Advancement of metal oxide nanomaterials on agri-food fronts

1 Advancement of metal oxide nanomaterials on agri-food fronts Georges Dubourga, Zoran Pavlovića, Branimir Bajaca, Manil Kukkara, Nina Finčurb, Zorica Novakovića, Marko Radovića a University of Novi Sad, Center for Sensor Technologies, Biosense Institute, Dr Zorana Đinđića 1,21000 Novi Sad, Serbia b University of Novi Sad Faculty of Sciences, Department of Chemistry, Biochemistry and Environmental Protection, Trg Dositeja Obradovića 3, 21000 Novi Sad, Serbia Keywords: Metal oxide nanomaterials, Agriculture, Food, Environment Highlights: - Metal oxide nanomaterials are applied in food control monitoring, food packaging and agricultural production. - Metal oxide nanomaterials are applied in agricultural environments for wastewater treatment and soil remediation. - The risks associated with deploying MOx nanomaterials in the agri-food sector are not fully addressed. Graphical abstract 2 Abstract The application of metal oxide nanomaterials (MOx NMs) in the agrifood industry offers innovative solutions that can facilitate a paradigm shift in a sector that is currently facing challenges in meeting the growing requirements for food production, while safeguarding the environment from the impacts of current agriculture practices. This review comprehensively illustrates recent advancements and applications of MOx for sustainable practices in the food and agricultural industries and environmental preservation. Relevant published data point out that MOx NMs can be tailored for specific properties, enabling advanced design concepts with improved features for various applications in the agrifood industry. Applications include nano-agrochemical 3 formulation, control of food quality through nanosensors, and smart food packaging. Furthermore, recent research suggests MOx's vital role in addressing environmental challenges by removing toxic elements from contaminated soil and water. This mitigates the environmental effects of widespread agrichemical use and creates a more favorable environment for plant growth. The review also discusses potential barriers, particularly regarding MOx toxicity and risk evaluation. Fundamental concerns about possible adverse effects on human health and the environment must be addressed to establish an appropriate regulatory framework for nano metal oxide-based food and agricultural products. 1. Introduction Nanotechnology is a key enabling technology that involves manipulating NMs at the atomic or molecular level. Their small size provides them with unique advantages compared to larger-scale counterparts, including remarkable physical, chemical, and optical properties with a large surfaceto-volume ratio. Nanoparticles (NPs), which are just a few nanometers in size, can be found in a wide range of consumer products like deodorants, toothpastes, and paints. They have the potential to transform various industries such as medicine, aerospace, and energy production. Today, NMs are being employed in the "agri-food sector" as a means to tackle the urgent challenges of increasing crop productivity to meet the ever-growing demands of the global population, while simultaneously reducing the environmental impact caused by current agricultural practices (Dhankhar and Kumar, 2023). In the last decade, numerous reviews have outlined the beneficial effects of NMs on the growth, yield, and protection of agricultural crops (Jafir et al., 2023, Verma et al., 2018; Shang et al., 2019; Singh et al., 2022), as well as their potential applications for food quality control and preservation (Torres-Giner et al., 2020; Shafiq et al., 2020; Ghosh et al., 2019; Jagtiani, 2022). Among NM, metal-oxide (MOx) nanostructures offer many advantageous features. 