Industrial Crops & Products 203 (2023) 117114

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Industrial Crops & Products

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

Gum arabic/guar gum based biopolymeric nanohydrogel for shelf-life

enhancement of grapes and photocatalytic dye reduction
Sweezee Thakur a, Aarti Bains b, Kandi Sridhar c, Ravinder Kaushik d, Vijai Kumar Gupta e,
Prince Chawla a, *, Minaxi Sharma f, *
a
Department of Food Technology and Nutrition, School of Agriculture, Lovely Professional University, Phagwara 144411, Punjab, India
b
Department of Microbiology, Lovely Professional University, Phagwara 144411, Punjab, India
c
Department of Food Technology, Karpagam Academy of Higher Education (Deemed to be University), Coimbatore 641021, India
d
School of Health Sciences, University of Petroleum and Energy Studies, Dehradun 248007, Uttarakhand, India
e
Biorefining and Advanced Materials Research Center, SRUC, Kings Buildings, West Mains Road, Edinburgh EH9 3JG, UK
f
Department of Applied Biology, University of Science and Technology, Meghalaya 793101, India

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

Keywords: Recently, natural food preservation systems composed of metal oxide nanoparticles (NPs) gained great attention
Metal oxide nanoparticles from the food manufacturers, however, toxicity of NPs is a major concern. Therefore, in this study we synthesized
Gum arabic multifunctional gum arabic/guar gum biopolymeric nanohydrogel embedded with NPs for the enhancement of
Guar gum
the shelf-life of the grapes and for photocatalytic dye reduction. Copper, zinc, and iron metal oxide NPs were
Nanohydrogel
Coating
tailored using chemical precipitation and co-precipitation methods and subjected to various characterization
Grapes processes. The smaller particle size was observed with iron oxide NPs (23.64 nm) as compared to other NPs (Cu
and Zn). All metal oxide NPs showed cell viability ranging from 90.73 – 99.94%. The average droplet size of the
formulated hydrogel samples was ranging from 240.6 to 345.8 nm with an irregular and rough morphology.
Nanohydrogels at varied concentrations embedded with metal oxide NPs showed cell viability in the range of
93.73–99.97%. Zinc metal oxide NPs embedded in hydrogel showed higher spreadability properties, while
hydrogel embedded with iron oxide NPs showed lower spreadability properties. Grapes coated with formulated
hydrogel did not affect the physicochemical attributes during the storage (10 days), hence it can be scaled up as
an effective natural preservation system.

1. Introduction
Metallic nanoparticles (NPs) especially oxide NPs are intended to
define, based on size, fabrication process, and toxicological principles
that are protective of human health (Sengul and Asmatulu, 2020).
Several metals including zinc, titanium, copper, aluminum, iron, mag­
nesium, nickel, silicon, and manganese can be utilized for the fabrication
of various oxide NPs such as iron oxide (Fe3O4), zinc oxide (ZnO), ti­
tanium dioxide (TiO2), manganese dioxide, aluminum oxide (Al2O3),
magnesium oxide (MgO2), nickel oxide (NiO2), silicon dioxide (SiO2),
and copper oxide (CuO) by employing pulse laser ablation method,
co-precipitation, sol-gel, wet chemical precipitation, and microemulsion
methods, respectively (Estévez Ruiz et al., 2023). Furthermore, metal
oxide NPs with various morphologies have been applied in food pro­
cessing, food packaging, and food preservation industries (Chawla et al.,
2021). In addition, NPs have been very well documented for exhibiting
excellent antimicrobial activity against a variety of food-pathogenic
microorganisms. Therefore, these nanomaterials have gained interest
in food industries, which also act as advanced and better agents for the
prevention or control of microbial spoilage (Alotaibi et al., 2022). Metal
oxides are widely used as antimicrobial agents, however, the use of such
NPs in various industrial applications introduced challenges allied to the
metal nature itself. Furthermore, the toxic effects of metal oxide NPs
tend to restrain the utilization of NPs for potential applications (Chawla
et al., 2021). The mechanism of different types of toxicity such as
chronic, subchronic, and delayed is significantly associated with reac­
tive oxygen species (ROS) production that causes oxidative stress, gen­
otoxicity, mitochondrial protein damage, and causes cellular
inflammation (Ahmed et al., 2018). NPs also lead to organ toxicity by
entering through the cell membranes and reaching the various organs

* Corresponding authors.
E-mail addresses: princefoodtech@gmail.com (P. Chawla), minaxi86sharma@gmail.com (M. Sharma).

