy (FE-SEM)
Micro-structure and surface morphology of freeze-dried hydrogel
samples were observed using a field emission SEM (FE-SEM, a Quanta™
3D DualBeam™ FEG-FIB-SEM system, Hillsboro, OR, USA) at a 20 kV ac-
celerating voltage. All samples were sputter-coated with gold for 2 min
prior to the analysis. The average width of the randomly selected 50
beads was calculated from the obtained micrographs using the ImageJ
software.

331
S. Liu, Q. Wu, X. Sun et al.
2.4. Structural characterization
The chemical and crystalline structure traits of freeze-dried
hydrogels were analyzed by Fourier transform infrared spectrometry
(FT-IR) and wide-angle X-ray powder diffraction (XRD). Prior to analy-
sis, the hydrogel beads were ground using a McCrone Micronizing Mill
(McCrone Group, Westmont, IL, USA) at room temperature. Then,
these powder samples were placed into a Zn/Se-ATR crystal chamber
of the Bruker Tensor-27 FT-IR analyzer (Bruker Optics Inc., Billerica,
MA, USA). Each sample was scanned 32 times over the range from
4000 to 400 cm−1 with a resolution of approximately 2 cm−1 using
the attenuated total reflectance (ATR) mode. The crystalline structure
was analyzed employing a Siemens/Bruker D5000 XRD (Siemens Co.,
Wittelsbacherplatz, Munich, Germany) at an accelerating voltage of
45 kV and a current of 40 mA. Samples were scanned in the two theta
(2θ) range from 5° to 65° in steps of 0.02°.
2.5. Water absorbency measurements
To study the effects of different physiological pH and salt solutions
on the equilibrium swelling behavior of the hydrogels, we used the
swelling ratio (SR) to measure their water absorption as described by
previous protocols [11,38]. Typically, dried hydrogel samples of 0.20-g
(Wd) were added to several solutions including 100 mL of deionized
water, Dulbecco's PBS solutions (pH values: 11, 10, 9, 8, 7, 6, 5, 4 and
3), 0.5 wt% saline solutions (NaCl, KCl, and CaCl2) and an alkali (0.5 wt
% NaOH) solution, respectively, allowing them to reach swelling equilib-
rium. The swollen hydrogels were taken out of the solution using a
stainless steel screen mesh at different time intervals (t, hour), and
were weighed (Wt, g). The swollen hydrogels were washed three
times with deionized water and the excess surface solution was
absorbed by clean and soft paper tissues. The specific sampling time in-
tervals were 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 24, 36, 48, 72, 96, 120,
144, 168, and 192 h after starting the test. Based on data from three in-
dependent replicates, SR (g/g) was calculated as:
W t −W d
SR ¼
Wd
where Wd represents dry hydrogel weight (g), and Wt represents wet
hydrogel weight (g) at a given time t.
To study the water-retaining behavior of hydrogels in soil, we also
investigated the water retention (WR%) in the mixed soil (sandy soil:
loam soil = 3:1; 25 mesh). Freeze-dried hydrogel samples (5 g) were
thoroughly mixed with 50.0 g of dry mixed soil and the mixture was
placed in a plastic container (15 cm in diameter). Subsequently,
100 mL of deionized water was added into the container. The weight
of the prepared container was measured (Wo, g). The container weight
(W, g) without the dried-hydrogels was recorded as control, while the
container weight (Wt, g) at the target times within the 60-day test pe-
riod was also recorded at room temperature. The WR (%) in mixed soil
was calculated according to the previous protocol [11] as follows:
W t −W
WRð%Þ ¼  100%
W o −W
2.6. NPK release measurements
2.6.1. Slow-release behavior in water
To understand the fertilizer release behavior of the hydrogels, we
performed a slow-release experiment with NPK-based hydrogels at
room temperature as described by Rashidzadeh and Olad [11]. Briefly,
a freeze-dried hydrogel sample (1.0 g) was added to 100 mL of deion-
ized water. For NPK determination, a 15-mL solution was sampled and
placed in a test vial with plastic lid at specific time intervals (i.e., 0, 1,
International Journal of Biological Macromolecules 172 (2021) 330–340
3, 5, 10, 15, 20, 25, 30, 45 and 60 days). To keep a constant amount of so-
lution, we added back an additional 15 mL of deionized water to the
containers. Three independent experiments were conducted. All water
samples for the release concentrations of N, P and K were analyzed.
The concentrations of K and P were run on a Varian Vista-MPX™ ICP-
OES analyzer (Thermo Fisher Scientific, Waltham, MA, USA), while the
total N level was analyzed on a Shimadzu TOC/TN analyzer (Shimadzu,
Kyoto, Japan). The cumulative release (CR%) of NPK fertilizer was ob-
tained:
n−1
V E ∑1 Ci þ V 0 Cn
CR ¼  100% ð3Þ
m0
where VE is the sampling volume (mL), V0 is the initial volume (mL), Ci
and Cn are the released NPK concentrations (mg mL−1) at time i and n,
respectively, and m0 is the weight of NPK fertilizers (mg).
2.6.2. Slow-release behavior in soil
For the investigation of the NPK release in soil, 1.0 g of freeze-dried
hydrogels were thoroughly mixed with 100 g of mixed soil (sand:
loam = 3:1; 25 mesh). The background values of total N, P and K of
the mixed soil was 21.2, 52.3 and 38.4 mg kg−1, respectively. To sepa-
rate the water sample from the mixture, a plastic container (500 mL)
with a filter membrane, a valve and a lid was employed. The valve
was closed when the mixture was filled into the container. Subse-
quently, 100 mL of deionized water was added to the soil container
until it reached the soil-water saturation point. Throughout the study
period, the water content in the container was kept approximately con-
stant by adding deionized water (25 mL). At the same specific time in-
terval as above, 15 mL of water samples were filtered by the filter
membrane and then collected from the container by opening the
valve. The levels of N, P and K in water samples were measured by the
ICP-OES and TOC/TN analyzer, respectively. The background concentra-
tion of N, P and K in the mixed soil was also analyzed using the same
protocols. Throughout the study, the detection of N, P and K in water
and soil were conducted in the Wetland Biogeochemistry Analytical
Services Center at Louisiana State University, Baton Rouge, LA, United
ð1Þ
States.
3. Results and discussion
3.1. Synthesis and morphology of hydrogels
Six SA-based hydrogels (i.e., pure SA, SA/NPK, SA/CNF, SA/CNF/NPK,
SA/CNF/PVA and SA/CNF/PVA/NPK) were prepared through blending
and crosslinking of CNFs and SA with and without hydrophilic PVA
and NPK fertilizers (Fig. 1). TEM micrograph shows that the average
width (± standard deviation) of the studied CNFs was 12.0 (±3.0)
nm (Fig. 1). CNFs had individualized fibers and formed an entangled
fiber network, which made it difficult to accurately determine the
length of individual CNFs. The size of the wet beads produced by combi-
nation of CNFs, SA, PVA and NPK averaged at 4.5 ± 0.5 mm. Freeze-
drying (−50 °C, 5 days) produced acceptable spherical hydrogel
beads. The freeze-dried beads shrank by more than half with a mean di-
ð2Þ
ameter of 1.9 ± 0.1 mm as shown on the SEM cross-section images.
The prepared hydrogels presented a microporous shell and a
macroporous core (Figs. 2–3). In particular, the core had numerous
pores with a diameter of 8–100 μm, while the shell, as a compact mem-
brane wrapping the core, had much smaller pores with an average di-
ameter of 4 ± 0.5 μm. Obviously, the morphology of this core-shell
structure was affected by the formation of chemical bonds and the
cross-linking action. In this system, an ‘egg-box’ junction [39] with a
dense/compact microporous chelated structure in the shell was
achieved through crosslinking of G units in alginate chains through
Ca2+ cations in the presence of PVA [40–42]. Moreover, the junctions
between the chains formed in this manner were relatively stable
332
S. Liu, Q. Wu, X. Sun et al. International Journal of Biological Macromolecules 172 (2021) 330–340

