A Review On Recent Developments and and Applications of Nanozymes

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Food Analytical Methods

https://doi.org/10.1007/s12161-021-01983-9

A Review on Recent Developments and Applications of Nanozymes


in Food Safety and Quality Analysis
Ananya Payal 1 & Srinivasan Krishnamoorthy 1 & Arunkumar Elumalai 1 & J. A. Moses 1 & C. Anandharamakrishnan 1

Received: 11 October 2020 / Accepted: 9 February 2021


# The Author(s), under exclusive licence to Springer Science+Business Media, LLC part of Springer Nature 2021

Abstract
Food is intricate, and food quality and safety are indispensable elements. With the rising public demands for safe and nutritious
food products, a range of innovative, interdisciplinary, and multidimensional concepts have emerged in the last few decades.
Nanozymes, apart from their therapeutic efficacies, are gaining increasing interest in safety and quality monitoring in the agri-
food sector. These enzyme-mimetic nanomaterials are proven to detect and monitor food safety in real-time with high selectivity,
stability, reliability, and recyclability. Nanozymes sourced from various nanomaterials like carbon, metal, and their oxides,
metal–organic frameworks, and others offer several advantages over natural enzymes in food-based applications. Apart from
real-time monitoring, these are also known for their robustness to harsh food processing environments, ease of production, and
smooth and facile surface modifications. Nanozymes undergo single and multiple enzyme pathways during food analysis
applications, facilitating the on-demand tailorable activity. In this context, this review briefly summarizes the working strategies
and factors affecting the catalytic activity of nanozymes; the emphasis is placed on the detection of targeted analytes in the food
matrix using nanozymes. Interdisciplinary tools, combined with nanozymes that aid in developing rapid on-spot identification,
including spectroscopies, smartphones, electrochemiluminescence, and ELISA, are elucidated systematically. Evidenced by the
rising number of nanozyme-based publications, many of the practical gaps in food analysis are narrowed. Simultaneously, some
challenges like variations in recognition-to-signal patterns, optimization of nanozymes, and reproducibility of methodology need
to be addressed in the future.

Keywords Nanozyme . Food safety . Food quality . Enzyme mimics . Immunosensing . Food contaminants

Introduction microbes, toxins, heavy metals, and pesticides have been iden-
tified by WHO (2019). Several analytical approaches, such as
Foodborne illness, be it due to pathogens, microbial toxins, or chromatographic methods, electrophoresis tools, and immu-
other contaminants, now directly affects an estimated 600 noassays like enzyme-linked immunosorbent assays (ELISA),
million people (almost 1 in 10 in the world) as highlighted are used to determine food contaminants. However, most such
by the World Health Organization (WHO) in 2020. Though approaches are time-consuming, expensive, and tedious sam-
substantial progress has been made in reducing foodborne and ple preparation processes, and demand expertise for operation
waterborne illness and its sequelae over the past few decades, (Thanushree et al. 2018). An emerging challenge that arises
daunting challenges are to the fore since several new concerns with the modern food processing sector is its contribution to
like listeriosis are incessantly emerging. Nearly 200 kinds of greenhouse gas emissions, which is calculated as around 26%
foodborne diseases due to food contaminants such as of the global carbon footprints. The enzymes and its mimics
are considered green alternatives to reduce the impacts of
food-based environmental impacts. The rapid expansion of
the global food enzyme market is projected to reach USD
* C. Anandharamakrishnan
anandharamakrishnan@iifpt.edu.in 3.2 billion by 2025 from an estimated 2.4 billion in 2019,
boosting novel food enzyme–based analytical developments
1
Computational Modeling and Nanoscale Processing Unit, Indian (Research and Markets 2020).
Institute of Food Processing Technology (IIFPT), Ministry of Food However, the inherent limitations in extraction, purifica-
Processing Industries, Government of India, Thanjavur, Tamil tion, and natural enzyme storage led to high production costs
Nadu 613005, India
Food Anal. Methods

and lower recyclability. Nanoscience-based novel technolo- 1D nanomaterials. Nanosheets and nanofilms are examples of
gies will be key in meeting the dual challenge of producing 2D nanomaterials, and nanocrystals and nanocubes are 3D
green materials and creating highly efficient food analytical nanomaterials. Metals and their oxide NPs, metal–organic
tools to ensure food safety and security (Soto et al. 2017). frameworks (MOFs), carbon nanomaterials like multi- and
“Artificial enzyme,” as termed and coined by Breslow, is a single-walled carbon nanotubes (SWCNTs and MWCNTs),
combination of metal catalytic group and a hydrophobic bind- and CDs, among others, are nanozymes that exhibit excep-
ing cavity that imitates the function of a typical natural en- tional catalytic activity. Fe 3 O 4 magnetic nanoparticles
zyme molecule (Breslow and Overman 1970). Artificial oxi- (MNPs) were the first discovered nanozymes and were found
dases, glycosidases, and esterases are few examples of artifi- to exhibit peroxidase (POD) enzyme-like catalytic activity in
cial enzyme molecules. These artificial enzyme-based food industrial food applications (Gao et al. 2007). Molybdenum
analytical methods are found superior and selective in detect- oxide nanorods synthesized from green tide algal biomass
ing proteins, ions, and various other contaminants or adulter- waste exhibiting food enzyme-like properties are a classic
ants. Likewise, biosensors with enzymatic mechanisms have example of an efficient and sustainable trend to replace bio-
gained enormous attention for their specificity, simplicity of logical enzymes in food safety management (Ren et al. 2019).
construction, and ease of operation. The novel biosensors re- These nanozymes have multiple functions besides catalytic
lying on newly invented nanoparticles (NPs) are being used as reactions and a large surface area for bioconjugation. The
functional materials for recognition and signal amplification robust detectability through sensors and transducers is an ad-
in food safety and quality assessment (Gopal et al. 2013). The ditional feature over the natural enzymes.
emergence of nanosensor-based portable devices which can Driven by systematic investigations on nanozymes and an
measure pathogens, toxins, and allergens in real-time is a ever-deepening understanding of nanosized particles, modern
promising field of biosensing with high sensitivity (Jin et al. nanozyme preparations consume less time and have proven to
2015). The “zyme” suffix is widely used for materials with meet a wide range of food analytical requirements. Once syn-
enzyme-like catalytic functions, and nanozymes are thesized, the nanozymes are recyclable and reusable, unlike
nanosubstances that imitate natural enzymes by catalyzing natural enzymes. Ferromagnetic NPs modified with chitosan
biological reactions with higher efficiencies (Manea et al. have been reported to possess excellent recyclability up to 10
2004; Gao et al. 2007). usages to detect phenolic pollutants (Jiang et al. 2018).
The “twofold” increase in research publications from 2010 Though complex procedures are required to modify active
to 2020 related to the search term “nanozymes in food appli- sites of the nanozymes, surface modification using antibodies,
cations” in PubMed and ScienceDirect (published until aptamer strands, molecular imprinting, and modulators like
December 2020) confirmed the growing interest of the scien- ions have been proven to alter the catalytic activity of
tific community towards the nanozymes and their applications nanozymes effectively to a remarkable extent (Liang et al.
in food analysis (Fig. 1). Nanomaterials that act as nanozymes 2017; Niu et al. 2018; Liu et al. 2019a). However, applications
can be of any shape or structure and can be categorized as of these vogue functional nanomaterials in food safety and
zero-dimensional (0D), one-dimensional (1D), two- quality monitoring are in the latent phase compared to their
dimensional (2D), and three-dimensional (3D) materials. exploitation in therapeutics. These catalytically active
Spherical structures like carbon dots (CDs) are 0D materials nanomaterials are recently found to exhibit a huge promise
while nanowires, nanorods, and nanotubes are categorized as to conquer the limitations of the traditional enzymes in detect-
ing foodborne pathogens, heavy metals, toxins, pesticides,
300
and adulterants in food products. Although the potential of
nanozymes in catalysis and chemical reactions has been
discussed in several reviews, very few studies exemplified
the mechanism, characteristics, and specific applications of
No. of. publications

200 192
nanozymes in the food industry.
Therefore, this review summarizes the catalytic principles,
influencing factors, and food analytical applications based on
93
100 the recent research findings and the challenges and percep-
60
tions of their future roles in food quality and safety.
34
2 5 2 2 5 10
1
0
2010 2011 2012 2013 2014 2015 2016 2017 2018 2019 2020
Year
Nanoparticles as Nanozymes