https://doi.org/10.1016/j.indcrop.2023.117114
Received 6 February 2023; Received in revised form 20 May 2023; Accepted 30 June 2023
Available online 10 July 2023
0926-6690/© 2023 Elsevier B.V. All rights reserved.
S. Thakur et al.
like kidneys, lungs, and liver (Patil et al., 2018). Causative factors for the
production of ROS are the size of NPs, solubility, composition, surface
charge, agglomeration, and transition metal (Girigoswami, 2018; Kim
et al., 2023). The agglomeration in metal oxide nanoparticles is due to
the metallic bonds which are not disrupted easily and reduce the me­
chanical properties. So, it is necessary to overcome the problems of
agglomeration and toxicity by formulating the hybrid nanocomposites
of metal oxide NPs using plant-based biological origin biopolymers
instead of disturbing the original structure of metal oxide NPs (Li et al.,
2023).
Therefore, the main challenge associated with the synthesis of
nanocomposites is to control the mechanical strength, surface chemis­
try, and also pore size for a long period. The interaction between
nanoparticle and polymer matrix provides higher stability, process­
ability, high biocompatibility, and low cost which also retains the
properties of nanoparticles (Nikolić et al., 2023). The stabilization of
NPs relies heavily on hydrogels and this nanogel contains hydrophilic
polymer chains that are strongly cross-linked physically or chemically.
The existence of functional hydrophilic sites in nanogels makes them
suitable to hold a large water volume (Wang et al., 2023). They can
expand better in solvents by holding the internal structures intact. The
nanohydrogel’s 3-D structure is composed of absorbing water and
cross-linking the hydrophilic copolymers (Ren et al., 2023). Swelling is
caused by the interaction of hydrophilic (water-loving) and hydrophobic
(water-repelling) molecules, as well as the degree of crosslinking and
ionization (Neamtu et al., 2017). The addition of different metal oxide
NPs to hydrogels brings numerous applications and results in a signifi­
cant increase in properties such as antimicrobial properties and a
decrease in cytotoxicity.
These NPs are always of great interest compared to other metallic
NPs like gold, silver, and platinum due to their cost effectiveness,
enormous accessibility, and compatibility in the field of the food in­
dustry, agriculture, and pharmaceuticals (Ashfaq et al., 2022; Bala et al.,
2023). Moreover, metallic oxide NPs are found effective (less toxic and
more biocompatible) against a broad range of pathogenic microorgan­
isms due to their nanoscale size (Bahrulolum et al., 2021). To achieve
this, therefore, nanoparticles can be embedded within the matrix of
nanohydrogel formulated of polymeric gelling and cross-linking agents.
Various plant-based gums are potentially used to formulate nano
hydrogels and enhance their water-absorbing properties (Pathania et al.,
2018). The ability to absorb water, softness, non-toxicity, swelling
behavior, and electrical, optical, and catalytic properties of these
nanohydrogels have all been improved. The medical field, biotech­
nology field, food industry, and water treatment plant are some of the
groundbreaking applications of hydrogels in various sectors (Nizam
et al., 2023). Grapes are globally popular fruits since they are tiny and
tasty and these are also excellent sources of carbohydrates, vitamins,
fats, organic acids, and other health-beneficial nutrients (Mengal et al.,
2020). In addition, during wine production, the ripeness, sugar content,
and acid are not sufficient for the prediction oenological potential of
grapes. The thin skin of the grape, on the other hand, makes it suscep­
tible to degradation due to mechanical impact and pathogen infestation
during processing, transportation, shipment, and storage (Ebersole,
2023). As a result, extending the life span and preserving the quality of
grapes is a crucial need. Only a few reports have been published and no
data is available for coated grapes to enhance their shelf life using
nanohydrogel-embedded metal oxide NPs.
Therefore, this research was designed based on the following ob­
jectives: i) synthesis of copper, zinc, and iron oxide NPs hybrid nano­
hydrogels, and their characterization, ii) cytotoxicity is the second factor
to consider, and, iii) shelf-life evaluation of grapes coated with nano­
hydrogel embedded with metal oxide nanoparticles. Overall, due to the
low cytotoxicity of hydrogels embedded with metal oxide nanoparticles,
it could be a remarkable antibacterial or microbial agent which can be
utilized to increase the shelf life of grapes at the commercial level.
Utilization of green and sustainable methods can result in a cost-
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Industrial Crops & Products 203 (2023) 117114
effective and edible hydrogel.
2. Materials and methods
2.1. Materials
In this research, ‘Analytical Reagent Grade’ chemicals such as crystal
violet, hydrochloric acid, sodium hydroxide, ferric chloride, zinc nitrate
hexahydrate, nitric acid, methylene blue, ethanol, and copper sulfate
pentahydrate were purchased from Sigma Aldrich, St. Louis, MO, USA.
Guar gum, gum acacia, pectin, and, antibiotic (ampicillin) of Hi-Media
Pvt. Ltd. Procured from (Mumbai, India). The human colon adenocar­
cinoma cells for cytotoxicity were procured from NCCS (National Centre
for Cell Science), Pune, Maharashtra, India. The Dulbecco’s Modified
Eagles Medium (DMEM) for the growth of the cells, was procured from
Cloud Clone-Corp Houston, USA, and dimethyl sulfoxide), L-glutamine,
and streptomycin was purchased from Sigma Aldrich, St. Louis, MO,
USA. Class “A” certified glassware washed with aqua-regia, Mili-Q water
during research work. Plates, plastic containers, and transwells were
obtained from Corning (NY, USA).
2.2. Methods
2.2.1. Copper oxide NPs fabrication
A wet chemical precipitation method was employed for the copper
oxide nanoparticle synthesis (Mayekar et al., 2014). Briefly, copper
sulfate pentahydrate solution was heated at 50 ◦ C temperature with
constant stirring and the pH of the hot solution was maintained at 8.0,
using 2 M sodium hydroxide. The addition of alkali resulted in the
precipitation of the copper to formulate the copper oxides and the so­
lution was then centrifuged at 10000g for 10 min at 27 ◦ C. Precipitates
were transferred to a glass petri plate and then subjected to drying in a
hot air oven for 4 h at 45 ℃. The obtained copper oxide NPs were stored
in air-tight glass vials for further characterization.
2.2.2. Zinc oxide NPs fabrication
The co-precipitation process by using zinc nitrate as metallic salt and
sodium hydroxide as a precursor was carried out for the fabrication of
zinc oxide NPs (Ahamed and Kumar, 2016). Briefly, an aqueous solution
of 0.1 M zinc nitrate hexahydrate was kept under constant stirring using
a magnetic stirrer at 600 rpm for 1 h to dissolve it completely. The
aqueous solution of 0.8 M NaOH was added dropwise by touching the
walls of the conical flask into completely dissolved zinc nitrate solution
under high-speed constant stirring for 45 min the reaction was further
allowed to complete for the next 2 h after the addition of a complete
volume of sodium hydroxide. The prepared solution was then allowed to
settle down overnight, and the supernatant was further separated with
the help of a pipette carefully. The remaining solution after the collec­
tion of supernatants was centrifuged at 10000g (10 min), and the pre­
cipitates were separated. The washing of precipitated ZnO nanoparticles
was carried out thrice with deionized water and ethanol and nano­
particles were subjected to hot air oven drying for 8 h at 50 ◦ C.
2.2.3. Iron oxide NPs fabrication
Iron oxide NPs were synthesized by the co-precipitation method
proposed by (AL-Latif et al., 2023). Herein, the ferric chloride solution
was heated to 55 ◦ C and the pH was adjusted to 9 by adding 2 M sodium
hydroxide dropwise. The iron chloride was co-precipitated by the