Fig. 1. SEM images and schematic illustrations of raw materials, synthesis process, and geometry of the CNF-SA-based hydrogels produced in the 0.1 wt% CaSO4 solution.

kinetically in the presence of cations that could be packaged and coordi-
nated. Detailed inspections of the surface structure also revealed that
during the dehydration process, the polymer network partially col-
lapsed, leading to cracks, wrinkles and micron-sized pores (Fig. 3). As
shown in Fig. 2m, the macroporous structure in the core of the
hydrogels significantly increased its surface area, helping promote the
mobility (or adsorption) of fertilizer ions (i.e., N, P and K in Fig. 2o)
and the capability of adsorbing water molecules within/between the
networks. Additionally, white flake-like fertilizer crystals were present
in the SA/NPK and SA/CNF/NPK hydrogel samples (Fig. 2), respectively.
For a better understanding of the alginate structure in the presence
of Ca2+, the crosslinking between pure G-rich alginate polymer chains
and Ca cations is also shown (Fig. 3). In this ‘egg-box’ model, pairs of
21-related helical chains were packed with Ca2+ located between
them [39,43]. Among those functional groups, the G groups [i.e., poly
(guluronate) units] in the alginate cross-linked with Ca cations in the
presence of PVA to form a semi-interpenetrating polymer network (s-
IPN)-like structure [29,44,45]. As one component of the hydrogels, the
cellulose in the s-IPN structure could interact with both SA and PVA in
a cross-linked network [14,15]. The incorporated CNFs (Fig. 3) were
well-dispersed in the PVA-SA matrices, which led to a significant in-
crease in the gels' mechanical properties [14,46–48]. For the core, the
network was formed by crosslinking SA and PVA in the presence of
the cellulose network [32,36], via hydrogen bonding and van-der-
Waals interactions to facilitate the formation of a three-dimensional hy-
drophilic network [14,47].

Fig. 2. FE-SEM micrographs of freeze-dried pure SA (a, b), SA/NPK (c, d), SA/CNF (e, f), SA/CNF/NPK (g, h), SA/CNF/PVA (i, j) and SA/CNF/PVA/NPK (k–o) hydrogels. The loading of SA, CNF,
PVA and NPK in these hydrogels are 1.5, 0.5, 0.5 and 1.5 wt%, respectively.

333
S. Liu, Q. Wu, X. Sun et al. International Journal of Biological Macromolecules 172 (2021) 330–340

Fig. 3. A SEM image of a sectioned dry gel and schematic representations showing shell-core structured SA/CNF/PVA/NPK hydrogels.

Furthermore, for the SA/CNF/PVA/NPK hydrogel, phosphate ions
(PO3−4 ), as the source of P element in the hydrogel, can provide covalent
bonding with carboxylate groups of SA and hydrogen bonding among
all three components. Besides, the other ions of NPK ingredients such
as potassium ion (K+) and ammonium ion (NH+ 4 ) are distributed on
the surface and also within the pores of the hydrogel composite. It
should be noted that the interlinked pores of the SA/CNF/PVA/NPK hy-
drogel can delay dissolution of loaded fertilizer into swelling medium
and results in the slow release behavior of the formulation.
3.2. Structural characterization of the hydrogels
FT-IR spectra of SA-based hydrogels were collected and are shown in
Fig. S1a. The FT-IR spectra of SA shows major peaks at 1600 cm−1 due
to C_O stretching of the carboxylic group, 2016 cm−1 (C\\H stretching
vibration), 3231 cm−1 (free\\OH groups). Moreover, 1414 cm−1 peak
was assigned to asymmetric and symmetric stretching of carboxyl anions
salt groups, while 1030 cm−1 corresponded to its saccharide structure
(C\\O\\C stretching from cyclic ether bridge) [58–60]. Analysis of the
SA/CNF/PVA hydrogel showed new FT-IR peaks. The weak peaks at
3238–4000 cm−1 appeared in comparison with those of the SA/CNF sam-
ples, indicating that the C\\H stretching was the main contributor
[23,25,26]. Additionally, two characteristic bands at 2876 and 665 cm−1
were present in the SA/CNF/PVA sample, which corresponded to the
C\\H stretching and out-of-plane O\\H vibrations of PVA, respectively
[22,24,49]. With respect to the SA/CNF hydrogels, some new peaks at
1800, 1967 and 2019 cm−1 could be due to the C\\H bending vibration,
C_O and C\\O stretching from acetate group [36].

Fig. 4. Equilibrium swelling of different freeze-dried hydrogels in deionized water. (a) Swelling of pure CNF hydrogels as a function of CNF concentrations, (b) Swelling of SA/CNF hydrogels
as a function SA loading (CNF loading = 0.5 wt%), (c) Swelling of SA/CNF/PVA hydrogels as a function of PVA loading (SA and CNF loadings of 1.5 and 0.5 wt%, respectively).