4 They can take on various structural geometries, exhibit metallic, semiconductor, or insulator characteristics, and possess unique physicochemical and photocatalytic properties (Song et al., 2015). These MOx-nanostructures, whose properties can be adjusted to fulfill specific objectives, offer viable solutions to address the challenges currently faced in various aspects of the agrifood industry such as crop cultivation, distribution, and food quality control. For instance, the use of MOx-based nanosensors, including electrochemical and biosensors, has become a prominent research method for sensing applications (George et al., 2018; Liu and Liu, 2019; Krishna et al., 2022). These advanced nanosensors can detect contaminants like food toxins, monitor flavor production, and identify pathogens, allowing for remote monitoring of food quality and safety with heightened effectiveness Galstyan et al., 2018, Ungureanu et al., 2022). Besides being used for monitoring and ensuring the quality of food, MOx-NMs possess the capacity to enhance plant growth and protect plants from diseases. The unique characteristics of MOx, including their small dimensions, large surface area, enhanced solubility, and antimicrobial properties, make them highly valuable in the development of fertilizers and pesticides (Hyder et al., 2023). Additionally, MOx materials can positively contribute to the process of soil remediation by efficiently purifying polluted soils from hazardous elements (Ali et al., 2023). This results in providing a fertile ground for agricultural practices. Furthermore, their excellent photocatalytic characteristics and photochemical stability can support the provision of clean and abundant freshwater, which is essential for agriculture (Singh, et al., 2023 ). This, in turn, can help reduce groundwater pollution caused by the use of other agricultural chemicals like pesticides or fertilizers (Pattnaik et al., 2023). However, despite the significant potential of MOx-based NMs for sustainable and viable agriculture with a reduced environmental impact, they remain controversial due to their potential 5 hazards to ecosystems and human health. There is a lack of understanding of the effects of MOxNMs on the environment and human health, which limits the development of regulations and legislation needed for the smooth transition of NM-based technologies into marketable products for the agri-food industry. This review article provides industry stakeholders and the research community with an overview of the latest advancements achieved in MOx-based NMs on the agri-food front. The article focuses on two distinct aspects: 1. the main front line, which highlights the positive implications of MOxNMs on several important sectors of the agri-food chain, such as crop productivity, food supply and environment, and 2. the back line, which defines the actual market barriers. In this section, we discuss the lack of knowledge regarding the impact of NMs on human and environmental health and how this affects the regulatory framework. 2. MOx NMs for food control and preservation 6 Figure 1. Schematic illustration of the role of MOx in the quality food control and monitoring process The quality and safety of food must be continuously monitored and controlled from processing and storage until the products reach the consumer's hands. This is done in order to protect human health against the risks of food poisoning and to potentially reduce food waste. The process involved in ensuring food safety is complex and encompasses the monitoring of various factors, including freshness, authenticity, toxin levels, presence of pathogenic bacteria, and adulterants, at every stage of the food supply chain. Additionally, efforts are made to develop intelligent food packaging that can protect food and prolong its shelf life. The utilization of MOx NMs can play a significant role in monitoring and preserving food quality throughout the food supply chain. In this section, we explore various types of MOx NMs that are utilized in the development and design of novel electrochemical nanosensors, electronic noses (E-nose), and nanobiosensors for the purpose of monitoring food quality. Additionally, the discussion will highlight the application of MOx NMs in food packaging, specifically their antimicrobial and photocatalytic properties that aid in safeguarding food products from potential contamination as illustrated in Figure 1. 2.1. Electrochemical Biosensors Biosensors represent a wide group of sensors that have been adopted by the food safety market due to their high reliability, speed precision and user-friendly nature. The increase in the demand for sensors in various diversified fields has boosted scientists and engineers to prioritize the development of mobile devices for on-the-go analysis, which are rapid, intuitive and economical as compared to traditional laborious laboratory methods. 