addition of alkali and iron oxide NPs were then collected by centrifu­
gation at 10000g for 10 min. Obtained nanoparticles were dried in a hot
air oven at 45 ℃ for 4 h and stored in acid washed glass vial for further
characterization.
S. Thakur et al.
2.2.4. Characterization method of metal oxide NPs
2.2.4.1. Determination of average particle size and zeta potential. The
characterization of the particle size distribution of the copper, iron, and
zinc metal oxide NPs was carried out using DLS (dynamic light scat­
tering) technique which was proposed by Patil and Behera (2023).
Herein, metal oxide NPs were dispersed in phosphate buffer (0.01 mM)
solution followed by ultra-sonication (Probe ultra sonicator), afterward,
the particle dispersion in the buffer solution was subjected to a computer
operated particle size analyzer (Zetasizer Nano ZS, Malvern Instruments
Ltd. Malvern, WR14 1XZ, UK). For zeta potential determination, metal
oxide NPs (5 mg) were dispersed in 5 ml of a phosphate buffer in a 25 ml
conical flask and placed on the magnetic stirrer at 200 rpm for 30 min.
Following, NPs were re-dispersed in 5 ml of distilled water and centri­
fuged, and then stirred continuously for 30 min. The NPs were diluted in
the water to measure their zeta potential by using Zetasizer (Nano-ZS)
from Malvern Instruments (software, Dispersion Technology Software).
2.2.4.2. Cytotoxicity of metal oxide nanoparticles. A tetrazolium-based
colorimetric assay was employed to determine the cytotoxicity of all
nanoparticles using the Caco-2 cell culture model as suggested by
Alnaim (2023). Herein, mature cells (1 × 105 cells) were seeded in 96
well plates, and plates were further kept for incubation under specific
conditions of 5% CO2 and 95% humidified atmosphere in an incubator
(Thermo Fisher Scientific, Mumbai, India) for 24 h at 37 ◦ C for cell
attachment. All metal oxide nanoparticles of different concentrations
(2–1000 µg/ml) were dispersed in media, transferred into the wells, and
kept on the plates for incubation at 37 ◦ C for 20 h. Furthermore, media
(90 µL) and 10 µL MTT (5 mg/ml) of media were carefully poured into
the seeded wells, and the media was decanted by inverting and flipping
the plate before washing the seeded cells with PBS (100 µL/well), the
plates were gently shaken and kept for incubation for 4 h at 37 ◦ C.
Moreover, 100 µL of DMSO was added to solubilize the formazan crys­
tals into each well, and 70 µL supernatant was removed during incu­
bation. The microplate reader was used to measure the absorbance (AB)
at 570 nm using the following Eq. (1).
[( ) ]
AB sample − AB negative control
Cell viability(%) = × 100
AB positive control − AB negative control
(1)
2.2.5. Nanohydrogel formulation
2.2.5.1. Formulation of emulsion. The formulation of emulsion by using
low energy method and flaxseed oil was used as an oil phase (Rostami
et al., 2018). Gum arabic was used as the emulsifier and Tween 80 was
used as the surface modifier component. Briefly, 250 mg of each metal
oxide nanoparticle was carefully dispersed in 25 ml water containing
250 mg gum arabic using a magnetic stirrer. Flaxseed oil (1 ml) con­
taining 250 µL of Tween 80 was added into the aqueous phase and
mixed well at 1000 rpm for 50 min in a magnetic stirrer. The milky
white solution appearance confirmed the formulation of the emulsion.
2.2.5.2. Conversion of emulsion into nanohydrogel. Emulsion-based guar
gum nano hydrogel was formulated by covalent bonding using pectin as
a cross-linker (Xiao et al., 2023). Briefly, 250 mg guar gum which acts as
a gelling agent, and 250 µL glycerol which acts as a connective linker
was used for the formulation of hydrogel using a magnetic stirrer at
1000 rpm for 30 min. The formulated hydrogel was then stored in
acid-washed glass vials for further characterization.
2.2.6. Characterization of nano hydrogel embedded with metal oxide
nanoparticles
2.2.6.1. Droplet size and zeta potential analysis. All hydrogels embedded
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Industrial Crops & Products 203 (2023) 117114
with NPs were added to a polystyrene latex cell and the measurements
were performed with a detector angle of 90◦ at 25 ◦ C at a wavelength of
633 nm. The total surface charge distribution of the hydrogel was
determined by a zeta potential analyzer. The sample was prepared by
mixing hydrogel with deionized water and then homogenized with an
ultrasonicator for 15 min for zeta potential analysis.
2.2.6.2. SEM (scanning electron microscopy) of nanohydrogel. The
morphological evaluation of nanohydrogel embedded with metal oxide
NPs was performed using a scanning electron microscope (JEOLJSM-
6510LV INCA, USA, 20 keVSE1 detectors) (Abubshait et al., 2023).
Briefly, osmium tetraoxide (1%) deionized water was used for fixing the
few nano hydrogel droplets. The fixed sample was then subjected to
centrifugation for 20 min at 10000g followed by washing with deionized
water. After repeating the process three times the upper layer was
removed and then washed and stabilized for 20 min before SEM
analysis.
2.2.6.3. Spreadability of hydrogel. To determine the textural properties
of the formulated nanohydrogel samples the TTC spreadability rig probe
of Texture Analyzer (TA. XT plus Texture Analyzer, Stable Micro System,
United Kingdom) was used (Cui et al., 2022). Both samples were
equilibrated at 27 ◦ C for texture analysis and the samples were allowed
to be set up in the center of the lower cone holder using a spatula up to
the surface leveled under a 23 mm diameter of TTC spreadability rig.
The probe was inserted into the nano hydrogel sample at 1 mm/s speed
until it attained 15 mm depth with a constant trigger force of 10 g. The
sample was then forced to flow outward between the spreadability rig
probe cone surface at 45º which indicated the degree of spreadability.
Using the inbuilt Texture Expert Exceed software (version 2.54), the
spreadability characteristic parameters such as firmness of gel, work of
shear, the stickiness of gel, and work of adhesion were evaluated from
the force-time curves.
2.2.7. Cytotoxicity of nano hydrogel
The cytotoxicity of the nano hydrogel embedded with metal oxide
NPs was evaluated by MTT [3-(4,5-dimethylthiazol-2-yl)− 2,5-diphenyl
tetrazolium bromide] assay using Caco-2 cell culture model (Liu et al.,
2020). Briefly, prior to the CO2 incubation for 24 h, the 96-well plates
were added with cells having the density of 1 × 105 cells per well fol­
lowed by the replacement of the cultured media with fresh media having
gel samples. After 6 h of incubation, each well of the fresh media was
then mixed with 100 µL of MTT solution (0.5 mg/ml). The purple for­
mazan crystals without media were dispersed in 100 µL DMSO with a
constant stirring for 15 min. The absorbance of the end solution was
performed using a microplate reader (Thermofisher scientific, USA) at
570 nm against CaCO-2 cells without any treatment and blank wells
without cells as a positive (+ve) control and negative (-ve) control
respectively. The viability of the cell was estimated by using Eq. (1).
2.2.8. Coating of grapes
Grapes were sorted carefully based on color & maturity and were
then washed thoroughly with double distilled water to remove dirt and
debris. For coating, grapes were emerged in the formulated hydrogels
(control hydrogel, copper hydrogel, iron hydrogel, zinc hydrogel) for
5 min followed by gentle air drying at 27 ◦ C for 30 min and then kept at
refrigerated temperature (4–7 ◦ C) for 15 days. Fresh uncoated grapes
were used as the control samples and the quality of grapes was examined
using texture analysis during 0th, 5th, and 10th days of storage.
2.2.9. Chemical composition and skin strength analysis of grapes
The grapes without any visible mechanical damage and with the
same characteristics of size and color were selected and further divided
into 4 groups. All groups for 10 days were maintained at 4–7 ◦ C to
evaluate the chemical composition and skin strength of grapes. To
S. Thakur et al. Industrial Crops & Products 203 (2023) 117114