Fig. 1 Year-wise publication record on nanozymes in food applications. As discussed in the above section, NPs possessing enzyme-
Source: Data collected from PubMed and ScienceDirect search engines like activity can be structured to form various shapes like
Food Anal. Methods

sheets, wires, rods, fibers, composites, and bundles. These can Similarly, Fe2O3 coated with Prussian blue exhibited im-
be synthesized from sources like metals and their derivatives, proved catalytic activity compared to Fe2O3 alone (Song
carbon materials, and polymers (Guo et al. 2017b; Luo et al. et al. 2016). Figure 2a represents the enzymatic activity of
2019; Boruah and Das 2020). This section explains the most gold NPs in sensing of acetamiprid pesticide, where step A
common nanostructures that are mimicking the food analyti- represents the POD-like activity of gold NPs in the presence of
cal enzymes with suitable examples. TMB. However, it can be inhibited by the conjugation of the
S-18 aptamer in step B. When the target analyte acetamiprid is
Metals, Noble Metals, and Metal Oxides present, the aptamer binds with the target and allows POD
reaction of gold NPs, resulting in a noticeable color change
The metal oxide-based nanozymes such as Fe3O4 MNPs were (step C).
the first discovered nanozymes which are chemically and bi-
ologically inert and possess superior magnetic and catalytic Metal Organic Frameworks
properties. Fe 3 O 4 MNPs, when added with 3,3′,5,5′-
tetramethylbenzidine (TMB) and other peroxidase substrates, Metal organic frameworks (MOFs) are crystalline nanostruc-
exhibit POD-like activity following Michaelis-Menten kinet- tures designed by coordinating inorganic metal ions with an
ics in a way similar to the natural enzyme horseradish perox- organic linker. These pseudo-enzymes are known for their
idase (HRP). The maximum catalytic activity has been report- porous structures and tunable active sites compared to natural
ed at a pH of 3.5 and a temperature of 40 °C for 30-nm–sized enzymes and other nanozymes (Wang et al. 2018a, b, c).
NPs. However, the amount of co-substrate (H2O2) required Pristine MOFs, MOFs-based composites, and MOFs with
was twice compared to HRP (Gao et al. 2007). Using these chemical modification are easily applicable for different bio-
MNPs, Ding and co-workers detected melamine in milk sam- sensing applications in food safety due to their versatile na-
ples with a limit of detection (LOD) around 2.5 ppm under ture. Pristine MOFs have high porous structures, large surface
optimized conditions of pH 4.0, incubation temperature 45 °C, area, and flexible active sites, and hence support efficient ca-
and a total assay time of 10 min (Ding et al. 2010). Inspired by talysis of biomolecules. Varieties of Material Institute
the superior properties of MNPs, researchers have also Lavoisier (MIL), for example, Fe–MIL–88NH2 that exhibited
worked on the enzyme mimicking properties of iron oxides POD-like activity in detecting H2O2 in milk samples, are in
like Fe2O3 (hematite) (Wu et al. 2018b), Cu2O (Dai et al. the category of pristine MOFs. When added with luminol,
2018), and MnO2 (Wu et al. 2019a). Metals, when utilized these MOFs catalyze the reaction efficiently, resulting in max-
as nanocomposites (Au-Pt, Pt-Pd, and Au-Fe3O4), exhibit imum chemiluminescence and accurate H2O2 quantification.
synergistic effects and, therefore, hike their catalytic potential The LOD was found to be 0.025 μmol/L (Li et al. 2017a).
as nanozymes (Lin et al. 2019a, b). Noble metals like Ag, Pt, Coordinatively unsaturated sites (CUS) on MOFs allow active
Au, and Pd, and their combinations are proved to exhibit site modification, thereby enhancing the functionality of these
POD-like activity (Wu et al. 2018a). In an exciting enzyme nanozymes. For instance, in the detection of choline and ace-
switching study, the effect of halide ion (I−, F−, Cl−, and Br−) tylcholine in milk samples, Valekar and others grafted MOFs
on casein protein-modified gold NPs, and their efficiency was with aliphatic diamines at CUS and assessed their POD-like
explored. Among all halides, I− showed rapid irreversible in- activity. The highest catalytic activity was noticed owing to
hibition of POD activity of the nanozyme and revealed that it the synergistic effect of the enhanced negative potential, pre-
is due to the bonding of Au with I, thereby blocking the active cisely controlling the molecular size of diamines (Valekar
sites. It is also proven that the compound halide’s switching et al. 2018). In another study made by Chen and co-workers,
efficiency was found to be dependent on the intrinsic property PtNPs/MOF hybrids made of copper, heme like Fe(III) tet-
and surface density of modifiers used (Liu et al. 2017). Su and ra(4-carboxyphenyl) porphine chloride (Cu-TCPP(Fe)) li-
Chen (2017) developed a reusable 3D printed multi-well plate gand, and embedded PtNPs were used in the detection of
using desktop filament extruder using Fe3O4 and Fe2O3 NPs H2O2. These hybrids exhibited excellent catalytic activity with
incorporated into polylactic acid (PLA) filaments. In the scan- a LOD of 0.357 μM compared to the individual components
ning electron microscope view, the extruded filaments that formed MOF hybrids and also avoided aggregation of
showed rugged surfaces, and Fe3O4 and Fe2O3 NPs were well PtNPs on ultrathin nanosheets (less than 10 nm) during
dispersed and mounted on the PLA filaments. Such filament growth (Chen et al. 2018).
surfaces with nanozymes explain their stability and protection
against contaminants. Fabricated 3D objects possess enhanced Molecularly Imprinted Polymers
POD-like activity and exhibit maximum activity at 5 g/kg of
iron oxide NPs. Research has also proved that Pt and Pd as Molecularly imprinted polymer (MIP)–based nanozymes are
composites exhibit enhanced catalytic activity due to their produced by the polymerization of monomers around a tem-
increased surface area to volume ratio (Yuan et al. 2014). plate molecule. This process creates active sites for the actual
Food Anal. Methods

reaction when the template molecule is removed. The prime (Zhang et al. 2017b). Resistance to external factors like high
objective of molecular imprinting is to increase the specificity temperature, mechanical stress, and chemical treatments is a
and selectivity of nanozymes along with enhanced activity merit of MIPs. Artificial receptors imprinted on the polymer’s
Food Anal. Methods