7 Key areas of the food safety value chain where biosensors based on NMs have found application include the detection of food borne pathogens, cell metabolites, heavy metal ions, toxins (pesticides, herbicides,), soil fertilizers (potassium (K), phosphorus (P), nitrogen (N)), drugs, flavors, and sweeteners. The most desired ones should be scaled down to a single chip (lab on a chip), for multiple detection purposes (Dkhar et al., 2023). A bioreceptor and a transducer are the two major components of an electrochemical biosensor. The bioreceptor is responsible for the recognition of the target analyte whereas the transducer transforms this recognition event into a quantifiable signal (Naresh and Lee, 2021). An analyte represents any micro or macro biomolecule, ion, heavy metals, toxins, bacteria, viruses etc. Depending on the analyte of interest, bioreceptor (biological recognition element) must be precisely chosen. Bioreceptors most commonly used are the enzymes, antibodies and aptamers as nucleic acid fragments, (Kukkar et.al., 2018, Huang et al., 2021, Podunavac et.al., 2023, Novakovic et.al., 2024). A typical construction of a biosensor with different types of receptors is shown in Figure 2. Figure 2. Schematic illustration of general concept of an electrochemical biosensor based on MOx NMs 8 The type of transducer determines the design of the sensor, and they can be broadly categorized as piezoelectric, optical, mechanical, acoustic, magnetic, and electrochemical, based on the detection principle involved (Hariri et al., 2023). Electrochemical biosensors are the most versatile and highly developed among chemical and biochemical sensors. The electrical signal is generated through the conversion of biochemical processes or electrochemical redox reactions. Enhancements in sensitivity and specificity of electrochemical sensors are achieved through the use of various materials such as noble metal and MOx NPs, carbon-based NMs, transition metal dichalcogenides, nitrides and carbides, ion-selective membranes, and field-effect transistors as signal amplifiers. Functionalized NM-based electrocatalysts can enhance the sensitivity of electrochemical sensors due to their unique electrocatalytic properties and by expanding the active electrochemical surface area where the reaction occurs (Li et al., 2013; Aftab et al., 2023). The electrochemical signals that are given to the electrode and measured as feedback signals, determine the type of sensor, which includes voltammetric, potentiometric, amperometric, conductometric, impedimetric, and coulometric sensors (Saputra, 2023). The advantages of using electrochemical biosensors are very good selectivity and sensitivity, reproducibility, miniature size, small sample volume required, and the possibility of simultaneous detection of more desired elements by lab on a chip design with various sensors (Novakovic et al., 2024). Other desired properties are low limit of detection (LOD), wide range of detection, rapid response, cost-effectiveness, easy to use, disposable, low power consumption, portable, reusable, easily integrable with micro-electronics, self-calibration, and self-cleaning (Grieshaber et al., 2008). Signal and data post-processing play a very important role in obtaining accurate and credible results of detection. 9 There are several generations of electrochemical biosensors developed yet. The first generation of biosensors detects the product of a chemically catalyzed reaction, which causes the electrochemical response at the electrode by redox reaction (e.g., hydrogen peroxide as a byproduct of the enzymatic reaction). The second generation of biosensors introduces specific molecules called 'mediators' (any good redox couple like ferrocene or ferro/ferricyanide) that transfer the charge between the enzyme and the electrode while an enzymatic reaction takes place to generate the electrochemical response (Dede and Altay, 2018). In the third generation of biosensors, the electrochemical response is caused by the reaction itself; the enzyme is placed into an integrated polymer matrix, or redox couples are