Fig. 1. Formulated emulsion-based nanohydrogel (A), and their average droplet size (B) and zeta potential (C).

impact of nano hydrogel coating on the skin strength of grapes was

Table 1
determined by the puncture test using a needle probe (P/2 N) equipped
Particle size, zeta potential, and polydispersity index of nanoparticles.
with a Texture Analyzer. All samples were equilibrated at 27 ◦ C and the
Parameters Copper oxide Iron oxide Zinc oxide samples were then mounted in the center under a needle puncture probe
Particle size (nm) 39.41 ± 1.64 23.64 ± 0.97 31.54 ± 1.02 on an HDP/90 perforated platform. The needle probe penetrated the
Zeta potential (mV) -10.4 ± 0.76 -13.11 ± 0.91 -9.6 ± 0.58 grape at a velocity of 1 mm/s until it attained a 3 mm distance to avoid
Polydispersity index 0.157 ± 0.29 0.128 ± 0.21 0.095 ± 0.05
any damage to the puncture probe. Using the software, the force-
deformation curve as a graph was acquired, and the characteristic
determine titratable acidity (TA), the endpoint of the titration of grape parameter of skin strength of coated grapes was determined from the
juice was considered as g of tartaric acid / 100 ml. The refractometer force-time curve on the 0th, 5th, and 10th day of storage.
was used to obtain the total soluble solid content (TSS) of grape juice. In
addition, the color values of grapes were determined using a Hunter lab 2.2.10. Photocatalytic dye reduction
color flex colorimeter (Hunter associates laboratory Inc., USA). The The adsorption ability of crystal violet and methylene blue dyes
(10 mg/L) on the nanohydrogel embedded with different metal oxide

4
S. Thakur et al.
Fig. 2. Viability of Caco-2 cells exposed to different concentrations of copper,
zinc, and iron oxide nanoparticles. The results were expressed as mean
± standard deviation of > 3 independent replicates.
NPs was done by using the technique proposed by Mahida and Patel
(2016). Briefly, the adsorption experiment was carried out in 25 ml of
dye solution under bright sunlight. For the determination of maximum
adsorption capacity, about 100 mg of the nanohydrogel of each metal
oxide NPs was added to the respective dye solution with constant stir­
ring. During varying time intervals (20, 40, 60, and 80 min), 2 ml of dye
solution was taken out and analyzed the absorption spectra of super­
natant under UV-Visible spectrophotometer in the range between 800
and 400 nm were after 10 min centrifugation at 10,000g.
2.2.11. Statistical data analysis
Obtained results were evaluated statistically by following the
method described by Bains and Chawla (2020). The difference between
means was determined by critical difference (CD value) and to calculate
a significant difference between the average values one-way analysis of
variance (ANOVA) was employed. The calculation of means and stan­
dard deviation by employing descriptive analysis of the inbuilt data
analysis tool of Microsoft Excel, 2019 was used.
Fig. 3. Micrographs of (A) control, (B) zinc, (C) iron, and (D) copper hydrogels.
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Industrial Crops & Products 203 (2023) 117114
3. Results and discussion
3.1. Average particle size, polydispersity index (PDI), and zeta potential
of NPs
The formulation of precipitates confirmed the synthesis of metal
oxide NPs visually (Fig. 1A). The pH of the metallic salt solution
(aqueous) was acidic initially and in this aqueous solution, the metallic
ions existed as an aqua-ion. After the addition of alkali, the pH of the
solution was increased and the metallic aqua-ions were hydrolyzed to
fabricate the oxide-ions, and finally, metal oxide NPs were synthesized
in form of precipitates. Furthermore, synthesized metal oxide NPs were
characterized based on the PDI, average particle size (Fig. 1B), and zeta
potential (Fig. 1C), and the results are represented in Table 1. The
particle size of all NPs ranged from 23.64 ± 0.97–39.41 ± 1.64 nm and
samples showed a significant (p < 0.05) difference in terms of average
particle size. Iron oxide NPs showed a significantly (p < 0.05) smaller
size (23.64 ± 0.97 nm), whereas a larger particle size was observed for
copper oxide NPs (39.41 ± 1.64 nm). During the synthesis process, the
triggered weak kinetic force of nucleation and rapid growth of copper
oxide crystals could be the reason for the higher average particle size of
copper oxide NPs. Furthermore, the dropwise addition of alkali solution
led to supersaturation in the aqueous metallic salt medium, and the
molecular energy released by the alkali was quite constant, hence,
diffusion of copper oxide nanoparticles took place, and the formation of
large nuclei was observed. The PDI was determined to reveal the uni­
formity of NPs (size distribution). The copper, zinc, and iron metal oxide
NPs showed 0.157 ± 0.29, 0.128 ± 0.21, and 0.095 ± 0.05, PDI
respectively, and all NPs samples showed a significant (p < 0.05) dif­
ference from each other. A PDI value less than 0.3 indicates the homo­
geneity, uniformity, and narrower nanoparticle distribution of the
sample, however, the NPs having a PDI value less than 0.1 could be
considered monodispersed (Esterrani et al., 2023). The difference in PDI
values of all the metal oxide NPs was due to the larger size distribution of
respective metal oxide NPs (Clayton et al., 2016). Surface charge den­
sities and the zeta potential of metal oxide NPs were measured. The zeta
potential of copper, iron and zinc metal oxide NPs were − 10.4 ± 0.76,
− 13.11 ± 0.91, and − 9.6 ± 0.58 mV, respectively. All the NPs samples
showed a significant (p < 0.05) difference in surface charge distribu­
tion. The variation in the zeta potential on the NPs was due to higher
S. Thakur et al. Industrial Crops & Products 203 (2023) 117114