ƒFig. 2 (a) Schematic representation of the GNPs exhibiting POD-like 2019; Savas and Altintas 2019). Palladium-carbon dot nano-
activity. (A) POD-like activity of gold NPs. (B) Conjugation of S-18 composites were also used to detect H2O2 and glucose in real
aptamer with gold NPs. (C) Formation of aptamer and target complex,
followed by the POD reaction of gold NPs with TMB. Copyright (2014),
samples, and LOD reported for H2O2 (0.3 μM) was mostly
with permission from ACS Publications (Weerathunge et al. 2014). (b) similar to the LOD value obtained by Chen and co-workers in
Schematic image for the synthesis of MIP-capped AgNPs@ZnMOF. (1) a similar type of study (Zhuo et al. 2019). The MNPs, when
Synthesis of MOFs. (2) Addition of AgNPs into MOF pores. (3) combined with carbon dots, offer rapid detection of the com-
Molecular imprinting using the substrate. (4) Elimination of substrate
template which resulted in the formation of target binding pockets on
mon foodborne pathogen Staphylococcus aureus. In this pro-
MIP-capped AgNPs@ZnMOF. Copyright (2018), with permission from cess, the silver-based nanoclusters (NCs) adhered to target
Elsevier (Bagheri et al. 2018). (c) The formation process of Fe-N-CDs sites of pathogen and formed sandwich immunocomplex,
and its POD mimetic activity. Copyright (2017), with permission from which aided in the oxidation of o-phenylenediamine (OPD).
Elsevier (Yang et al. 2017b)
In this case, the pathogen dose was directly proportional to
color change, and LOD was found to be 4.9 CFU/mL (Yao
et al. 2020). Nickel and nitrogen co-doped graphene nano-
surface can be regenerated and reused irrespective of their
tubes loaded with PtNPs exhibited POD-like activity in the
storage conditions, and hence considered an excellent alterna-
detection of glucose. This nanostructured catalyst was proved
tive for natural receptors (Rane et al. 2015).
to be efficient in immobilizing the glucose oxidase enzyme,
In a study to enhance POD specificity of Fe 3 O 4
thus detecting the amount of glucose, using a microfluidic
nanozymes, its surface was imprinted by TMB through the
paper-based sensor (Fakhri et al. 2019). Figure 2c shows the
adjustment of the zeta potential (the electric charge on the
process of synthesis of Fe-N-CDs and their enzymatic activity
NP surface). This resulted in the formation of substrate bind-
in the detection of patulin.
ing pockets, and a 100-fold increase in specificity was ob-
served compared to non-imprinted nanozymes (Zhang et al.
2017b). Fan and team worked on enhancing the glucose oxi-
Preparation of Nanozymes
dase mimicking the activity of Au-Pt nanozymes by molecular
imprinting method. These alloy NPs showed maximum activ-
Different nanozymes with high catalytic performance are cre-
ity when taken in a 1:1 ratio and were combined with magnet-
ated continuously by establishing the connections between the
ic microspheres for better stability and easy separation. After
catalytic nanomaterials’ functional characters with their chem-
the addition of glucose template molecules, glucose-bindable
ical structure and surface morphology. Many physicochemical
aminophenyl boronic acid was used for imprinting. Glucose-
and crystal properties are involved in the de novo synthesis of
binding pockets were formed after the removal of template
an ideal nanozyme (Jiang et al. 2019). The surface lattice
molecules, and these pockets exhibited 200-fold higher cata-
arrangement, surface valence, composition, and architecture
lytic efficiency than AUNPs (Lin et al. 2019a). In a study on
of the active sites are considered critical factors in the design
the quantification of patulin present in fruit juices, MIPs mod-
and development of a nanozyme (Wang et al. 2020b). To
ified with AuNPs, carbon dots, and chitosan were employed.
mimic the cascade of reactions and multifaceted functions of
The compound 2-oxindole acted as a dummy template, while
the biological enzyme, nanozymes are synthesized through
ρ-aminothiophenol was a functional monomer. Usage of CDs
the bonding of hybrid co-catalyst particles. Recently, encap-
and chitosan increased the electron transfer rate, electrode
sulation of nanomaterials with catalytic property has been
surface area, and signal strength, which was detected electro-
shown to enhance their specificity and selectivity.
chemically. The LOD was found to be 7.57×10–13 mol L−1
Gao et al. 2007 demonstrated the peroxidase-like activity in
(Guo et al. 2017b). Figure 2b explains the synthesis of MIP-
magnetic iron oxide nanoparticles, an interesting phenomenon
capped AgNPs@ZnMOF. This figure represents the prepara-
that drove focus towards further synthesis and application of
tion of MOFs and incorporation of AgNPs into pores followed
nanozymes. Solvothermal or hydrothermal synthesis is the
by molecular imprinting of MOFs using patulin.
most widely used technique for the synthesis of nanozymes
with controlled dimensions. Guo and co-workers synthesized
Carbon Dots and Graphene Quantum Dots Ni–MOF nanoplates using the hydrothermal method and
thereby detected Pb2+ in the food matrix. In this procedure,
Nanoengineered carbon molecules can be transformed into an organic ligand, metal ions, and dimethylformamide (DMF)
various forms such as single- and multi-walled carbon nano- were dispersed in deionized water and transferred to a reactor
tubes, CDs, graphene dots (GDs), and quantum dots which are maintained at a controlled time and temperature. A serial of
zero-dimensional nanomaterials. These exhibit excellent centrifugation, precipitation, and purification processes were
phospholuminiscence characteristics, high chemical stability, made and at last Ni-MOF nanoplates were created for suitable
and low cytotoxicity, making them an ideal candidate for bio- food safety applications (Guo et al. 2017a). Though the for-
chemical sensing and imaging applications (Ahmed et al. mation of single crystals is considered the main advantage of
Food Anal. Methods

the hydrothermal technique, this technique also has its limita- azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) (ABTS),
tions such as degradation of heat-sensitive compounds, and OPD, and amplifu red (AR) occurs using H2O2 as a co-sub-
generation of explosive and corrosive solvent waste. strate. If the analyte is present in the sample, nanozymes tend
(Sharanyakanth and Radhakrishnan 2020). to catalyze the reaction using the analyte as the substrate,
Besides, a chemical reduction process has been used to thereby ceasing the reaction with externally added substrate
prepare catalytic materials in recent days. Benedetti and his quantitatively. The amount of visible color change produced
colleagues elucidated the acid dealloying of carbon-supported due to the reaction will be directly proportional to the quantity
Pt-Ni NPs. This process involves the reaction of a surfactant of analytes present in the sample. To understand single-
with Pt and Ni NPs and the etching of carbon-supported NPs enzyme pathways and POD-like activity, a recent study con-
with nitric acid (Benedetti et al. 2018). The deposition of gold ducted by Lien and others on amorphous cobalt hydroxide/
NPs on graphene paper for the electrochemical detection of oxide-modified graphene oxide nanohybrids that acted as a
glucose is one of the recent examples of the synthesis of single natural enzyme (peroxidase) is explained. This
nanozymes by the solid thermal dewetting process CoOxH-GO hybrid nanozyme catalyzed the oxidation of
(Scandurra et al. 2019). Meanwhile, co-precipitation, electro- POD substrate in the absence of a target analyte. However,
chemical deposition, polymerization, sol-gel method, and the presence of heavy metal cyanide ion inhibited the oxida-
electrospinning are other techniques commonly used for syn- tion of peroxidase substrate AR to reddish resorufin, quanti-
thesizing nanozymes. Polymerization of nanozymes is highly tatively. The higher concentration of a metal ion in the sample
practiced during the synthesis of MIPs. Fe3O4/MWCNT resulted in lesser visibility of the red color to the naked eye
nanocomposites employed in detecting H2O2 were synthe- (Lien et al. 2018). Figure 3a shows the single-enzyme path-
sized by co-precipitation technique and possessed benefits way of nanozymes.
like simplicity, stability, and cost-effectiveness (Salarizadeh Other nanozymes like OXD mimics, CAT mimics, and su-
et al. 2018). Electrospun nanofibers exhibit large surface area peroxide dismutase (SOD) mimics can also be related to single-
to volume, high aspect ratio, and tunable compositions and enzyme pathways. Unlike POD mimics, OXD mimics catalyze
structures (Song et al. 2019). Despite enormous developments substrates that release H2O2 or superoxide radical species that
in the preparation of nanozymes, several enzyme mimics lack help in further oxidation of colorless substrates into corre-
selectivity while engineering the heterogeneous surface struc- sponding colored products that result in the detection of various
ture of nanosized particles. analytes. For instance, a portable paper-based sensor employed
with manganese oxyhydroxide nanowires (NWs) as OXD
nanocatalysts and TMB as a chromogenic indicator was devel-
Catalytic Pathways and Working Strategies oped to detect organophosphorus pesticides. MnOOH NWs
of Nanozymes oxidized TMB to blue-colored products in the absence of
analytes proving their OXD-like activity and single-enzyme
Although various nanozymes were investigated, nanozymes nature, followed by 93.1 to 105.4% recovery during spectral
and their catalytic reaction pathways are complex to under- detection of omethoates and dichlorvos in Chinese cabbage
stand yet. POD, oxidase (OXD), and catalase (CAT)-like en- samples (Huang et al. 2019a). In a very recent study on the
zyme mimics are the most common nanozymes used to detect detection of carbendazim in tea and rice samples, graphene-
food analytes that are elucidated here to understand the prin- like MoS2/multi-walled carbon nanotube (MWCNT)–based
ciple of enzymatic pathways. Some NPs mimic a single natu- electrochemical nanozyme sensor coupled with machine learn-
ral enzyme and carry reaction catalysis, whereas others behave ing exhibited excellent OXD mimicking activity with a lower
like more than one enzyme, either inherently or in response to LOD (7.4 nM). R2 value above 0.99 obtained after neural usage
the changing environment, thus catalyzing multiple substrates. networks instead of regression proved the model’s suitability in
There are also possibilities for other strategies to occur, as real-time detection of carbendazim (Zhu et al. 2020). SOD is
discussed later in this section. the antioxidant enzyme that can remove excess reactive oxygen
species, thus preventing oxidative stress. Fullerene and its de-
Single-Enzyme Pathway rivatives are found to exhibit SOD-mimic properties (Wu et al.
2019b). CAT mimics act as antioxidant nanozymes and medi-
In the single-enzyme pathway, nanozymes act as a single nat- ates the conversion of H2O2 into the water, preventing its ac-
ural enzyme. Nanocatalysts tend to remain and catalyze reac- cumulation. Co3O4 nanozymes exhibiting single-enzyme cata-
tions as single enzymes, irrespective of the external influenc- lase activity were found to have good selectivity and reproduc-
ing conditions. Some of the common enzymes that mimic ibility in detecting calcium present in milk samples with a LOD
carrying out a single-enzyme pathway in detecting food con- of 4 μM (Mu et al. 2014). Table 1 represents the typical single-
taminants are discussed here. In the case of POD-like step reactions carried out by enzymes and examples of respec-
nanozymes, the oxidation of substrates like TMB, 2,2′- tive nanozymes.
Food Anal. Methods