covalently bound to the enzyme for direct electron transfer to the electrode during the enzymatic reaction (Juska and Pemble, 2020). Nonenzymatic, so-called “fourth generation” of biosensors is based on the electrochemical signal of direct oxidation/reduction of biomolecules of interest on the NM-modified substrate, without any additional biorecognition elements and mediators (Taha et al., 2020). The most studied enzymatic biosensors are glucose sensors, which are important detection devices in the beverage, food quality control, and fermentation manufacturing sectors. These sensors, depending on the type of enzyme used, dehydrogenase (glucose dehydrogenase (GDH)) or oxidize (glucose oxidase, graphene oxide (GOx)) glucose molecules, and provide an electrical response that corresponds to the glucose concentration (Yoo et al., 2010). Enzyme immobilization is one of the crucial steps in developing highly sensitive and stable enzymatic biosensors since it affects the bioactivity of the enzymes. The creation of new NMs opens up possibilities for customizing enzyme characteristics and optimizing immobilization. In electrochemical sensorics, functional nanostructured transition MOx materials are promising in catalytic-based sensorics, due to their stability, excellent catalytic activity, cost-effectiveness, and ease of fabrication. Manganese Oxide 16 beverages, etc. (Ariño et al., 2017). Most of them, when present in higher amounts, are known to be toxic and carcinogenic, and due to that, reliable onsite detection is in high demand. The World Health Organization has classified organophosphorus pesticides (OPPs) as extremely dangerous neurotoxic chemical compounds which are often utilized for the crop’s protection from pests (Bhattu et al., 2021). Thus, due to their intensive use and high toxicity, a high-performance electrochemical sensor for the monitoring of pesticide contamination is urgently needed. Electrochemical detection of toxins by using various MOx NPs and MOx-metal nanocomposites as the electrochemical sensing platform gives promising results in sensitivity, rapidity, high surface area, and high selectivity. A nonenzymatic electrochemical sensor for carbofuran (CBF) and carbaryl (CBR) compound detection based on CoO on rGO was devised by Wang et al., 2014, in which they showed that it is possible to detect both carbamate pesticides simultaneously. The sensor displayed a low LOD of 4.2 μg/L for CBF and 7.5 μg/L for CBR, and a linear relationship is obtained over a wide concentration window of 0.2–70 μM (R =0.9996) for CBF and 0.5–200 μM (R = 0.9995) for CBR. Gao et al., 2019 created a robust and accurate electrochemical sensor for methyl parathion pesticide residues in Chinese cabbage samples using the Au/ zirconium dioxide (ZrO2)/graphene/ glassy carbon electrode (GCE) material. Due to their strong affinity for phosphoric groups, ZrO2 NPs exhibit remarkable selectivity in detecting organophosphorus pesticides (OPs), and the presence of phosphate groups and ZrO2 enhances the adsorption of methyl parathion on the electrode surface. Zirconia or graphene-modified electrodes (Au/ZrO2-graphene/GCE) showed a better electrocatalytic response towards MP oxidation compared to the Au NPs where linear current with the concentrations of MP was in the range of 1-2400 ng /mL, with the LOD of 1 ng/mL. 17 Many research groups have reported productive results about the electrochemical detection of heavy metal ions with various MOx catalytic NMs, doped with other metal ions, or even as a composite NM. One of the most common forms of iron oxide used to detect heavy metals is Fe3O4, but there are only a few reports using iron oxide without any other additional ions, because iron oxide NPs may become non-conductive due to aggregation. Most studies functionalize iron oxide NPs or combine them with other materials, which produce spinel ferrites that can enhance more sensitive detection of heavy metals. Studies done by Zhou et al., 2015 on manganese ferrite (MnFe2O4) to detect different heavy metals showed a good linear response of arsenite (As (III)) concentrations between 10 and 100 ppb, with a LOD was 1.95 ppb and a sensitivity of 0.295 μA/ppb. In a subsequent investigation, glassy carbon electrodes were modified with