334
S. Liu, Q. Wu, X. Sun et al.
To explore the cross-linking mechanism between NPK and SA, CNF
and PVA, we also investigated the FT-IR spectrum of the SA/CNF/NPK
and SA/CNF/PVA/NPK (Fig. S1a). The FT-IR spectrum of the SA/CNF/
NPK with respect to the SA/CNF samples showed slight shifts in the
peaks because of the NPK. Moreover, a significant new peak at
606 cm−1 caused by the phosphate (PO3− 4 ) vibration [11] was observed,
suggesting that the formation of\\OC\\O\\P bond with Ca2+ complex,
while P element presented in the SA/CNF/NPK beads (Fig. S1a). For SA/
CNF/PVA/NPK hydrogel, after crosslinking in case of PO3− 4 , the charac-
teristic peak (C_O stretching of the carboxylic (\\COOH) group) of
SA was changed due to the formation of \\OC\\OP bonding through
the interaction of hydroxyl (\\OH) groups of H3PO4 environment with
acetate group (\\COO−) of SA [36]. Interestingly, P\\O remained intact
and did not participate in the reaction, which could be confirmed by the
presence of a peak 2001 cm−1 due to P_O bonding. Owing to the for-
mation of\\P\\O\\C bond, a new peak at 2142 cm−1 was also observed
[13,55,57].
The WXRD patterns of six prepared hydrogel samples were mea-
sured (Fig. S1b). A weak and broad diffraction peak of pure SA sample
at around 41.5° (2θ) was recorded, which is a characteristic pattern
for amorphous alginate [13,19,23,50]. In the XRD patterns of the SA/
CNF hydrogels, two new diffraction peaks at 2θ = 22.3° (sharper
peak) and at 2θ = 16.2° (weaker peak) were observed, corresponding
to the (200) and (110) reflection planes of the typical cellulose I struc-
ture [14,30]. Compared with the SA/CNF hydrogels, the SA/CNF/PVA
sample showed three new and weak diffraction peaks at around 21.0°,
31.7° and 34.3°, due to the orthorhombic lattice structure of semi-
crystalline PVA [23]. In the case of NPK, six strong characteristic peaks
of NPK fertilizer at 2θ = 11.6°, 21.0°, 28.2°, 40.4°, 45.4° and 50.1° were
observed, demonstrating that the crystalline nature of NPK compounds
in the SA-based hydrogels was retained in the hydrogel nanocomposites
[11,50,51]. All the XRD patterns of SA/CNF/PVA-based hydrogels show
associated characteristic peaks of PVA, SA, and CNFs. Among them,
these sharp diffraction peaks indicate the existence of the components
in the SA/CNF/PVA/NPK hydrogels. Interestingly, functional groups
after crosslinking were undergone significant changes in structure and
crystalline behavior of hydrogels, indicating effect on micro/nano-
structure and pore-interconnectivity of the hydrogels [14,36].
3.3. Water-retention characteristics and swelling kinetics
To obtain a proper CNF concentration for the preparation of SA-
based hydrogels with strong capacity of water absorption and retention
in water and soil, we synthesized five different pure CNF hydrogels. The
Fig. 5. Time-dependent swelling of different freeze-dried hydrogels in deionized water for 200 h. (a) Pure SA, SA/NPK, SA/CNF and SA/CNF/NPK hydrogels. (b) SA/CNF/PVA and SA/CNF/
PVA/NPK hydrogels.
335
International Journal of Biological Macromolecules 172 (2021) 330–340
swelling kinetics and equilibrium water-absorption capacity of these
freeze-dried CNF hydrogels in deionized water are shown in Figs. 4
and S2. The swelling ratios of all pure CNF hydrogel samples increased
rapidly during the initial hours (from 0 to 20 h; Fig. S2a), which was
mainly due to a large number of free adsorption sites on the pore surface
of these hydrogels [52]. The swelling ratios depended on the polymer
hydrophilicity, degree of crosslinking, and presence of electrical
charges. Subsequently, their growth rate slowed down until the equilib-
rium water-absorption capacity was reached. In comparison with the
other four CNF hydrogels, the highest swelling ratio was 8.0 g/g at
0.5 wt% CNF concentration (Fig. 4a). Since CNFs had many hydroxyl
groups on their surface, the CNF-based hydrogels were formed at a
low concentration by the entanglement of the nanofibers [14,48]. Sev-
eral studies also reported that at low solid content of about 0.5%, the fi-
bril dispersion was reversible for a physical gel that was held together
by fibril entanglement (e.g., [27,53]). Accordingly, the equilibrium
swelling ratio of the CNF-based hydrogels was affected by the applied
CNF concentration.
For further investigation of the effects of SA-based hydrogel compo-
sitions on water absorption capacity, hydrogel samples with different
compositions were synthesized and measured (Figs. 4, S2). In the pres-
ence of 0.5 wt% CNF, the swelling ratios of the SA/CNF hydrogels first in-
creased and then decreased as the SA dosage increased, and the highest
equilibrium ratio of 12.42 g/g was shown at the 1.5 wt% SA concentra-
tion. The equilibrium swelling ratios for samples with 0.5, 1.0, 2.0, and
2.5 wt% SA were 95.5, 100.9, 112.4, and 91.6 g/g, respectively. An expla-
nation for this finding is that the increased crosslinking density with
higher SA concentrations resulted in a closer and smaller network
space in the polymer matrix to accommodate water swelling, while
lower SA concentrations did not form a three-dimensional hydrophilic
network with effective water swelling [35,42,54]. This phenomenon
mainly depends on the diffusion of water and the ionization of the
groups during the swelling process [55]. As stated by Rehage et al.
[56], if the ionization rate was much slower than diffusion, the ioniza-
tion rate was limited by the non-Fickian swelling kinetics. With the in-
crease of SA dosage, more groups (e.g., \\COOH and \\COONa) were
ionized resulting in an increase in the ionization rate but in a decrease
in the kinetic exponent. After freeze-drying, however, these groups syn-
thesized at lower SA concentrations could be impeded in a compact
structure. Moreover, the equilibrium swelling ratios of PVA/SA
hydrogels were generally enhanced with increased PVA concentration
because PVA was more hydrophilic compared with SA [57]. In the pres-
ence of 1.5 wt% SA and 0.5 wt% CNF in these hydrogels, higher PVA
amount hindered physical crosslinking, making it more difficult for
S. Liu, Q. Wu, X. Sun et al. International Journal of Biological Macromolecules 172 (2021) 330–340

Fig. 6. Digital photographs of different hydrogels after 200 h swelling. (a) SA, (b) SA/NPK, (c) SA/CNF/NPK, (d) SA/CNF, (e) SA/CNF/PVA and (f) SA/CNF/PVA/NPK hydrogels.