Fig. 4. Force-time curve by TTC spreadability rig probe to evaluate the firmness, work of shear, stickiness, and work of adhesion of (A) control, (B) copper, iron, and
zinc hydrogels, (C) viability of Caco-2 cells exposed to hydrogels. CHG, copper oxide hydrogels; ZHG, zinc oxide hydrogels; IHG, iron oxide hydrogels.

6
S. Thakur et al.
Table 2
Force-time data by TTC spreadability rig probe to evaluate the firmness, work of
shear, stickiness, and work of adhesion of hydrogels.
Samples Firmness Work of shear Stickiness Work of adhesion
(Force in g) (Area in g.sec) (Force in g) (Area in g.sec)
Control 110.590 117.179 -90.309 -50.367
Copper 163.559 153.708 -140.296 -48.867
Iron 135.383 125.030 -128.724 -40.686
Zinc 228.816 211.460 -238.956 -70.850
bond energy per atom and it was primarily due to the number of atoms
present inside the NPs and on the surface. Therefore, particular metallic
ions might be much more smoothly released from the surface which
causes voids on the surface and, thus, enhance the surface charge (Joshi
et al., 2023). Our finding is well supported by the results of Subhan et al.
(2020) and Dias et al. (2022), who observed a similar trend of results for
iron, copper, and zinc oxide NPs.
3.2. Influence of nanoparticles on Caco-2 cell viability
The cellular toxicity of copper, zinc, and iron NPs was investigated to
explain the cellular response and the results are represented in Fig. 2.
With varied concentrations, all-metal oxide NPs showed cell viability
between the range of 90.73 ± 2.64–99.94 ± 2.92%. The findings of this
test showed the viability of the cells in which iron oxide NPs were
exposed to 6–40 mg/ml concentration showed a significant (p < 0.05)
higher than copper and zinc oxide NPs. Moreover, copper oxide and zinc
oxide NPs, exposed to all concentrations, showed an insignificant
(p > 0.05) difference in cell viability. Moreover, at the concentration of
0–4 mg/ml all metal oxide NPs revealed an insignificant (p > 0.05)
difference in terms of cell viability. The least cell toxicity during expo­
sure to iron oxide NPs could be a result of differences in overall surface
properties and reactivity. Moreover, copper and zinc oxide NPs released
more Cu and Zn ions, which were toxic to the cells (Karlsson et al.,
2008). Least cycotoxic profile exerted in the cell line by the iron oxide
nanoparticles indicates that these nanoparticels do not act as indis­
criminate cellular toxins. Our results correlated well with the results of
Szűcs-Somlyó et al. (2023) and Ude et al. (2017), who exposed the
Caco-2 cells against the varied concentration of copper and iron oxide
nanoparticles and observed cell viability, and reported even at a higher
concentration no toxicity of copper nanoparticles.
3.3. Formulation, average droplet size, and zeta potential of
nanohydrogel
A schematic presentation of the emulsion micellar process is shown
in (Fig. 1). The presence of milky white color during the low-energy
emulsion formulation process confirmed emulsion synthesis. Further­
more, to formulate the gel and for micellar polymerization, gelling
agent, connective linker, and cross-linker were added, and the emulsion
was then aggregated in the form of spherical micelles as the critical
micelle increased. The reaction was continued until the surface tension
decreased and the invasion of hydrophobic monomers in the vicinity of
the micelle, at which point exhaustion was done in all monomer droplets
that help in the growth of micelle-containing monomers in their size.
The appearance of a white gel structure confirmed the formulation of the
control hydrogel, whereas the appearance of black, light brown, and
dark brown color changes confirmed the formation of copper, zinc, and
iron metal oxide nanoparticle-embedded hydrogel. The average droplet
size of hydrogels embedded with metal oxide nanoparticles ranged from
240.6 ± 10.78–345.8 ± 13.16 nm. Control hydrogel showed signifi­
cantly lower droplet size as compared to other samples, whereas CHG
showed significantly higher droplet size. Herein, with the embedding of
metal oxide NPs into the hydrogel, the average particle size was
increased considerably. The zeta potential of control hydrogel (CH),
7
Industrial Crops & Products 203 (2023) 117114
copper oxide embedded hydrogel (CHG), zinc oxide embedded hydrogel
(ZHG), and iron oxide embedded hydrogel (IHG), were − 11.9 ± 3.10,
− 14.6 ± 4.58, − 14.9 ± 4.69, and − 22.1 ± 2.94 mV respectively. All
the nanohydrogel samples showed a significant (p < 0.05) difference in
their zeta potential values and control hydrogel showed significantly
(p < 0.05) higher zeta potential values as compared to other counter­
parts. Copper and zinc oxide metal nanoparticles embedded showed an
insignificant difference in terms of zeta potential, however, IHG showed
a significantly different zeta potential value as compared to other sam­
ples. Zeta potential can be an important feature to understand the
physical and thermal stability of the nanohydrogel by the electrostatic
repulsion in the adjacent molecules. Moreover, the occurrence of
negative charge on the nanohydrogels surface was attributed to the
distribution of polymeric molecules containing surface active agent, oil
phase, and the metal oxide NPs through the hydrophobic binding moi­
ety. A high negative (-ve) surface charge tends to have good stability by
controlling the aggregation of different size particles to each other
(Prashar et al., 2022). The results from surface charge measurements
showed a negative (-ve) charge indicating relatively good stability. Re­
sults are well correlated with the findings of Khan et al. (2018), who
reported specific interaction of polymeric molecules with continuous
phase and surfactants resulting in the negative surface charge distribu­
tion of nanohydrogel.
3.4. Morphology of metal oxide embedded nanohydrogel
The FE-SEM (Field emission scanning electron microscopy) was used
to evaluate the surface structure of dried control and metal oxide NPs
embedded nanohydrogel and the results are represented in Fig. 3 (A-D).
SEM analysis revealed the different morphological structures of all the
nanohydrogel samples. Control nanohydrogel exhibited an open
network of porous and smooth structures as highlighted in Fig. 3.
Moreover, asymmetrical and irregular morphology was observed for the
hydrogel embedded with metal oxide NPs, whereas an even and smooth
surface was observed for the control nano hydrogel. The metal oxide NPs
embedded in the hydrogel was confirmed by the presence of tiny,
radiance polygonal-shaped structures disseminated on flat foils. Results
were well supported by the finding of Pasqui et al. (2011), who reported
an even and smooth surface for the CMC (carboxymethyl cellulose)–
TiO2 embedded hydrogel and DAP (di-ammonium phosphate).
3.5. Spreadability
Texture measurements provided a reliable overview of hydrogel
embedded with different metal oxide nanoparticles on different textural
parameters, such as work of adhesion, work of shear, stickiness, and
firmness. Fig. 4 (A-C) showed a curve of different characteristic pa­
rameters between the force and displacement. The composition of
nanohydrogel and the number of gelling agents are responsible for their
viscosity and textural properties, whereas, the strength of gel structure is
of great importance for firmness under compression. For shelf-life
extension, gel adhesiveness is an expected parameter that is related to
gel bioadhesives. By comparing the control hydrogel with the metal
oxide nanoparticle-loaded hydrogels, it is noticeable in Table 2 that the
texture of hydrogel embedded with metal nanoparticles has been
affected to some extent by increasing the work of shear and firmness and
by decreasing the stickiness, and adhesive force values. The addition of
the metal nanoparticles weakens the gel structure and leads to a more
disaggregated structure which will be responsible for the easy flow of gel
and provide less resistance for the conical probe. The stickiest the
sample is, the more negative the value of stickiness will be which was
previously reported. Whereas adhesiveness, work of shear, stickiness,
and firmness of control nanohydrogels seem to be lower than hydrogels
embedded with metal oxide nanoparticles. The gel cohesiveness was
measured directly by TPA under the single compression of a probe into
the gel sample which was measured as the curve area for force.
S. Thakur et al. Industrial Crops & Products 203 (2023) 117114