Fig. 3 Schematic representation


of single-enzyme and multi-
enzyme pathways of nanozymes

Multi-enzyme Pathway show POD-like, OXD-like, and CAT-like activities simulta-


neously as represented in Fig. 3d (Zhao et al. 2019). Also, two
On the other hand, some nanozymes act on substrates by act- or more nanozymes can combine to form composites and
ing like more than one enzyme either inherently or with var- perform catalytic reactions. In a study reported by Liu and
iations in pH, temperature, and other external factors. co-workers, MOF/Ce-based nanozyme composites were used
Figure 3b, c, and d explain the various multi-enzyme path- to eliminate S. aureus bacterial films. Here, MOF acted as
ways followed by nanozymes. For example, copper NCs sta- DNase and disrupted the biofilms while cerium-based
bilized with metallothionein (MT-CuNCs) exhibit inherent nanozymes showed POD-like activity that resulted in bacteri-
CAT-like activity but showed POD-like activity owing to its cidal effects (Liu et al. 2020b). In a study, using cobalt and
high affinity towards TMB substrate and H2O2, when added, iron NPs, a bimetallic MOF was developed to exhibit both
thus aiding in the detection of Pb(II) and Hg(II). MT-CuNCs- POD-like activity and OXD-like activity in the detection of
H2O2 while exhibiting CAT-like activity produced an absorp- H2O2 colorimetrically (Yang et al. 2017a).
tion peak at 240 nm. When Pb(II) and Hg(II) and TMB were
added to the MT-CuNCs-H2O2 solution, self-oxidation of Other Functional Strategies
H2O2 occurred, followed by oxidation of TMB by OH* quan-
titatively based on Pb(II) and Hg(II) concentrations, showing Apart from the most common catalytic pathways explained in
absorption peak at 450 nm. This shift in absorption peak con- sections “Single-Enzyme Pathway” and “Multi-enzyme
firms the POD-like activity of MT-CuNCs (Liu et al. 2019e). Pathway,” they can also act as multifunctional sensing ele-
Heme-like single-atom nanozymes with Fe-N4 as active sites ments. The interfacial adsorption ability of nanozymes is a

Table 1 Catalytic equations and corresponding nanozymes of natural enzymes

S. No. Natural enzymes Catalytic reaction Some corresponding nanozymes References


reported in the literature

1 Peroxidase 2AH + H2O2 ➔ 2A + 2H2O AUNCs, Zhang et al. (2020c)


2AH + ROOH➔ 2A+ ROH+ H2O Hemin-CDs, Wang et al. (2018b)
CoN NWs Li et al. (2017b)
2 Oxidase AH + O2 ➔ A + H2O Dithiothreitol-capped Pd, Xu et al. (2019)
AH + O2 + H2O ➔ A + H2O2 NiO, Li et al. (2018)
MnCo2O4 Huang et al. (2018)
3 Catalase H2O2 ➔ O2 + 2H2O Maghemite, Palmqvist et al. (2017)
GO-Fe2O3, Song et al. (2016)
CuNCs Liu et al. (2019e)
4 Super oxide dismutase 2O2*- + 2H+ ➔H2O2+ O2 Citrate capped Pd, Moglianetti et al. (2020)
Cu-Zn, Mn, Fe Wu et al. (2019c)
Food Anal. Methods

strategy by which the labeling step can be avoided, leading to samples, respectively (Hassan et al. 2019). The bimetallic gold-
label-free operations (Huang et al. 2019b). Nanozyme-based platinum functionalized silica NPs were used as signal labels
ELISA method developed by Wang and co-workers used against E. coli O157: H7 detection in milk samples. After
hemin-concanavalin A hybrid nanozymes instead of enzyme antigen-antibody reaction on T-line, T-line was cut and added
labels. These hybrids were adsorbed onto the Escherichia coli, with H2O2 leading to the production of O2. The logarithmic
catalyzing the oxidation reaction. The linear range of detection concentration of E. coli is a direct measure of the height of the
was found to be 101–106 CFU/mL with a lower detection foam generated by trapping released oxygen in sodium dodecyl
limit of 4.1 CFU/mL (Wang et al. 2018b). Metal nanozymes sulphate (Liu et al. 2019d).
have an affinity towards the magnetic field and can be used in
the separation of analytes by eliminating the need for centri-
fugation. The nanozymes as signal tags can establish a pro- Factors Affecting the Catalytic Activity
portional relationship with the analyte amounts to be detected of Nanozymes
by catalyzing reactions. An efficient approach for signal am-
plification with the self-catalyzed growth of gold NPs has The importance of NPs as nanozymes was realized when re-
been reported in an immunochromatographic assay to detect searchers unraveled their superior properties such as dominant
pathogenic Salmonella enteritidis. Gold nanoparticles facets, charges, coatings, and loadings with multicatalytic ac-
(GNPs), after catalyzing the reaction between HAuCl4 and tivities. Based on these features, the structural and surface
NH2OH·HCl, produce more GNPs on the surface of existing properties of these novel nanozyme molecules could be
GNPs, leading to signal amplification (Bu et al. 2018). engineered to allow target-dependent catalytic activities apart
ELISA and lateral flow immunoassays (LFIA) are com- from target compound recognition. Unlike natural catalysts,
mon techniques being used in the detection of various food nanozymes are considered to be biologically and chemically
contaminants. ELISA is based on antigen-antibody recogni- inert. However, the process parameters like pH, substrate con-
tion, while LFIA is a point-of-care bioassay on a paper-based centration, temperature, and structure can influence the cata-
device. In a study conducted by Urusov and co-workers, anti- lytic properties to various extents. The factors determining the
aflatoxin B1 antibodies were immobilized on the surface of activity of nanozymes required to be optimized for specific
MNPs in the detection of aflatoxin B1 (AFB1) from barley conditions so that maximum efficiency can be obtained during
and maize samples. The use of nanozymes instead of the con- applications involving the detection of targeted analytes.
ventional ELISA technique provided benefits in terms of de- In a study, LFIA with Pd-Pt NP solution was used to detect
creased incubation time, increased surface area, and reduced E. coli O157: H7 in milk samples. Different concentrations of
total assay time. The LOD was found to be 20 pg/mL, and the anti-E. coli O157: H7 monoclonal antibodies (mAb) solution and
total assay time was 20 min (Urusov et al. 2014). Nanozymes Pd-Pt NPs were tested at varying pH levels. Out of this, pH 7.5,
can be mainly used as signal tags in ELISA for improved anti-E. coli O157: H7 mAb and Pd-Pt NP concentrations of 3.8
reproducibility as they do not lose activity, unlike convention- μg/mL and 20 μg/mL, respectively, were optimized based on the
al horse radish PODs. With platinum NPs integrated with signal intensities obtained (Han et al. 2018). Pd-Au nanorods as
MIPs and non-imprinted polymers as enzyme labels, Yan nanozymes were found to be more stable over a broad tempera-
and co-workers carried out a comparison study to detect ture range of 4–70 °C, showing high POD like activity from pH 2
Triazophos. SERS fingerprints reported a higher linear range to 6 in the colorimetric detection of malathion, an organophos-
(1–10,000 ng/mL) while it was 5–1000 ng/mL in the colori- phorus insecticide. The ratio of Pd-Au nanorod concentration
metric method; LOD was 1 ng/mL in both the methods. MIPs was also optimized, which otherwise might have suppressed
as enzyme labels exhibited a significantly lower percentage of the intensity of the lateral surface plasmon resonance (LSPR)
cross-reactivity compared to NIPs (Yan et al. 2019). due to the aggregation and growth of those nanorods (Singh
In the case of LFIA, the concentration of NPs has a significant et al. 2017). It is also reported that mercaptopropionic acid can
role in the signaling mechanism. When a substrate is added onto inhibit the activity of Ag/Pt NCs; however, if incubated along
the test line, the visual signal is enhanced on either the test line or with Cu2+ ions, these phenomena weaken, leading to the cataly-
control line based on the analyte’s quantitative presence to be sis of TMB quantitatively in the presence of H2O2. This, in turn,
detected. In a recent study, a cost-effective fluorescent lateral thereby can be used to detect metal concentrations colorimetri-
flow immunoassay (FLFIA) was reported for detection of cally in an economical way (Wu et al. 2017a, b).
E. coli O157: H7 in beef and river water based on the non- Crystal structures and particle size-related characteristics
radioactive energy transfer between quantum dots and graphene also have a key role in determining the catalytic efficiencies
oxide. Here, the ratio of photoluminescence of FLFIA strips of nanozymes (Bahreini et al. 2018). Hence, NPs must be
before and after the addition of the analyte was calculated and characterized before conducting biosensing assays. Among
used to estimate bacterial load present in the test samples. The Fe-C3, Fe-N3/C, Fe-N4/C, and Fe-N5/C structures tested for
LOD was found to be 178 and 133 CFU/mL in beef and water oxidase mimicking efficiency, O2 was more adsorbed to Fe-
Food Anal. Methods