MnFe2O4 and graphene oxide for improved analytical performance in the detection of metal ions such as copper ions (Cu (II)), lead cation (Pb (II)), mercury cation (Hg (II)), and cadmium cation (Cd (II)), demonstrating LODs of sub-mM concentration in river water analysis (Zhou et al., 2016). Wei et al., 2012 reported linear ranges of 20 to 140 nM for cadmium (Cd) and 1 to 30 nM for lead, with very low sensitivities and limits of detection in the 10-12 M and 10-11 M ranges using magnesium oxide (MgO) nanoflowers modified glassy carbon electrodes. For metal ion detection purposes, many researchers used certain ion-selective membrane cocktails to cover the working electrode to selectively detect the ions of interest. QDs are nano-sized particles with a size of 1 to 10 nm with many exceptional properties owing to their structural differences, due to quantum mechanical phenomena, such as large specific surface areas, excellent electrical properties, abundant active sites, easy functionalization, and good aqueous dispersibility. A range of two-dimensional (2D) QD NMs has been created using materials 18 such as graphene, nitrides, transition MOx and dichalcogenides, Mxenes, and black phosphorus (Zhang et al., 2022a). Much research has been conducted on using various types of QDs with adjustable surface modifications to detect ions, biomolecules, and living cells. With their high affinity for biomolecules, QDs have been widely applied in electrochemical biosensing as electrode modifiers, electron transfer accelerators, and carriers of sensitive elements, for enhancing the selectivity and sensitivity of detecting the desired analyte. Field Effect Transistor (FET) electrochemical sensors hold significant promise for a wide range of detection applications. In FET biosensors, bioreceptors are immobilized on a semiconductor channel or sensing material connecting the source and drain electrodes. The interface of this material plays a critical role in the transduction process of FET sensors. A bias voltage is applied to the semiconductor material, allowing for modulation of its electronic properties, including electrical conductivity, by a third electrode (gate). The captured analytes induce changes in the material's conductance through mechanisms such as electrostatic gating and/or Schottky barrier modulation, resulting in a measurable signal that enables determination of analyte concentration (Sedki et.al.,2021). FET configuration may be back-gated wafer-based with source and drain electrodes, while as a back gate, the bulk wafer could directly function (Pham et al., 2019). Many 2D and threedimensional (3D) NMs may be grown on a wafer of dielectric material (e.g., silicon dioxide (SiO2)) deposited on a conducting substrate (e.g., Si). Another possible FET structure liquid-ion gatebased, with the gate function of the ionic liquid. At the liquid-channel interface a double-layer is created, at which the electric change happens. Back-gate capacitance may be many times smaller in comparison to an ionic-liquid gate capacitance via various substrates (Lieb et al., 2019). 19 MOx, as the most varied types of solids, may be good candidates for the library of 2D materials used for transistor fabrication with high electron mobilities higher than 10 cm2 V−1 s−1, and a large band gap energy range of 2.3–4.9 eV. All those properties guarantee high sensitivity and low signal-to-noise ratio in biosensing applications. MOx have been applied a lot in bio/chemical detection as electrochemical transducers. Some of the most used are tungsten trioxide (WO3), molybdenum trioxide (MoO3), tantalum trioxide (TaO3), and gallium trioxide (Ga2O3) as well as SnO2, ZnO, CuO, and indium trioxide (In2O3) (Sedki et al., 2020). One of the interesting transition MOx, In2O3 was used in many FET biosensors giving good sensitivity. Chen et al., 2017 developed a 2D In2O3-based non-enzymatic FET biosensor for the glucose detection with an extremely low LOD of less than 7 fM, showing the linear response over a broad dynamic range of glucose from 10−11 - 10−5 M. Boronic acid was used as a receptor of glucose molecules. The device's performance was better than that of other non-enzymatic FET sensors for glucose when it used the recognition molecule boronic acid and semiconductor channels made from carbon-based NMs. Some examples of MOx NMs-based biosensors for agrifood applications are presented in Table 1. TABLE 1. Summary of MOx commonly used in biosensors. 