Fig. 5. Skin strength of the nanohydrogel coated grapes during storage. (A) 0 days, (B) 5 days, and (C) 10 days.

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S. Thakur et al. Industrial Crops & Products 203 (2023) 117114

Table 3A
Skin strength and color of gel-coated grapes during storage.
Skin strength

Samples Storage days

0 5 10

Skin strength (Force in g) Skin strength (Force in g) Skin strength (Force in g)

Uncoated grapes 113.19 ± 6.01 87.43 ± 5.06 82.92 ± 4.87

Control gel grapes 126.09 ± 8.01 110.33 ± 6.95 100.70 ± 6.12
Copper gel grapes 114.42 ± 6.15 111.55 ± 5.78 104.40 ± 4.06
Iron gel grapes 120.50 ± 5.91 115.29 ± 5.99 110.67 ± 5.54
Zinc gel grapes 112.35 ± 5.63 106.33 ± 5.27 103.67 ± 4.98
Copper iron zinc gel grapes 133.00 ± 8.09 130.70 ± 7.85 127.25 ± 7.46
Color
Samples Storage days
0 5 10
L* a* b* L* a* b* L* a* b*
Uncoated grapes 29.76 ± 3.31 -7.64 ± 2.12 2.32 ± 2.99 49.96 ± 5.32 -4.36 ± 1.22 8.67 ± 1.47 76.85 ± 7.21 -2.29 ± 0.85 16.09 ± 0.64
Control gel grapes 56.39 ± 5.24 -5.76 ± 3.16 20.51 ± 3.06 61.23 ± 4.36 -4.12 ± 1.92 24.96 ± 2.18 69.22 ± 3.71 -3.22 ± 1.19 29.99 ± 1.84
Copper gel grapes 42.47 ± 4.83 -5.79 ± 1.94 13.34 ± 2.73 47.27 ± 3.17 -5.21 ± 2.14 14.28 ± 2.73 51.89 ± 4.72 -4.88 ± 1.57 16.96 ± 1.65
Iron gel grapes 43.99 ± 5.01 -5.07 ± 2.92 13.12 ± 2.68 48.23 ± 3.61 -4.76 ± 2.31 14.89 ± 2.86 52.37 ± 5.14 -4.29 ± 1.43 17.27 ± 2.35
Zinc gel grapes 46.24 ± 5.24 -6.28 ± 2.38 15.62 ± 3.73 54.84 ± 5.39 -6.00 ± 1.85 17.12 ± 2.03 58.24 ± 2.94 -5.62 ± 1.53 20.89 ± 1.84