non-covalent crosslinking of PVA [58]. Consequently, the equilibrium the freeze-dried SA/CNF/PVA/NPK hydrogels increased as the pH in-
swelling capacity of the SA/CNF/PVA hydrogels decreased with in- creased from 3.0 to 6.0, then stabilized over a pH range of 6.0 to 8.0
creased PVA concentrations, although all five hydrogels exhibited simi- (maximum at pH 7.0), and decreased at higher pH levels from 8.0 to
lar tendencies of swelling kinetics. at 11.0 (Fig. 8), indicating a pH-sensitive swelling behavior. In an acidic
Previously, Xie et al. [55] reported that the SA/PVA hydrogels (at solution, most carboxylate (\\COO−) groups are protonated into car-
5 wt%) cross-linked with calcium chloride using a freeze-thaw process boxylic acids (\\COOH), thus preventing anion–anion electrostatic re-
exhibited a low swelling ratio of 20.0 g/g. For swelling kinetics of six tar- pulsion [11,55]. In the pH range from 6.0 to 8.0, the \\COOH groups
get hydrogels, accordingly, the SA/CNF/PVA and SA/CNF/PVA/NPK tend to be ionized into\\COO− groups, which eventually enhance the
hydrogels presented a higher equilibrium swelling capacity (between network stretching and the swelling capacity of the hydrogels resulting
60 and 70 g/g) than the other hydrogels (at around 120 g/g; Fig. 5). from the increasing electrostatic repulsion between negatively charged
After analysis, the order of equilibrium swelling capacity is: SA/CNF/ carboxylates [23,30]. Consequently, the water absorption capacity of the
PVA > SA/CNF/PVA/NPK > SA/CNF > SA/CNF/NPK ≥ SA/NPK > SA hydrogels was significantly decreased. At pH levels higher than 8.0, the
(Fig. 6). Collectively, the optimum amounts of CNF, SA and PVA are Na+/K+ in the solution could be exchanged with the Ca2+ in the
0.5, 1.5, and 0.5 wt%, respectively, which led to a higher water absor- homopolymeric poly(guluronate) (G-block) and poly(mannuronate)
bency capacity for the prepared hydrogels. (M-block) of the alginate/SA structure, resulting in the breakdown of
To understand the water retaining characteristics of prepared
hydrogels in natural soil, we carried out a water-retention investigation
with the mixed soils (sandy soil: loam soil = 3:1; Fig. 7). During the 60-
day measurement period, the addition of freeze-dried SA/CNF/PVA and
SA/CNF/PVA/NPK hydrogels in the mixed soil maintained soil moisture
well and reduced water evaporation. On the 60th day, the water-
retention ratio of prepared hydrogels is in the following order: SA/
CNF/PVA/NPK > SA/CNF/PVA > SA/CNF/NPK > SA/CNF > SA/
NPK > SA > Control (Fig. 7). The leveling tendency of most of the
hydrogels suggested that they became more stable gradually near the
50th day. Therefore, this finding indicates that the hydrogel networks
composed of PVA, SA and CNFs improved the soil water retention
after they were incorporated into the mixed soil.
From a thermodynamic point of view, the swelling behavior of
hydrogels depends on the delicate equilibrium between Gibbs free en-
ergy of polymer-water mixing and Gibbs free energy associated with
the elastic properties of polymer networks [19,30,40]. When the water
absorption swelling balance is reached, the partial molar amounts of
these free energies become equivalent [52,59]. The presence of specific
functional groups along the hydrogel backbone polymer chain, the
swelling behavior of hydrogels, and associated release kinetics may be
sensitive to physiological conditions and therefore rely on physiological
Fig. 7. Water retention as a function of time in the mixed soil with freeze-dried pure SA,
pH and ionic strength [20,23,30]. In this study, the swelling behavior of SA/NPK, SA/CNF, SA/CNF/NPK, SA/CNF/PVA and SA/CNF/PVA/NPK hydrogels. The control
SA/CNF/PVA/NPK hydrogels at various pH values between 3.0 and 11.0 group had no added hydrogels, and all groups had 100 mL of deionized water, 50.0 g of
was also measured (Figs. 8, S3). The equilibrium swelling capacity of dry mixed soil and 5.0 g of any hydrogels.

336
S. Liu, Q. Wu, X. Sun et al. International Journal of Biological Macromolecules 172 (2021) 330–340

Fig. 8. Equilibrium swelling of freeze-dried SA/CNF/PVA/NPK hydrogels at different solution pH levels (a) and in different saline and alkali solutions (b). All saline and alkali solutions had
0.5 wt% concentrations.

Fig. 9. NPK releasing as a function of time from freeze-dried SA/NPK (a, b), SA/CNF/NPK (c, d), and SA/CNF/PVA/NPK (e, f) hydrogels in deionized water (a, c, e) and mixed soil (b, d, f). The
loading rates of SA, CNF, PVA and NPK in these hydrogels are 1.5, 0.5, 0.5 and 1.5 wt%, respectively.