20 MOx composite Analyte Detection Technique Linear Range LOD Linear Range (real sample) LOD (real sample) Ref. MnO2/ MWCNT H2O2 Amperometry 5-200 μM & 0.2-1 nM 2 μM - - Hao et al., 2020 SnO2 (QD)/rGO urea Amperometry 1.6×10−14 - 3.9×10−12 M 11.7 μM - - Dutta et al., 2014 Fe3O4-NH2 aflatoxin B1 Cyclic voltammetry/ EIS 0.5 to 30 μg/mL 9.47 μg/mL - 3.79μg/mL (peanut) Barbieri et al., 2023 Fe3O4@grap hene Salmonell a CV/ DPV 2.4 × 102 - 2.4 × 107 cfu/mL 2.4 × 102 cfu/mL - 1.18 × 103 cfu/mL (milk) Feng et al., 2022 TiO2 Listeria monocytog enes, Salmonell a EIS 104 to 108 cfu/ml for L. monocytog enes 2.4 × 102 cfu/mL for Salmone lla, 4.7×102 cfu/mL for L. monocyt ogenes. - - Wang et al., 2008 rGO-TiO2 Salmonell a enterica DPV 108 to 101 cfu mL-1 101 cfu mL−1 - - Muniandy et al., 2019 Chitosan/ (FTO) malathion DPV 0.001–10 ng/mL 1 pg/ml 0.01 μg/mL, − 0.001 ng/mL Lettuce/soil sample 0.001 ng/ml Prabhaka et al., 2016 MoS2/TiO2n anobeads/A u NPs microcysti n-LR DPV 0.005–30 nM 2 pM - - Liu et al., 2019a 21 The possibilities for improving electrochemical detection of foodborne pathogens, heavy metal ions as soil and water contaminants, and toxins in food production processes lie in the discovery of more sensitive, selective, stable, catalytically active, non-toxic, and biocompatible novel NMs. The approach to NM synthesis plays a crucial role in the stability of electrocatalysts and the reproducibility of detection results. By adjusting the properties of electrocatalytic NMs such as particle and pore size, morphology, effective surface area, electron transfer properties, adsorption capacity, and the detection mechanism, the LOD should be improved. Incorporating chemical Carbon electrodes/ CoO nitrite ion CV - 0.3 μm - - Puspalak et al., 2022 Ag@iron oxide/SPCE nitrate CV/ Amperometry - 30 uM - - Bonyani et al., 2015 CoO/rGO carbofuran (CBF) and carbaryl (CBR) CV/DPV 0.2-70 μM for CBF and 0.5200 μM for CBR 4.2 μg/L for CBF and 7.5 μg/L for CBR 0.5–200 uM (fruit/vegeta ble) 0.50 uM Wang et al., 2014 Au/ ZrO2)/graph ene/GCE methyl parathion CV/EIS/ Square wave voltammetry - - 1-2400 ng /mL (cabbage) 1 ng/mL Gao et al., 2019 Mn/Fe2O4 heavy metals Square wave anodic stripping voltammetry( SWASV)/CV 10 - 100 ppb 1.95 ppb for As (III) - 9.56 ppb (water) Zhou et al., 2015 GCE/MnFe2 O4/GOx Cu (II), Pb (II), Hg (II), Cd (II) SWASV/CV/ EIS 10 -110 ppb. 3.37 ppb - sub-mM (water) Zhou et al., 2016 MgO/GCE Pb (II), Cd (II) CV/Stripping voltammetry 2.1 pM for Pb and 81 pM for Cd 3.3 to 22 nM for Pb(II) and 40 to 140 nM for Cd(II) 1.0 to 30 nM for Pb (II) and 20140 nM for Cd(II) (Water) 6.07 ppb for Pb(II) Wei et al., 2012 In2O3 glucose Chronoamper ometry 10−11 - 10−5 M less than 7 fM - - Chen et al., 2017 22 functional groups onto MOx NMs can allow for the detection of target molecules like immobilized enzymes, DNA molecules, or antigen/antibody complexes. Various electrode pretreatments, enzyme/protein engineering, immobilization/conjugation strategies, and procedures involving biological recognition elements can significantly affect the LOD. The use of molecularly imprinted polymers (MIP), specially designed NMs with electrocatalytic activity similar to biorecognition elements, specific ion-selective membranes, and electronically tuned semiconductive properties of field-effect transistors could potentially lead to the detection of analytes at femto/attomolar levels, including the detection of single binding events (Lahcen et al., 2023 ). To put certain bio-electrochemical sensor prototypes into a practical application, as a lab-on-achip replacement of traditional lab detecting methods, much effort still has to be done in discovering of novel 2D and 3D biofunctionalized multifunctional NMs combined with MOx and biorecognition elements, with better stability under the operational conditions, and more affordable in terms of cost-effectiveness. Nowadays, there is already extensive work being published on various functional NMs and on their potential application in electrochemical sensors, but not many sensing devices appeared in the market, even if there is a huge demand for the practical application and various sensing activities. Emphasis should be placed on the engineering expertise required for designing and manufacturing sensors, as well as a thorough understanding of electrochemical methods and processes. It is also important to grasp the various reaction mechanisms that occur at the surface of catalytic NMs in order to develop functional and applicable devices. 