obtained which indicated the synergistic effect of the nanohydrogel and

Table 3B the cell structures (Karlsson et al., 2022). Our results correlated well
Soluble solids and acidity of gel-coated grapes during storage.
with the findings of Chawla et al. (2021) and Ude et al. (2017), who
Samples Storage days exposed the Caco-2 cells against the varied concentration of copper and
0 5 10 0 5 10 iron oxide NPs and observed cell viability and revealed no toxicity of
TSS TSS TSS TA (g) TA (g) TA (%) copper NPs at higher concentrations. Our all it could be inferred that the
(◦ Brix) (◦ Brix) (◦ Brix) least cycotoxic profile exerted in the cell line by the nanohydrogels
Uncoated 17.97 21.98 24.66 0.564 0.362 0.295 embedded with iron oxide nanoparticles indicates that these colloidal
grapes ± 0.04 ± 0.04 ± 0.18 ± 0.08 ± 0.04 ± 0.03 sturctures do not act as indiscriminate cellular toxins.
Control gel 17.98 20.56 22.02 0.563 0.499 0.406
grapes ± 0.08 ± 0.08 ± 0.13 ± 0.09 ± 0.09 ± 0.04
Copper gel 17.98 19.96 21.39 0.565 0.508 0.435
grapes ± 0.07 ± 0.07 ± 0.03 ± 0.08 ± 0.07 ± 0.05 3.7. Effect of storage on chemical composition and skin strength of grapes
Iron gel 17.98 19.30 20.55 0.565 0.510 0.482
grapes ± 0.06 ± 0.16 ± 0.02 ± 0.05 ± 0.05 ± 0.07 Control and coated grapes were subjected to skin strength analysis
Zinc gel 17.96 18.02 18.95 0.565 0.539 0.523 and the results are represented in Fig. 5 (A-C) and Table 3A. Herein, the
grapes ± 0.03 ± 0.05 ± 0.08 ± 0.06 ± 0.09 ± 0.04
coating of hydrogel embedded with NPs did not affect the skin strength
during the 0, 5th, and 10th days of storage. The change of 22.75% in skin
Generally, to check the cohesiveness of gel during TPA, the probe is strength was confirmed in control grapes during the 5th day (i.e. 87.436
compressed two times into the hydrogel samples, as it is determined as ± 5.06 g) of storage and it was increased to 26.74% during the 10th day
the ratio of an area on the second compression cycle which is produced (i.e. 82.923 ± 4.87 g), whereas, significantly fewer changes in skin
on the first compression cycle during a particular time under the force- strength of coated grapes (ranging from 1.72% to 8.75%) were observed
time curve. Our results were well in accordance with the finding of during the 0, 5th, and 10th days of storage. Furthermore, control
Hurler et al. (2012), who observed similar spreadability characteristics hydrogel showed a significantly higher change in skin strength as
of the hydrogel. compared to other test gel-coated grape samples. Based on visual
monitoring, the shiny surface characteristic was observed in the coated
grapes sample, whereas, the opaque surface characteristic was observed
3.6. Influence of metal oxide NPs embedded hydrogel on cell viability in the control sample of grapes. There was no visual growth of the fungus
on the surface of coated grapes and coating also improved the other
The cytotoxicity of hydrogel embedded with copper, zinc, and iron textural properties without affecting the fruit quality. In most fruits,
NPs was investigated to explain the cellular response, and the results are ripening accelerates the softening of tissues of grapes which causes
presented in Fig. 4. With varied concentrations, all hydrogels embedded certain changes such as a decrease in skin strength and exposing it to
with metal oxide nanoparticles showed cell viability between the range quality deterioration. Uncoated grapes showed a rapid loss. However,
of 93.73 ± 6.93–99.97 ± 7.14%. The findings of this test showed the the coating of hydrogel embedded with metal oxide nanoparticles im­
viability of the cells in which hydrogel embedded with iron oxide NPs parts quality improvement parameters by delaying the ripening process
were exposed to 4–40 mg/ml concentration showed a significantly and improving skin strength. Coating decreases chemical degradation
(p < 0.05) higher difference than that of copper and zinc oxide NPs. and reduces respiration (oxygen around the fruit), and water loss to
Moreover, copper oxide and zinc oxide NPs, exposed to all concentra­ maintain the quality of the fruit. These results were in accordance with
tions, showed an insignificant (p > 0.05) difference in cell viability. the findings of Lemes et al. (2017), who revealed no growth of micro­
Moreover, at the concentration of 0–2 mg/ml all metal oxide NPs had an organisms up to 7 days of storage of Benitaka grapes with the edible
insignificant (p > 0.05) difference in terms of cell viability. Herein, all coating of a hydrogel loaded with NPs and even did not affect the color
the nanohydrogel samples embedded with metal oxide NPs exhibited intensity and texture properties of grapes.
least toxicity as compared to the bare NPs as discussed in previous Furthermore, color values were measured and all grape samples
section. This could be due to that fact that polymeric three dimensional showed significantly different color values during the storage of grapes
network prohibited the degradation of ionic structures of the NPs. (Table 3A). As discussed in the previous section that nanohydrogels
Metabolic process of the cell was disturbed and more viable cells were embedded with nanoparticles showed distinct colors in appearance and