337
S. Liu, Q. Wu, X. Sun et al.
some\\CO2−\\Ca2+\\−2OC\\ crosslink points and thus the reduction
of swelling capacity [23,50,52].
Nevertheless, the ionic strength of environmental physiology affects
the swelling of the hydrogels. The swelling ratios of the SA/CNF/PVA/
NPK hydrogels in all salt and alkali solutions were markedly lower
than those in deionized water (Figs. 8, S3), which could be attributed
to the osmotic pressure and elastic traits of the hydrogel networks
[11,60]. Besides, the charge-blocking effects or shielding of the
\\COO− anions from the monovalent cation helped reduce repulsive
forces and osmotic pressure, thereby reducing the swelling ratio of the
hydrogel network [60]. The polyvalent cations (e.g., Ca2+) could form
new crosslinks in the hydrogels, resulting in an increased crosslinking
density of the network and decreasing swelling ratio of the hydrogels,
while the monovalent cations break the crosslinks (Fig. S3; [52,55,61]).
3.4. NPK slow-release behavior in water and soil
The fertilizer-release behavior and corresponding swelling capacity of
prepared hydrogels are generally the result of crosslinking (i.e., tiepoints
or junctions), permanent entanglement, ionic interactions, or association
of microcrystalline regions of various chains [17,19,20,32,52,62]. To inves-
tigate the release mechanisms of hydrogel-loaded fertilizers in different
media, we examined the NPK-release dynamics of three synthesized
hydrogels (i.e., SA/NPK, SA/CNF/NPK and SA/CNF/PVA/NPK hydrogels)
in deionized water and in mixed soils (Fig. 9).
In water, a rapid 10-day maximum release in the SA/NPK hydrogels
was observed. The cumulative release ratios of N, P, and K in SA/NPK
hydrogels was 0.54%, 0.57%, and 1.00% on the first day, and 7.58%,
6.87% and 8.62% on the tenth day, while the K release was clearly higher
than N and P (Fig. 9a). This rapid, small amount of release behavior is
due to the fact that in the presence of Ca2+, pure SA formed a micro-
porous ‘egg-box’ shell but exhibited a macroporous core. Upon
crosslinking with SA, CNF and/or PVA, the cumulative release of NPK fer-
tilizers in SA/CNF/NPK (Fig. 9c) and SA/CNF/PVA/NPK hydrogels
(Fig. 9e) was higher and slower than those in SA/NPK hydrogels
(Fig. 9a). The N, P and K in SA/CNF/PVA/NPK hydrogels released
14.03%, 11.95%, 7.33% within a day and 67.90%, 70.78%, and 71.12%
within 30 days. The release of N, P and K from SA/CNF/PVA/NPK
hydrogels was, respectively, 0.06%, 0.01%, and 0.01% within 1 day and
24.82%, 36.21%, and 50.17% within 30 days. Since the total release of
the target fertilizer was reduced by 15% on the first day and by no
more than 75% on the 30th day, the slow-release properties of the two
hydrogels are in line with the slow-release fertilizer standard of the
European Committee for Standardization [63].
In the soil, except for the NPK release of SA/NPK and SA/CNF/NPK
hydrogels, the NPK-release pattern of all hydrothermal hydrogels was al-
most similar to those in water (Figs. 9b, d, f), which could be attributed to
the ionic properties of the soil that reduced the swelling capacity and sub-
sequently affected the amount of fertilizer released [40,50,51]. An alterna-
tive explanation is that less free-water in soils induced lower water
exchange rates, resulting in the reduction of the fertilizer-release rate
[11]. A slower NPK-release process in soils was observed in SA/CNF/
PVA/NPK hydrogels (Fig. 9f). In particular, the cumulative release of N, P
and K was 24.73, 18.59, and 25.92% on day 10 and 64.52, 53.72, and
64.08% on day 30, respectively. These were lower than the NPK-release
amounts on the same days in water, although the N-release at the 60th
day in soils was higher than that in water (79.48% vs. 72.73%; Fig. 9e).
To understand the slow-release mechanism of fertilizer-loaded
hydrogels, we employed the release kinetics model proposed by
Korsmeyer et al. [64]:
Mt
¼ Kt n ð4Þ
M∞
where Mt represents the amount of fertilizer-release at t, M∞ represents
the current total release amount, K is the kinetic constant, and n is the
338
International Journal of Biological Macromolecules 172 (2021) 330–340
diffusion parameter for determining the kinetic mode (i.e., n ≥ 0.5 for
Fickian diffusion, 0.5 < n < 1.0 for abnormal diffusion or erosion,
n = 1.0 for Case II transport/release controlled to zero by polymer relax-
ation, and n > 1.0 for Super-Case II transport/release controlled by ero-
sion). In the current work, the n values from SA/CNF/NPK and SA/CNF/
PVA/NPK hydrogels releasing in both water and soil are less than 0.5,
whereas the n values from SA/NPK hydrogels are more than 1.0
(Table S2). These findings suggest that the NPK-release of the SA/CNF/
NPK and SA/CNF/PVA/NPK hydrogels in water and soil was controlled by
Fickian diffusion, while the release in SA/NPK hydrogels is controlled by
erosion as Super-Case II transportation [50,56,64]. Based on the
Korsmeyer-Peppas model, we hypothesize the release mechanism of SA/
CNF-based hydrogels in the medium (water or soil) as follows. First, the
freeze-dried SA/CNF-based gels were slowly swelled by water and con-
verted to hydrogels in the medium. Subsequently, the NPK fertilizers en-
capsulated in the hydrogel were slowly dissolved. Second, the fertilizers
were slowly released to the medium by dynamic exchange (or by diffusion
control) between the inside and outside of the hydrogels [32,34,52]. With
the increase of swelling ratio, the macroporous size in the three-
dimensional networks was enlarged to facilitate diffusion of the fertilizer
to the medium [10,17,58]. Finally, the release rate of the fertilizers in the
medium was reduced, approaching a constant value at the end.
4. Conclusions
In this work, we presented the SA/CNF/PVA/NPK nanocomposite
hydrogels as a novel slow-release fertilizer to overcome long standing
challenges of convention fertilizers (e.g., over-use and uncontrolled