N3/C through side-on configuration, thereby exhibiting higher maintain healthy trade practices. In recent decades, boosted by
OXD activity (Wang et al. 2019). In a study, the effect of the rapid advancements in nanotechnology, nanozymes have
strain on nanozyme activity was reported. Pd octahedral and exhibited immense promise to food analytical techniques.
icosahedral structures possessing POD-like activity were ap- Therefore, in this section, the outlook of the latest developments
plied with tensile and compressive strain, among which Pd in the detection of food contaminants is systematically discussed.
icosahedron structure exhibited higher catalytic efficiency
(2-fold) due to more amplification of surface strain field when Detection of Food Toxins
tensile strain is applied (Xi et al. 2019).
Activity modulation is another influencing factor, and this Toxins are produced by plants and microbes to protect them-
corresponds to various properties of NPs that can be tailored to selves from unsuitable conditions. These cause harmful impacts
render them active, followed by catalysis in either of the above like nerve poisoning, loss of fluids from the body, and even death
two discussed mechanisms. For example, Fe3O4, when modified if consumed in significant amounts by humans. Cyanobacterial
with histidine residues, showed a tenfold increase in the apparent toxins, algal toxins, and mycotoxins such as ochratoxin and
affinity (KM) for H2O2 and a twentyfold increase in catalytic fumonisins are some of the common toxins in foods.
efficiency (kcat/KM) (Fan et al. 2017). The effect on catalytic Therefore, it is necessary to eliminate or reduce the food toxin
activity due to modification in the hydrophobicity of nanozyme levels according to international food safety and regulatory bod-
ligands using methyl, benzyl, and tolyl groups was also studied. ies’ specifications. Hence, diversified analytical techniques are
Among these, tolyl ligands modified nanozyme showed higher used for this purpose, out of which nanozymes are of recent
affinity (KM = 9.8 μM) towards the substrate by exhibiting hy- origin with great impact. For the detection of ochratoxin A
drophobic surface functionality (Cao-milán et al. 2017). (OTA), Tian and co-workers reported a cascade colorimetric
aptasensor assay in which OTA aptamer was immobilized along
with alkaline phosphatase streptavidin (SA-ALP) and DNase
Applications of Nanozymes in Food Safety using a biotin-streptavidin reaction. SA-ALP reduced ascorbic
and Quality Evaluation acid-2-phosphate to ascorbic acid (AA), supporting the reaction
between MnO2, TMB, and OTA. LOD was found to be 0.069
Owing to the high vulnerability and less stability of the natural nM (Tian et al. 2019). Abrin is a protein compound found in
enzymes to the harsh environmental conditions, the artificial Abrus precatorius which if ingested causes inhibition in protein
enzyme mimics emerged as promising alternatives with robust synthesis and eventually cell death. A colorimetric aptamer-
features. However, artificial enzymes lack reproducibility, based sensor equipped with GNPs was employed to detect abrin
consume time, and demand expertise, apart from providing and it was found that LOD (0.05 nM) and detection time (1 h)
inaccurate results. Among the various types of artificial differed significantly when compared to various other traditional
enzyme-like molecules, catalytic nanomaterials (nanozymes) methods like ELISA (7.8 ng m/L, 15 h) (Hu et al. 2015).
have been accepted as the next-generation enzymes and are Figure 5a and d explain the nanozyme-linked immunoassays in
projected to be extensively investigated for their nanoscale the detection of AFB1 and OTA, respectively. In another study,
properties (Wang and Gunasekaran 2020). However, manganese cation substituted cobalt oxide (MnCo2O4) submi-
nanozyme-equipped biosensing systems or immunoassays cron spheres were bound to anti-OTA aptamer to imitate oxi-
with low LOD can be a potential alternative for several dases and detect ochratoxin in maize samples. This nanozyme
existing procedures to detect contaminants. Figure 4 briefly possessed a 50-fold higher affinity towards OTA than the natural
explains the typical flow of the steps involved in the utilization enzyme, HRP. An increase in OTA concentration resulted in
of nanozymes in food safety and quality monitoring, right increased oxidation of TMB, thus giving color change at 652
from their synthesis to application in the detection of food nm. LOD was found to be 0.08 ng/mL (Huang et al. 2018).
contaminants. Nanozymes synthesized from nanoparticles Table 2 lists some other studies reported in the detection of food
using various methods will be characterized using advanced toxins using different nanozymes.
techniques followed by testing for their activity under differ-
ent influencing factors. Then, these catalytically active mate- Detection of Foodborne Pathogens
rials will be employed to evaluate food safety either by
immunosensing or biosensing, as explained in the figure. Coliforms, Salmonella, Bacillus, etc., are the common pathogens
Contaminants, if present above the permissible limits in foods, that invade foods leading to various physical, chemical, and bi-
can lead to serious health concerns. Genetically modified foods ological changes that are undesirable. Salmonellosis, cholera,
and high-risk foods like milk, meat, and several other commod- viral infections, gastroenteritis, listeriosis, Staphylococcal poison-
ities should be monitored consistently for quality and safety. The ing, and other ill effects to humans are reported to be conse-
maximum residual limit in case of pesticides and antibiotics, and quences of microbial contamination (Majumdar et al. 2018).
permissible levels of microbes and toxins are to strictly comply to Microbiological tests, polymerase chain reaction, and other
Food Anal. Methods

Fig. 4 Steps involved in a typical application of NPs as enzyme mimetics in biosensing and immunoassays

well-established techniques are effective in quantifying the mi- change, which can be detected using an ultrasensitive electro-
crobes but consume enormous time, materials, and effort. Hence, chemical method that utilizes a disposable carbon screen-
the nanocatalysts or their combination with ELISA-like tech- printed electrode (Das et al. 2019). This group also studied the
niques can be a better alternative. Fluorescent AuNCs synthe- detection of E. coli with the above-explained principle and
sized and functionalized under UV radiation exhibited established a LOD of 10 CFU/mL while it was 60 CFU/mL in
peroxidase-like activity in screening S. aureus, and its the previous study (Das et al. 2020).
Staphylococcal enterotoxin B. Bacteria like B. subtilis and Cascade reactions involving loop-mediated isothermal ampli-
E. coli were chosen for validating the selectivity of the above- fication for gene recognition and treatment with propidium
reported sensor, and LOD was found to be 1 × 102 CFU/mL (Xie monoazide for detecting viable cells, followed by
et al. 2019). Das and co-workers reported the application of immunochromatographic test functionalized with Fe3O4 MNPs,
GNPs for the detection of Pseudomonas aeruginosa. In the ab- were reported for detection of Enterobacter sakazaki (Zhang
sence of a pathogen, Pseudomonas aeruginosa–specific et al. 2017a). Nano-iron sulfide (nFeS) obtained from
aptamers (F23) bind to GNPs, thereby inhibiting the POD-like organosulfur compound present in garlic was proved to kill bac-
activity. In contrast, when target pathogens are present in the teria and prevent biofilm formation by releasing polysulfanes.
medium, the aptamer binds to the pathogen, allowing the These nFeS get oxidized in the presence of H2O2, which is no-
GNPs to catalyze the reaction. This results in a colorimetric ticed by a color change and structure vibration (Liu 2019).
Food Anal. Methods