9
S. Thakur et al.
Fig. 6. UV-Visible spectra of photocatalytic degradation of dyes over time by nanohydrogel embedded with metal oxide nanoparticle. Crystal violet dye reduction:
(A) copper hydrogel, (B) iron hydrogel, (C) zinc hydrogel; methylene blude dye reduction: (D) zinc hydrogel, (E) iron hydrogel, and (F) copper hydrogel.
that significantly changed all the color values. Herein, during the 0th day
copper, iron, and zinc gel coated showed 42.47–46.24 L* values in
comparison to the control 29.76, which was increased up to 76.85
during the 10th of storage, whereas, grapes coated with nanohydrogel
embedded with NPs did not show an excessive change in L* value during
10th day of storage. A similar trend was observed for a* and b* values
during the storage of the grapes, respectively. The a* value close to zero
indicates the accumulation of anthocyanin which can be related to the
ripening of grapes, whereas the b* values also declined in all treated
samples as compared to the control samples, however, treated grape
samples with nanohydrogel showed insignificantly (p > 0.05) difference
from each other. Similar findings were obtained by Lemes et al. (2017),
who reported the color of Benitaka grapes was retained by applying
gelatin-based hydrogel coating which was loaded with curcumin nano­
particles after storage for 7 days at a condition of 25 ◦ C temperature. In
addition, the TSS of the grapes tends to be enhanced during the ripening
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Industrial Crops & Products 203 (2023) 117114
of fruit, and the analysis of the TSS of the grapes was observed at
17.96◦ Brix during the 0th day (Table 3B). This parameter extended for
control gel grapes (22.02 ◦ Brix) as well as grapes tested with hydrogels
embedded with copper, iron, and zinc NPs (21.39 ◦ Brix), (20.55 ◦ Brix)
and (18.95 ◦ Brix) during storage, respectively. Biological processes
including respiration, loss of moisture by evaporation, and inversion of
insoluble materials into soluble fractions could be considered as major
key factors for increasing the TSS during storage. On other hand,
metabolic activity showed several variations during the ripening of the
fruits, resulting in the conversion of complex carbohydrates and car­
boxylic acids into sugars. However, in our study, treatment indicated an
increase in TSS due to the fractionation of sucrose into sugars (i.e.
fructose and glucose). These results were well supported by the findings
of Diab et al. (2001), who studied the storage life of strawberries for 12
days at 20 ◦ C with the treatment of pullulan coating. Results revealed
that the SSC content of strawberries was lower than uncoated samples.
S. Thakur et al.
Moreover, the titrable acidity (TA) observation of the grapes was 0.565
± 0.07 g during the 0th day and with storage slight decrease in values of
TA was observed for all groups (Table 3B). During 10 days of storage, the
TA values of grapes were 0.40 ± 0.03, 0.43 ± 0.05, 0.48 ± 0.05, and
0.52 ± 0.04% (equivalent to tartaric acid) treated with control gel,
copper, iron, and zinc hydrogel, respectively. The degradation of
organic acids in grapes is responsible for this decrease in TA content.
Besides the sugars, the organic acids are the most prevalent solids which
are indicated as TA solids in the fruit’s acidity scale. Tartaric, malic, and
a trace amount of citric are the major organic acids present in grapes.
Malate and citrate concentrations decreased as the fruit ripened, a sign
that organic acids were being metabolized. These results were in line
with the finding of Melo et al. (2018), who reported that the coating of
chitosan-based nanohydrogel on grapes shows lower SSC values, and
also a few changes were observed in the TA content in comparison with
uncoated fruits.
3.8. Photocatalytic dye reduction ability
The results of the photocatalytic dye reduction activity of hydrogel
embedded with copper, zinc, and iron metal oxide NPs against crystal
violet and methylene blue dyes are represented in Fig. 6 (A-F). From the
results, hydrogels embedded with metal oxide nanoparticles reduced the
dyes efficiently under bright sunlight. Hydrogel embedded with
different nanoparticles reduced the dark color to the light color of crystal
violet and methylene blue dye under continuous stirring of 80 min. The
results of the photocatalytic degradation reaction of dyes clearly showed
the reduction in absorption spectrum with the increase in the time in­
terval which could be due to interactions between the anionic charge
distribution on hydrogel embedded with nanoparticles and positively
charged molecules of dyes. These results were consistent with those
obtained by Abubshait et al. (2023), who observed the 85% degradation
of methylene blue dye within 112 min in the presence of c0-doped zinc
oxide nanoparticles embedded in Polyvinylalcohol hydrogel under
bright sunlight.
4. Conclusion
Metal oxide NPs with different morphological features have been
applied in various food technological applications. The cellular toxicity
of metal oxide NPs can restrain their potential utilization for various
applications. Therefore, the formulation of nanohydrogel hybrid metal
oxide nanocomposites was approached to overcome this problem.
Different potential methods including wet chemical precipitation and
co-precipitation methods were used to fabricate the copper, zinc, and
iron oxide NPs and iron oxide nanoparticles revealed smaller particle
sizes. The cellular viability response of Caco-2 cells was obtained and
iron oxide NPs were found to be the least toxic. The low-energy assisted
O/W emulsion was formulated and by the addition of a suitable gelling
agent and cross-linkers, nanohydrogel hybrid metal oxide nano­
composites were tailored. Nanoscale droplet size and scanning electron
microscopy confirmed an open network of porous and smooth structures
for control and irregular and rough morphology of the composite
nanohydrogels. At varied concentrations, nanohydrogels embedded
with metal oxide nanoparticles showed good cell viability and adhe­
siveness, and work of shear, stickiness, and firmness was higher in zinc
metal oxide nanoparticle-embedded hydrogel. Grapes coated with
hydrogel embedded with nanoparticles revealed good skin strength
during the 0th, 5th, and 10th days of storage. In conclusion, coating
maintained the sugar content, acidity, and color and minimized the rate
of respiration of fruit, and water loss to sustain the fruit quality, there­
fore, nanohydrogel hybrid metal oxide nanocomposites could be scaled
up as an effective food preservative system, and potential coating agent
at the industrial level.
11
Industrial Crops & Products 203 (2023) 117114
CRediT authorship contribution statement
Sweezee Thakur: Methodology, Data curation, Conceptualization,
Software, Formal analysis, Writing – original draft; Aarti Bains: Formal
analysis, Visualization, Software, Writing –review & editing; Kandi
Sridhar: Formal analysis, Software, Writing – review & editing; Rav­
inder Kaushik: Software, Writing – review & editing; Vijai Kumar
Gupta: Writing – review & editing; Minaxi Sharma: Supervision,
Conceptualization, Methodology, Software, Visualization, Writing – re­
view & editing; Prince Chawla: Supervision, Conceptualization, Soft­
ware, Visualization, Formal analysis, Writing – review & editing,
Resources.
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.
Data Availability
Data will be made available on request.
Acknowledgment
Support provided by the Central Laboratory Facility, Lovely Profes­
sional University is gratefully acknowledged.
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