chemical releases). The hydrogels were fabricated via blending and
crosslinking SA, CNF and PVA in the presence of NPK fertilizers without
using toxic solvents. The hydrogels had a macroporous flexible core re-
inforced with CNFs via inter-/intra-molecular hydrogen bonds and a mi-
croporous rigid semi-IPN shell through chelation and covalent bonding
of SA-PVA with Ca cations. Such materials and structure configuration
significantly improved mechanical strength and water absorption capa-
bility, while maintaining the crystalline nature of NPK in the hydrogel. A
good physiological pH and salt/alkali sensitivity was recorded, and NPK
fertilizers in the SA/CNF/NPK and SA/CNF/PVA/NPK systems were
slowly released following the Fickian diffusion process in distilled
water and mixed soil. We envision that the hydrogel systems presented
herein holds a great deal of promise as a slow-release fertilizer and soil/
water regulating agent in the drought-prone environments for future
precision agriculture and horticulture applications.
CRediT authorship contribution statement
S.L. and Q.W. conceived the concept. S.L. and X.S. carried out exper-
imental work. S.L., Y.Y., and R.Y. performed data analysis and modelling.
S.L. drafted the manuscript. B.T., H.N.C. and Q.W. edited the manuscript.
All authors have read and agreed to the current version of the
manuscript.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgments
This collaborative study was carried out with supports from the
USDA Specialty Crop Block Grant Program-Farm Bill (SCBGP-FB, USA),
the Louisiana Board of Regents [LEQSF(2020-23)-RD-B-02], the
Chengdu Science and Technology Department, Sichuan, China [2019-
YFYF-00040-SN] and the Sichuan Landscape and Recreation Research
Center, Sichuan, China [JGYQ2019025]. Mention of trade names or
S. Liu, Q. Wu, X. Sun et al.
commercial products in this publication is solely for the purpose of pro-
viding specific information and does not imply recommendation or en-
dorsement by the U.S. Department of Agriculture (USDA). USDA is an
equal opportunity provider and employer.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.ijbiomac.2021.01.063.
References
[1] A.M. Senna, J.B. do Carmo, J.M.S. da Silva, V.R. Botaro, Synthesis, characterization and
application of hydrogel derived from cellulose acetate as a substrate for slow-release
NPK fertilizer and water retention in soil, J. Environ. Chem. Eng. 3 (2015) 996–1002,
https://doi.org/10.1016/j.jece.2015.03.008.
[2] M. Liu, R. Liang, F. Zhan, Z. Liu, A. Niu, Synthesis of a slow-release and superabsor-
bent nitrogen fertilizer and its properties, Polym. Adv. Technol. 1 (2006) 430–438,
https://doi.org/10.1002/pat.720.
[3] D. Norse, X. Ju, Environmental costs of China’s food security, Agric. Ecosyst. Environ.
209 (2009) 5–14, https://doi.org/10.1016/j.agee.2015.02.014.
[4] S.I. Sempeho, H.T. Kim, E. Mubofu, A. Hilonga, Meticulous overview on the con-
trolled release fertilizers, Adv. Chem. 2014 (2014) 1–16, https://doi.org/10.1155/
2014/363071.
[5] J.B.D. do Carmo, C. Neill, D.C. Garcia-Montiel, M. de Cássia Piccolo, C.C. Cerri, P.A.
Steudler, et al., Nitrogen dynamics during till and no-till pasture restoration se-
quences in Rondônia, Brazil, Nutr. Cycl. Agroecosys. 71 (2005) 213–225, https://
doi.org/10.1007/s10705-004-2213-8.
[6] F.G.E. Nogueira, N.T. Do Prado, L.C.A. Oliveira, A.R.R. Bastos, J.H. Lopes, J.G. De
Carvalho, Incorporation of mineral phosphorus on leather waste (collagen): a new
NcollagenPK-fertilizer with slow-liberation, J. Hazard. Mater. 176 (2010) 374–380,
https://doi.org/10.1016/j.jhazmat.2009.11.040.
[7] L. Wu, M. Liu, R. Liang, Preparation and properties of a double-coated slow release
NPK compound fertilizer with superabsorbent and water-retention, Bioresour.
Technol. 99 (2008) 547–554, https://doi.org/10.1016/j.biortech.2006.12.027.
[8] K. Zhong, Z.T. Lin, X.L. Zheng, G.B. Jiang, Y.S. Fang, X.Y. Mao, et al., Starch derivative-
based superabsorbent with integration of water-retaining and controlled-release
fertilizers, Carbohyd. Polym. 92 (2013) 1367–1376, https://doi.org/10.1016/j.
carbpol.2012.10.030.
[9] J.B. do Carmo, M.C. Piccolo, A.A. Cristiano, C.E.P. Cerri, J.B. Feigl, F.S. Neto, et al., Short-
term changes in nitrogen availability, gas fluxes (CO2, NO, N2O) and microbial bio-
mass after tillage during pasture re-establishment in Rondônia, Brazil, Soil. Till.
Res 71 (2007) 250–259, https://doi.org/10.1016/j.still.2007.06.002.
[10] M. Teodorescu, A. Lungu, P.O. Stanescu, C. Neamţu, Preparation and properties of
novel slow-release NPK agrochemical formulations based on poly(acrylic acid)
hydrogels and liquid fertilizers, Ind. Eng. Chem. Res. 48 (2009) 6527–6534,
https://doi.org/10.1021/ie900254b.
[11] A. Rashidzadeh, A. Olad, Slow-released NPK fertilizer encapsulated by NaAlg-g-poly
(AA-co-AAm)/MMT superabsorbent nanocomposite, Carbohyd Polym 114 (2014)
269–278, https://doi.org/10.1016/j.carbpol.2014.08.010.
[12] H. El-Rehim, E.S.A. Hegazy, H. El-Mohdy, Radiation synthesis of hydrogels to en-
hance sandy soils water retention and increase plant performance, J. Appl. Polym.
Sci. 93 (2004) 1360–1371, https://doi.org/10.1002/app.20571.
[13] G.R. Mahdavinia, S. Mousanezhad, H. Hosseinzadeh, F. Darvishi, M. Sabzi, Magnetic
hydrogel beads based on PVA/sodium alginate/laponite RD and studying their BSA
adsorption, Carbohyd. Polym. 147 (2016) 379–391, https://doi.org/10.1016/j.
carbpol.2016.04.024.
[14] Y. Yue, J. Han, G. Han, A.D. French, Y. Qi, Q. Wu, Cellulose nanofibers reinforced so-
dium alginate-polyvinyl alcohol hydrogels: Core-shell structure formation and
property characterization, Carbohyd. Polym. 147 (2016) 155–164, https://doi.org/
10.1016/j.carbpol.2016.04.005.
[15] Q. Zhang, G. Yu, Q. Zhou, J. Li, Y. Feng, L. Wang, et al., Eco-friendly interpenetrating
network hydrogels integrated with natural soil colloid as a green and sustainable