Fig. 5 Schematic illustration of the (a) nanozyme and aptamer-based luminol. If quenched CL intensity is used as the reference signal, a novel
immunosorbent assay (NAISA) for AFB1 detection. Mesoporous SiO2/ CL “turn-on” concept is formed. Copyright (2012), with permission from
Au-Pt was prepared to act as signal labels exhibiting high catalase-like ACS Publications (Guan et al. 2012). (c) AuNZ-PAD colorimetric sens-
activity, aptamer was adopted to specifically recognize with AFB1, and ing mechanism for Hg2+ ions (Han et al. 2017). As Hg2+ ions are intro-
MNP facilitated to realize magnetic separation. Copyright (2020), with duced onto the Au nanozyme-PAD, the TMB–H2O2 catalytic reaction is
permission from Elsevier (Wu et al. 2020). (b) Chemiluminescence (CL) enhanced by the formation of Au–Hg amalgam, resulting in blue staining
switching at the surface of Fe3O4 NPs in the detection of EP. Dissolved of the paper chip. (d) PBNP-Induced signal amplification on an LFIA
oxygen is converted into superoxide anions at the surface of Fe3O4 nano- strip for OTA detection. (A) Synthesis of PBNP-Ab2 followed by assem-
particles, then the resultant superoxide anions are scavenged by ethanol; blage of the lateral flow strip. (B) Migration of PBNP-Ab2-analyte driven
hence, no light emission is observed after adding luminol. Alternatively, by capillary force to the test line on nitrocellulose membrane. (C)
pesticide EP molecules are added into the Fe3O4 colloidal solution, and Capturing of PBNP-Ab2-analyte complexes by Ab1 on test line and the
then they bind onto Fe3O4 nanoparticles through the coordinative reaction excess PBNP-Ab2 will migrate to the adsorbent pad. Copyright (2020),
with surface Fe2+ ions. The bound EP molecules inhibit the scavenging of with permission from Elsevier (Tian et al. 2020)
superoxide anions so that a strong CL emission is seen after adding

Table 3 lists various other studies reported in the detection of Monomethylarsonic acid is an intermediate product of arsenic
foodborne pathogens using different nanozymes. that is not absorbed by humans leading to arsenic-induced carci-
nogenesis. When reacted with cysteine-rich protein, cadmium
Detection of Heavy Metals causes hepatotoxicity, followed by nephrotoxicity and replace-
ment of Zn, thereby limiting its free radical scavenging activity
Plumbism and minimata are well-known diseases caused by the (Jaishankar et al. 2014). Hence, monitoring and controlling these
release of heavy metals in potable water and food supply chain. elements in water and various food sources have become a key
Heavy metals such as mercury, lead, arsenic, and cadmium when issue. Figure 5c explains the schematic flow of mercury ion
ingested even in trace amounts may cause dreadful impacts. detection using gold nanozymes.
Food Anal. Methods

Table 2 Applications of nanozymes in food toxin detection

2 Copyright (2018) with permission from Elsevier3 Copyright (2017) with permission from ACS Publications4 Copyright (2021) with permission from
Elsevier

Huang and team elucidated the use of non-noble metal mo- chitosan (CS-MoSe2) NS for detecting mercury (II). Mercury
lybdenum (IV) selenide nanosheets (NS) functionalized with enters the food chain through any means would behave as a

Table 3 Applications of nanozymes in foodborne pathogen detection

Pathogens Nanozyme used Mechanism/ Assay Transduction Detection time Linear range LOD (CFU/mL) Reference
methodology (CFU/mL)

Salmonella POD mimics Colorimetric 20 min 11 -1.10 ×105 11 Wu et al.


enterica ZnFe2O4-reduced (2017)
graphene oxide
nanostructures

Listeria Wang et al.


monocytogenes LFIA Colorimetric 10 min - 3.7 × 106 (2017)
AuNPs

E. coli NLISA Fluorometric - 1.7×101 - 0.06 Wei et al.


1.7×107 (2016)
Cu3(PO4)2
nanocomposites

Francisella 43.4
tularensis

Yersinia pestis LFIA Optical 15 min - 45.8 Wang et al.


(2018b)
AuNPs
Bacillus 357
anthracis

Staphylococcus Co3O4 magnetic Magnetophoretic Colorimetric - 10-10,000 8 Liu et al.


aureus nanozyme chromatography (2020a)
1 Copyright (2017) with permission from Elsevier 3 Copyright (2016) with permission from ACS Publications
Food Anal. Methods

neurotoxic, upon ingestion. Hence, this strategy was researched Detection of Pesticides
in which Hg(II) was reduced on CS-MoSe2 surface, and TMB
was oxidized, followed by a color change in the solution. About 1.8 billion of the population engaged in agriculture use
Detection limits were found to be more when a smartphone pesticides to protect food and commercial products. It was also
(8.5 nM) was used as a tool for on-site detection than in the estimated that around 25 million agricultural workers experience
colorimetric method (3.5 nM) (Huang et al. 2019c). Graphene accidental pesticide poisonings each year (Carvalho 2017).
oxide nanozyme–modified screen-printed electrode plated with Carbamates, organochlorines, fumigants, etc., are different clas-
bismuth film was able to aid in detection of heavy metals like ses of pesticides that interfere with the human body’s normal
cadmium and lead, due to its high electrical conductivity and functioning, resulting in malfunctioning of the kidneys, nervous
LOD were found to be 0.5 μg/L and 0.8 μg/L for cadmium system, and respiratory system. Hence, the rapid and real-time
and lead ions respectively (Ping et al. 2014). Seventeen kinds monitoring of these contaminants is of paramount importance. A
of tea samples were discriminated based on 12 metal ions present study using gold nanorods exhibited superior POD-like activity
(Sn2+, Fe3+, Cu2+, Ag+, Pb2+, Mg2+, Mn2+, Ca2+, Al3+, Cr2+, Ni+, than HRP and detected malathion to a LOD of 1.78 μg/mL
Ba2+) using a sensor array with three types of laccase-mimicking (Biswas et al. 2016). On the other hand, Singh and co-workers
nanozymes (Cu-ATP, Cu-ADP, and Cu-AMP). Among various combined Pd with Au nanozyme to detect malathion. This bime-
pH tested, pH 6 at 50 μM concentration exhibited good accuracy tallic nanozyme exhibited high POD-like activity from pH 2 to 6
(100%). The linear discriminate analysis allowed a good amount with a LOD of 60 ng/mL, confirming the advantage of Pd’s
of separation of ions at 0.01 μM (Li et al. 2019). Most of the addition to Au (Singh et al. 2017). Polyacrylic acid-coated ceri-
nanozymes detect inorganic forms of heavy metals. However, um oxide NPs (PAA-CeO2), when incubated with organophos-
organic forms of metal ions also significantly affect the environ- phorus pesticides (OPs), TMB and AchE, and thiocholine for-
ment and biological materials (Unnikrishnan et al. 2019). Future mation from acetylcholine, are suppressed due to OPs. This ac-
research should find an alternative approach for investigating the tivity allows nanozymes to carry OXD-like activity with TMB,
organic form of metal ions as a food contaminant. Table 4 lists resulting in visual colorimetric signals followed by convincible
various other studies reported in the detection of heavy metals LODs (Zhang et al. 2016). Figure 5b represents the nanozyme-
using different nanozymes. mediated reactions involved in the detection of pesticide

Table 4 Steps involved in a typical application of NPs as enzyme mimetics in biosensing and immunoassays

Metals Nanozyme Mechanism/ Transduction Detection Linear range LOD Reference


Assay methodology time

Silver (Ag+) POD mimics Colorimetric 6 min 10-2-104 nM 80 pM Gao et al. (2017)

Platinum nanocubes

Mercury (Hg2+) Adsorption Electrochemical - 0.25–1000 ppb 3.24 ppb Maric et al.
(2019)
Pt halloysite nanoclay

Signal 0.13–53.33 0.07 nmol/L Ouyang et al.