modifier for slow release of agrochemicals, J. Clean. Prod. 269 (2020), 122060,
https://doi.org/10.1016/j.jclepro.2020.122060.
[16] Y. Li, D. Maciel, H. Tomas, J. Rodrigues, H. Ma, X. Shi, pH sensitive laponite/alginate
hybrid hydrogels: swelling behaviour and release mechanism, Soft Matter 7
(2001) 6231–6238, https://doi.org/10.1039/c1sm05345k.
[17] H. Bian, L. Wei, C. Lin, Q. Ma, H. Dai, J.Y. Zhu, Lignin containing cellulose nanofibril-
reinforced polyvinyl alcohol hydrogels, ACS Sust. Chem. Eng. 6 (2018) 4821–4828,
https://doi.org/10.1021/acssuschemeng.7b04172.
[18] K.Y. Lee, D.J. Mooney, Alginate: properties and biomedical applications, Prog. Polym.
Sci. 37 (2012) 106–126, https://doi.org/10.1016/j.progpolymsci.2011.06.003.
[19] H.S. Samanta, S.K. Ray, Synthesis, characterization, swelling and drug release behav-
ior of semi-interpenetrating network hydrogels of sodium alginate and polyacryl-
amide, Carbohyd. Polym. 99 (2014) 666–678, https://doi.org/10.1016/j.carbpol.
2013.09.004.
[20] J. Sun, X. Zhao, W.R.K. Illeperuma, O. Chaudhuri, K.H. Oh, D.J. Mooney, et al., Highly
stretchable and tough hydroge, Nature 489 (2012) 133–136, https://doi.org/10.
1038/nature11409.
[21] K. Aftab, K. Akhtar, A. Jabbar, Batch and column study for Pb-II remediation from in-
dustrial effluents using glutaraldehyde–alginate–fungi biocomposites, Ecol. Eng. 73
(2014) 319–325, https://doi.org/10.1016/j.ecoleng.2014.09.091.
339
International Journal of Biological Macromolecules 172 (2021) 330–340
[22] J.P. Fuenzalida, P.N. Nareddy, I. Moreno-Villoslada, B.M. Moerschbacher, M. Swamy,
J.S. Pan, On the role of alginate structure in complexing with lysozyme and applica-
tion for enzyme delivery, Food Hydrocolloid 53 (2016) 239–248, https://doi.org/10.
1016/j.foodhyd.2015.04.017.
[23] S. Hua, H. Ma, X. Li, H. Yang, A. Wang, pH-sensitive sodium alginate/poly(vinyl alco-
hol) hydrogel beads prepared by combined Ca2+ crosslinking and freeze-thawing
cycles for controlled release of diclofenac sodium, Int. J. Biol. Macromol. 46 (2010)
517–523, https://doi.org/10.1016/j.ijbiomac.2010.03.004.
[24] H.S. Mansur, C.M. Sadahira, A.N. Souza, A.A.P. Mansur, FTIR spectroscopy character-
ization of poly (vinyl alcohol) hydrogel with different hydrolysis degree and chem-
ically crosslinked with glutaraldehyde, Mat. Sci. Eng. C: Mater. 28 (2008) 539–548,
https://doi.org/10.1016/j.msec.2007.10.088.
[25] B. Bolto, T. Tran, M. Hoang, Z. Xie, Crosslinked poly(vinyl alcohol) membranes, Prog.
Polym. Sci. 34 (2009) 969–981, https://doi.org/10.1016/j.progpolymsci.2009.05.003.
[26] C. Lu, C. Blackwell, Q. Ren, E. Ford, Effect of the coagulation bath on the structure and
mechanical properties of gel-spun lignin/poly(vinyl alcohol) fibers, ACS Sustain.
Chem. Eng. 5 (2017) 2949–2959, https://doi.org/10.1021/acssuschemeng.6b02423.
[27] N. Peng, D. Hu, J. Zeng, Y. Li, L. Liang, C. Chang, Superabsorbent cellulose-clay nano-
composite hydrogels for highly efficient removal of dye in water, ACS Sust. Chem.
Eng. 4 (2016) 7217–7224, https://doi.org/10.1021/acssuschemeng.6b02178.
[28] D. Wu, Y. Gao, W. Li, X. Zheng, Y. Chen, Q. Wang, Selective adsorption of La3+ using a
tough alginate-clay-poly(n-isopropyl acrylamide) hydrogel with hierarchical pores
and reversible re-deswelling/swelling cycles, ACS Sust. Chem. Eng. 4 (2016)
6732–6743, https://doi.org/10.1021/acssuschemeng.6b01691.
[29] J. Wang, X. Zhou, H. Xiao, Structure and properties of cellulose/poly(N-isopropyl ac-
rylamide) hydrogels prepared by SIPN strategy, Carbohyd. Polym. 94 (2013)
749–754, https://doi.org/10.1002/pat.1616.
[30] M. Li, Q. Wu, K. Song, S. Lee, Y. Qing, Y. Wu, Cellulose nanoparticles: structure–
morphology–rheology relationships, ACS Sust. Chem. Eng. 3 (2015) 821–832,
https://doi.org/10.1021/acssuschemeng.5b00144.
[31] S. Ummartyotin, H.A. Manuspiya, A critical review on cellulose: from fundamental to
an approach on sensor technology, Renew. Sust. Energ. Rev. 41 (2015) 402–412,
https://doi.org/10.1016/j.rser.2014.08.050.
[32] C. Chang, L. Zhang, Cellulose-based hydrogels: present status and application pros-
pects, Carbohyd. Polym. 84 (2011) 40–53, https://doi.org/10.1016/j.carbpol.2010.
12.023.
[33] M.K. Shin, G.M. Spinks, S.R. Shin, S.I. Kim, S.J. Kim, Nanocomposite hydrogel with
high toughness for bioactuators, Adv. Mater. 21 (2009) 1712–1715, https://doi.
org/10.1002/adma.200802205.
[34] J. Jang, J. Lee, Y. Seol, Y.H. Jeong, D. Cho, Improving mechanical properties of alginate
hydrogel by reinforcement with ethanol treated polycaprolactone nanofibers,
Compos. Part. B Eng. 45 (2013) 1216–1221, https://doi.org/10.1016/j.compositesb.
2012.09.059.
[35] M. Park, D. Lee, J. Hyun, Nanocellulose-alginate hydrogel for cell encapsulation,
Carbohyd. Polym. 116 (2015) 223–228, https://doi.org/10.1016/j.carbpol.2014.07.
059.
[36] A. Kumar, Y. Lee, D. Kim, K.M. Rao, K. Jisoo, S. Park, et al., Effect of crosslinking func-
tionality on microstructure, mechanical properties, and in vitro cytocompatibility of
cellulose nanocrystals reinforced poly (vinyl alcohol)/sodium alginate hybrid scaf-
folds, Int. J. Biol. Macromol. 95 (2017) 962–973, https://doi.org/10.1016/j.ijbiomac.
2016.10.085.
[37] D. Wilcox, B. Dove, D. McDavid, D. Greer, UTHSCSA Image Tool for Windows Version
3, The University of Texas Health Science Center in San Antonio, USA, 2000http://
ddsdx.uthscsa.edu/dig/itdesc.html.
[38] C. Zhou, Q. Wu, A novel polyacrylamide nanocomposite hydrogel reinforced with
natural chitosan nanofibers, Colloid. Surface. B 84 (2011) 155–162, https://doi.org/
10.1016/j.colsurfb.2010.12.030.
[39] G.T. Grant, E.R. Morris, D.A. Rees, P.J.C. Smith, D. Thom, Biological interactions be-
tween polysaccharides and divalent cations: the egg-box model, FEBS Lett. 32
(1973) 195–198, https://doi.org/10.1016/0014-5793(73)80770-7.
[40] K. Park, W.S.W. Sharaby, H. Park, Physical gels, Biodegradable Hydrogels for Drug
Delivery, Technomic Publishing, Lancaster, PA, 1993 , (ISBN: 9781566760041).
[41] A. Kikuchi, M. Kawabuchi, M. Sugihara, Y. Sakurai, T. Okano, Pulsed dextran release
from calcium-alginate gel beads, J. Control. Release 47 (1997) 21–29, https://doi.
org/10.1016/S0168-3659(96)01612-4.
[42] P. Sikorski, F. Mo, G. Skjåk-Bræk, B.T. Stokke, Evidence for egg-box-compatible inter-
actions in calcium-alginate gels from fiber X-ray diffraction, Biomacromolecules 8
(2007) 2098–2103, https://doi.org/10.1021/bm0701503.
[43] I. Braccini, S. Pérez, Molecular basis of Ca2+-induced gelation in alginates and pec-
tins: the egg-box model revisited, Biomacromolecules 2 (2001) 1089–1096,
https://doi.org/10.1021/bm010008g.
[44] C.M. Roland, in: K. Shiro, M. Klaus (Eds.), Encyclopedia of Polymeric Nanomaterials:
Interpenetrating Polymer Networks (IPN): Structure and Mechanical Behavior,
Springer-Nature Press, Berlin, Germany, 2014.
[45] J. Sethi, M. Illikainen, M. Sain, K. Oksman, Polylactic acid/polyurethane blend rein-
forced with cellulose nanocrystals with semi-interpenetrating polymer network
(S-IPN) structure, Eur. Polym. J. 86 (2017) 188–199, https://doi.org/10.1016/j.
eurpolymj.2016.11.031.
[46] D. Aoki, Y. Teramoto, Y. Nishio, Cellulose acetate/poly(methyl methacrylate) inter-
penetrating networks: synthesis and estimation of thermal and mechanical proper-
ties, Cellulose 18 (2011) 1441–1454, https://doi.org/10.1007/s10570-011-9580-5.
[47] M. Suzuki, Y. Nakajima, M. Yumoto, M. Kimura, H. Shirai, K. Hanabusa, Effects of hy-
drogen bonding and van der Waals interactions on organogelation using designed
low-molecular-weight gelators and gel formation at room temperature, Langmuir
19 (2003) 8622–8624, https://doi.org/10.1021/la034772v.
S. Liu, Q. Wu, X. Sun et al.
[48] M. Jonoobi, J. Harun, A.P. Mathew, K. Oksman, Mechanical properties of cellulose
nanofiber (CNF) reinforced polylactic acid (PLA) prepared by twin screw extrusion,
Compos. Sci. Technol. 70 (2010) 1742–1747, https://doi.org/10.1016/j.compscitech.
2010.07.005.
[49] H. Aloui, K. Khwaldia, M. Hamdi, E. Fortunati, J.M. Kenny, G.G. Buonocore, et al., Syn-
ergistic effect of halloysite and cellulose nanocrystals on the functional properties of
PVA based nanocomposites, ACS Sust. Chem. Eng. 4 (2016) 794–800, https://doi.
org/10.1021/acssuschemeng.5b00806.
[50] A. Olad, H. Zebhi, D. Salari, A. Mirmohseni, A.R. Tabar, Slow-release NPK fertilizer en-
capsulated by carboxymethyl cellulose-based nanocomposite with the function of
water retention in soil, Mat, Sci, Eng, C: Mater 90 (2018) 333–340, https://doi.org/
10.1016/j.msec.2018.04.083.
[51] R. Liang, M. Liu, L. Wu, Controlled release NPK compound fertilizer with the function
of water retention, React. Funct. Polym. 67 (2007) 769–779, https://doi.org/10.
1016/j.reactfunctpolym.2006.12.007.
[52] M.E. Byrn, K. Park, N.A. Peppas, Molecular imprinting within hydrogels, Adv. Drug
Deliv. Rev. 54 (2002) 149–161, https://doi.org/10.1016/S0169-409X(01)00246-0.
[53] K. Syverud, S.R. Pettersen, K. Draget, G. Chinga-Carrasco, Controlling the elastic mod-
ulus of cellulose nanofibril hydrogels-scaffolds with potential in tissue engineering,
Cellulose 22 (2015) 473, https://doi.org/10.1007/s10570-014-0470-5.
[54] K. Varaprasad, G.M. Raghavendra, T. Jayaramudu, J. Seo, Nano zinc oxide–sodium al-
ginate antibacterial cellulose fibres, Carbohyd. Polym. 135 (2016) 349–355, https://
doi.org/10.1016/j.carbpol.2015.08.078.
[55] L. Xie, M. Jiang, X. Dong, X. Bai, J. Ton, J. Zhou, Controlled mechanical and swelling
properties of poly(vinyl alcohol)/sodium alginate blend hydrogels prepared by
freeze-thaw followed by Ca2+ crosslinking, J. Appl. Polym. Sci. 124 (2012)
823–831, https://doi.org/10.1002/app.35083.
[56] G. Rehage, O. Ernst, J. Fuhrmann, Fickian and non-Fickian diffusion in high polymer
systems, Discus. Farad. Soc. 49 (1970) 208–221, https://doi.org/10.1039/
DF9704900208.
340
International Journal of Biological Macromolecules 172 (2021) 330–340
[57] M.D. Kurkuri, U.S. Toti, T.M. Aminabhavi, Synthesis and characterization of blend
membranes of sodium alginate and poly(vinyl alcohol) for pervaporation separa-
tion of water-isopropanol mixtures, J. Appl. Polym. Sci. 86 (2002) 3642–3651,
https://doi.org/10.1002/app.11312.
[58] F. Martínez-Gómez, J. Guerrero, B. Matsuhiro, J. Pavez, In vitro release of metformin
hydrochloride from sodium alginate/polyvinyl alcohol hydrogels, Carbohyd. Polym.
155 (2017) 182–191, https://doi.org/10.1016/j.carbpol.2016.08.079.
[59] V.R. Babu, K.S.V.K. Rao, M. Sairam, B.V.K. Naidu, K.M. Hosamani, T.M. Aminabhavi,
pH sensitive interpenetrating network microgels of sodium alginate-acrylic acid
for the controlled release of ibuprofen, J. Appl. Polym. Sci. 99 (2006) 2671–2678,
https://doi.org/10.1002/app.22760\.
[60] A. Pourjavadi, H. Ghasemzadeh, R. Soleyman, Synthesis, characterization, and swell-
ing behavior of alginate-g-poly(sodium acrylate)/kaolin superabsorbent hydrogel
composites, J. Appl. Polym. Sci. 105 (2007) 2631–2639, https://doi.org/10.1002/
app.26345.
[61] Y.O. Iwaki, M.H. Escalona, J.R. Briones, A. Pawlicka, Sodium alginate-based ionic
conducting membranes, Mol. Cryst. Liq. Cryst. 554 (2012) 221–231, https://doi.
org/10.1080/15421406.2012.634329.
[62] J. Han, T. Lei, Q. Wu, Facile preparation of mouldable polyvinylalcohol-borax
hydrogels reinforced by well-dispersed cellulose nanoparticles: physical, viscoelas-
tic and mechanical properties, Cellulose 20 (2013) 2947–2958, https://doi.org/10.
1007/s10570-013-0082-5.
[63] European Committee for Standardization (CEN), Slow-release Fertilizers: Determi-
nation of the Nutrients-method for Coated Fertilizers. EN 13266:2001, European
Committee for Standardization, Brussels, Belgium, 2002.
[64] R.W. Korsmeyer, R. Gurny, E. Doelker, P. Buri, N.A. Peppas, Mechanisms of solute re-
lease from porous hydrophilic polymers, Int. J. Pharm. 15 (1983) 25–35, https://doi.
org/10.1016/0378-5173(83)90064-9.