Lead (Pb2+) amplification Optical 11 min nmol/L (2018)
AuNPs

Silver (Ag+) POD mimics Optical 50 min 0.5-1000 μM 500 nM Tian et al. (2021)
Au-Pt nanozyme

10–200 μg/L & 3.8 μg/L & 2.4


Hg(II), Cd(II) MnO3 NPs OXD mimics Colorimetric - 5–100 μg/L μg/L Wang et al.
(2020a)

1 Copyright (2017) with permission from Elsevier


2 Copyright (2018) with permission from John and wiley sons
4 Copyright (2021) with permission from Elsevier
Food Anal. Methods

Table 5 Applications of nanozymes in pesticide detection

Pesticides Nanozyme used Mechanism/ Assay Transduction Detection time Linear range LOD Reference
methodology

Atrazine POD mimics Colorimetric 40 min 2 - 20 μg/L 2.98 μg/L Boruah and Das
(2020)

Fe3O4-TiO2/rGO

Triazophos Bio-barcode - 2.5 × 10-2 - 40.0 1.96*10-2 ng/mL Du et al. (2018)


amplification - ng/mL
AuNPs competitive
immunoassay

Nanozyme based
Parathion electrochemical Electrochemical - 0.1–30 μM 0.024 μM Khairy et al.
sensing (2018)
NioNPs

50 min
Methyl POD mimics Colorimetric 0.1–50 pM 14 fM Liang and Han
paraoxon (2020)
GeO2

Chlorpyrifos Ag3PO4 NPs OXD mimics Colorimetric 3 min - 9.97 ppm Kushwaha et al.
(2020)

1 Copyright (2020) with permission from Elsevier


2 Copyright (2018) with permission from Elsevier
3 Copyright (2018) with permission from Elsevier
4 Copyright (2020) with permission from John and Wiley Sons

Ethoprophos (EP). Nanoceria was employed as a catalyst in dual- colorimetric output produced, and visible change was ob-
mode detection of OPs, where the nanozyme catalyzes the con- served above the concentration of 11 ng/mL (Yu et al.
version of OPs to p-nitrophenol producing a bright yellow color 2017). Later, in another study on the detection of amantadine
that was directly proportional to the concentration of OPs (Wei residues, Yu and co-workers developed a highly sensitive
et al. 2019). Table 5 lists various other studies reported in the NLISA method that includes three steps: conventional indirect
detection of pesticides using different nanozymes. competitive enzyme-linked immunosorbent assay, Fenton re-
action regulated oxidation of cysteine, and gold nanoparticle
Detection of Antibiotics and Drug Residues aggregation. This method aided in the detection of amantadine
residues present in poultry meat at much lower levels (0.095
Antibiotics and drugs are generally administered to food- ng/mL) (Yu et al. 2018). Chitosan-modified photoresponsive
producing animals to increase disease resistance, and improve AgI/TiO2 heterojunction nanozymes were used as signal tags
physiological function and growth. However, when these an- in a colorimetric immunoassay, and the attempt was found
imals are converted to meat, residues of the drugs accumulate reliable when applied for food samples with no significant
and cause severe ill effects on consumption. Antimicrobial differences in detection limits (Chang et al. 2017). A compar-
drug resistance, carcinogenicity, teratogenicity, disruption of ison study on detection of streptomycin was carried out
intestinal normal flora, and hypersensitivity are some of the among conventional LFIA using AuNPs, a novel LFIA based
adverse effects on human health reported so far (Bamidele on Au-Pt as a visual tag, and enhanced LFIA with Au-Pt as
Falowo and Festus Akimoladun 2020). Hence, quality testing POD mimics and 3-amino-9-ethyl-carbazole as chromogenic
should ensure that the drug and antibiotic residues present are substrate. This research reported the latter as the most feasible
at permissible levels. Nanozymes can be an efficient way of method due to obtaining lower detection limits even upon the
determining and quantifying these substances within less time reduction of nanozyme concentration by fivefold, thereby
and with more accuracy. Yu and co-workers applied proving it as an effective tool for food safety (Wei et al.
nanozyme-linked immunosorbent assay (NLISA) method to 2020). Kanamycin, another antibiotic, was detected using
detect cloxacillin and reported glucose oxidase-controlled platinum nanozyme, a POD mimic that catalyzed gas genera-
growth of AuNPs as the principle for signal amplification. tion reaction onpolyanaline nanowires functionalized with re-
The presence of cloxacillin is inversely related to the duced graphene oxide frameworks (Zeng et al. 2018). Hybrid
Food Anal. Methods

approaches such as integrating computer skills with limit of 0.27 ppm and 67-fold better than undoped CuO was
nanozyme-based sensing for enhanced detection and quantifi- reported. This nanocatalyst also determined the quenching
cation of drug residues and antibiotics in food products are property of antioxidants, thereby quantifying tartaric acid, tan-
potential future innovations in food quality control. nic acid, and AA and revealing the antioxidants’
concentration-dependent scavenging effect (Nagvenkar and
Detection of Food Adulterants Gedanken 2016). Pt-Ru nanozymes were combined with al-
cohol oxidase and methylamine oxidase to form bioelectrodes
The growing awareness of the importance of food authenticity in amperometric biosensors. Replacement of natural peroxi-
and traceability in the food supply network emphasizes adopting dases with bimetallic Pt-Ru nanozymes resulted in enhanced
novel interdisciplinary techniques with proven accuracy. POD-like activity and detection of ethanol and methylamine
Although various existing analytical methods based on physio- in wine and kefir samples (Stasyuk et al. 2019). IrO 2
chemical, chromatographic, spectroscopic, and molecular as- nanozymes synthesized by pulsed laser ablation and dispersed
pects are in practice for food adulteration analysis, nanozyme- on GO formed nanocomposites that mimic peroxidases. This
led modern detection tools are increasingly popular. The food nanocomposite was used to detect the AA in food samples
adulteration is carried out both intentionally and unintentionally, under optimized pH, temperature, and buffer concentrations,
affecting the quality of the final food material (Johnson 2014). and the sensor’s sensitivity was 324 nM (Sun et al. 2020). Pd
Wu and the team reported a novel immunosensing method using nanozymes stabilized with carboxylated chitosan (CC-
AgNPs to detect melamine, a common adulterant in milk prod- PdNPs) were masked by iodine ions added, thereby inhibiting
ucts. In this nano approach, anti-melamine antibodies were its POD-like activity. This mechanism was developed to de-
immobilized on the surface of colloidal AgNPs and were tested tect iodine ions using colorimetric assay, and LOD was found
for cross-reactivity and stability. Interestingly, the developed to be 0.19 nM (He et al. 2019). A group of researchers suc-
immunosensor exhibited no cross-reactivity and excellent stor- cessfully developed GNP-doped covalent organic framework
age stability for almost 1 year at room temperature. Furthermore, nanozymes mimicking the nitroreductase activity. This en-
this on-site detection strip was employed to detect melamine in zyme mimic catalyzed 4-nitrophenol to 4-amino thiophenol
liquid milk and animal feed samples and found reproducible with through surface-enhanced Raman scattering technology
a LOD of 0.75 and 0.875 ppm, respectively (Wu et al. 2019d). coupled with ELISA. This smartphone-based biosensor can
Sudan I, an intentional food adulterant in various red-colored detect allergenic proteins such as β-lactoglobulins in the milk
food samples, was detected using lanthanum-doped Co3O4 samples, as shown in Fig. 6. The LOD was observed to be
nanocube–based screen-printed electrochemical sensor. In this 0.01 ng/mL (Su et al. 2019). The discovery of nanozymes
study, the highest oxidation currents in response to the addition with exciting features has unraveled impressive connections
of La3+ were recorded at 480 mV, followed by the oxidation of between the nanomaterials and the food safety system.
Sudan I. The concentration of Sudan I present is linearly related
to the current produced at La3+-doped Co3O4 screen-printed elec-
trode, thus producing linear response ranges between 0.3 and
300.0 μM (Mahmoudi-Moghaddam et al. 2019). To detect ni- Challenges and Future Research Directions
trites, present in sausage samples, graphene oxide–modified
histidine-capped AuNCs (His@AuNCs/rGO) that exhibit The privilege to tailor the nanozymes at the nanoscale level for
OXD-like activity were used. This nanocomposite oxidizes ni- effectively mediating the biological events in food safety is
trite present in the sample, thereby inhibiting the oxidation of considered a promising feature to improve food contamination
TMB quantitatively and producing color change in inverse rela- supervision. The monitoring and detection of exogenous con-
tion to the concentration of nitrites (Liu et al. 2019c). Table 6 taminants and endogenous ingredients are becoming reliable
represents the list of nanozymes used to detect antibiotics/ and rapid through the adaptation of nanozyme-based food
adulterants used in food systems. analysis. The integration of a multifunctional food safety de-
tection platform and the ability to customize the sensing strat-
Detection of Biological Compounds egies imply their superior competitiveness with other latest
developments.
Sugars, proteins, organic acids, and other foods in foods have
vital roles like antioxidant capacity and preservative effect. 1. Although the past few decades have acknowledged the
Quantifying these biological compounds accurately at less exciting features of nanozymes like stability, efficiency,
cost and time is essential to monitor their activity levels over and recyclability, they are considered in the latent phase in
the shelf-life period. A superior POD-like nanozyme, i.e., Zn- food sensing applications. Strong insight into this research
doped CuO (Cu0.89Zn0.11O), detects glucose based on the glu- field may resolve the limitations associated with these
cose oxidase enzyme mechanism, with the lowest detection enzyme mimics and could raise new opportunities
Food Anal. Methods

Table 6 Applications of nanozymes in antibiotic/adulterant detection

1 Copyright (2018) with permission from Elsevier


3 Copyright (2020) with permission from Elsevier
4 Copyright (2019) with permission from Elsevier

(Zhou et al. 2017). Enormous efforts are urgently required 3. Locating the active site precisely and investigating the origin
to address and advance the following trends. of catalytic activity are a promising research challenge due to
2. Types of nanozymes, specificity and selectivity, rational the heterogenous elemental structure and complex
designing, nanotoxicity, and other aspects of nanozymes nanoarchitecture of the nanozymes. This drawback can be
are to be elucidated yet so that their applicability can be overcome through either bioconjugation or nanozyme im-
enhanced widely (Singh 2019). In another study, mobilization (Liu and Liu 2017). Additionally, the lower
nitrogen-doped carbon nanozymes were also reported to densities of active sites of nanozymes lower the turnover
determine the antioxidant capacity of commercial bever- number of enzymes (Lin et al. 2014). Therefore, optimiza-
ages and other juice samples which can be a potential tion of size, structure, and catalytic sites of the nanozymes
direction of food research in the future (Lou et al. 2019). should be evaluated in future food safety–based applications.

Fig. 6 Schematic illustration of


the gold NPs–doped covalent or-
ganic frameworks nanozyme–
based surface-enhanced Raman
scattering immunosorbent to de-
tect β-lactoglobulins in milk
samples (modified from Su and
co-workers) (Su et al. 2019)
Food Anal. Methods

4. Focus is being shifted to exploring the co-factors of should be done to solve these nanozyme-based issues and
nanozymes that enhance the enzymatic activity as in explore more applications in food safety and quality systems.
natural enzymes (Zhang et al. 2020a). Recently,
bioorthogonal nanozymes with improved specificity
and catalytic activity are emerging in this field (Cao- Conclusion and Outlook
milán et al. 2017). The reactivity of nanozymes with
interfering substances in the food matrix must be con- Efficient and robust detection strategies of food contaminants
trolled to avoid non-specificity and non-selectivity. An are of enormous importance in guarding food safety. The re-
example of inhibition of natural enzyme activity is cent innovation of nanozymes has provided many potential
discussed here. Goretta and co-workers studied the ef- opportunities in addressing some of the emerging challenges
fect of food components on angiotensin-converting en- in food quality control. The major limitations like the time-
zyme (ACE) activity. When assayed for the ACE ac- consuming process of microbiological and/or analytical pro-
tivity in flavanol-rich foods, they observed strong in- cedures in food contaminant detection and lack of reproduc-
hibition towards the enzyme; activity inhibition was ibility are resolved with the advent of the nanozyme concept.
directly proportional to the level of flavanols present In this review, the food safety–based nanozyme applications
in the food sample (Actis-Goretta et al. 2006). Hence, and their mechanisms in the detection of food analytes such as
nanozymes as mimicking materials for natural en- toxins, foodborne pathogens, microbial toxins, and heavy
zymes may also be associated with the above condi- metals are highlighted. Owing to the complex food matrix
tions. To avoid such limitations, Zhang and co-workers and the trace level of food contaminants, applying nanozymes
reported an encapsulation-based approach was used to in food safety brings many opportunities and challenges.
protect the active sites of bioorthogonal AuNPs in un- Novel multimode nanozymes should be developed through
favorable environments that may otherwise degrade interdisciplinary tools such as surface plasma resonance,
the catalytic activity of nanozymes (Zhang et al. smartphones, electrochemiluminescence, and ELISA to over-
2020b). Further research in this aspect can be an excit- come the current limitations. Evidenced by the increasing re-
ing trend, thereby revealing more possible areas in the search and publications, these nanocatalyst molecules if opti-
field of nanozymes. mized promptly can make enormous advancements in food
5. Most of the current experiments with nanozymes rely on safety from farm to fork and would be a promising tool in
the colorimetric principle, which has its limitations in de- evading future outbursts of foodborne diseases.
tection and accuracy. Therefore, combinatory signaling
assay approaches such as the lateral flow strip utilization
approaches should be investigated to ensure food safety. Abbreviations ABTS, 2,2′-azino-bis (3-ethylbenzothiazoline-6-sulfonic
6. Designing a portable device for on-site monitoring or de- acid; AFB1, Aflatoxin B1; AR, Amplifu red; ACE, Angiotensin-
tection of food poison or allergen using nanozymes has converting enzyme; AA, Ascorbic acid; CDs, Carbon dots; CAT,
Catalase; CUS, Coordinatively unsaturated sites; DMF, Dimethyl form-
excellent potential in maintaining the future food safety amide; ELISA, Enzyme-linked immunosorbent assay; EP, Ethoprophos;
system. The integration of advanced sensors with FLFIA, Fluorescent lateral flow immunoassay; GNPs, Gold nanoparti-
smartphone-like portable tools for in-field analysis is an cles; GDs, Graphene dots; HRP, Horse radish peroxidase; LFIA, Lateral
emerging field of food contaminant detection (Su et al. flow immunoassay; LSPR, Lateral surface plasmon resonance; LOD,
Limit of detection; MNPs, Magnetic nanoparticles; MOFs, Metal–organic
2019). Likewise, the development of low-cost test strips frameworks; MWCNTs, Multi-walled carbon nanotubes; NPs,
with a nanozyme-based mechanism for the detection of Nanoparticles; NS, Nanosheets; NWs, Nanowires; NLISA, Nanozyme-
foodborne pathogens and toxins will draw increasing inter- linked immunosorbent assay; OTA, Ochratoxin A; OPD, o-
est soon. Phenylenediamine; OPs, Organophosphorus pesticides; OXD, Oxidase;
POD, Peroxidase; PLA, Polylactic acid; rGO, Reduced graphene oxide;
SWCNTs, Single-walled carbon nanotubes; SOD, Super oxide dismutase;
Nanozymes are also being incorporated in microfluidic de- TMB, 3,3′,5,5′-Tetramethylbenzidine
vices in biomedicine, which can also be extended to food
sensing applications (Ko et al. 2019). The inclusion of com- Data Availability Not applicable
putational research in applications of nanozymes may also
Code Availability Not applicable
help in the better unveiling of various aspects of these novel
catalytic molecules. However, before addressing these chal-
lenges in the future, researchers should pay more attention to Declarations
exploit the nanozyme itself for its biosafety and bioavailabil-
Ethical Approval This article does not contain any studies with human
ity. Investigations and publications on nanozyme properties, participants or animals performed by any of the authors.
optimization, and its diverse applications are minimal com-
pared to the traditional enzymes. Therefore, more research Informed Consent Not applicable
Food Anal. Methods

Conflict of Interest The authors declare no conflict of interest. Das R, Chaterjee B, Kapil A, Sharma TK (2020) Aptamer-nanozyme
mediated sensing platform for the rapid detection of Escherichia coli
in fruit juice. Sens Bio-Sens Res 27:100313. https://doi.org/10.
1016/j.sbsr.2019.100313
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