2.2. Electrochemical gas sensors Electrochemical gas sensors utilizing MOx-NMs have garnered significant interest for detecting volatile compounds (VOCs) in food products and beverages (Wawrzyniak, 2023). Among volatile 23 organic compounds (VOCs), amine gasses such as trimethylamine (TEA) and dimethylamine (DMA), as well as ammonia (NH3) and hydrogen sulfide (H2S)are crucial indicators in food quality control (Andre et al., 2022, Wang and Zeng, 2018, Wang et al., 2022a). In contrast to electrochemical biosensors that use MOx NPs to improve sensor performance, MOx NMs in gas sensors function as the detecting component responsible for identifying the targeted gas molecules. The adsorption and desorption processes of the targeted gaseous species on the MOx structure surface, leading to changes in the material's electrical characteristics, form the basis for the sensing mechanism of MOx-based electrochemical gas sensors (Wawrzyniak, 2023). Some MOx NMs like SnO, TiO2, ZnO, and CuO have been utilized for the electrochemical detection of amine gases and hydrogen sulfide. Prospective sensors must exhibit outstanding gas sensitivity and selectivity along with efficient operation at ambient temperatures, in order to decrease energy consumption and off-chip instrumentation. Challenges arise when using MOx nanostructure-based sensors as they often require high operating temperatures for optimal sensitivity and selectivity. Various approaches have been explored to address this issue, such as doping, catalysts, and modifying material structure (Figure 3). 24 Figure 3. General strategies used in MOx-based electrochemical gas sensors working at RT For instance, Xu et al., 2020 demonstrated the creation of a room temperature (RT) TMA sensor with high sensitivity to TEA by increasing oxygen vacancy concentration in a porous SnO thin layer. The effect of exposed facet of copper (I) oxide (Cu2O) NPs on the gas sensing performance toward NH3 has been discussed by Zhao et al., 2023. They showed that the exposed high-index facet has superior NH3 gas adsorption and surface charge activity, resulting in the enhancement of NH3 sensing characteristics. Another example of sensors using Cu2O involves the formulation of Cu2O/Ti3C2Tx nanocomposites (Zhou et al., 2022a). The research demonstrated that this particular formulation led to a significantly greater sensitivity to triethylamine, with levels 3.5 times higher compared to the initial Cu2O nanospheres. Moreover, in order to improve sensor capabilities at RT, a variety of ZnO nanostructures were created. Srinivasan et al., 2018 conducted interesting research in which NH3 sensors were created using twisted ZnO nanowires to enhance the response 25 characteristics of the NH3 sensors. The research findings demonstrated that twisted ZnO exhibits a more favorable ratio between the intensity of polar and non-polar diffraction peaks compared to other orientations of ZnO nanowires. This leads to an increased number of adsorption sites on the surface, thereby improving the gas sensor's sensitivity towards NH3. Further research showed that ZnO thin films, when co-doped with Fe and aluminum (Al), demonstrate increased sensitivity to NH3 in comparison to pure ZnO. This is because the doping creates a more direct path for charge carriers, thereby increasing the electrical conductivity of the sensing material (Vijayakumar et al., 2020). In a study conducted by Radhi Devi et al., 2020, a comparable method was employed utilizing zinc oxide (ZnO) doped with strontium (Sr) to develop a sensor for detecting NH3 at RT. The findings revealed that the sensor incorporating Sr-doped ZnO exhibited heightened sensitivity and improved recovery properties in the presence of NH3 in comparison to pure ZnO. Nanocomposite of ZnO/NiO was executed for NH3 gas sensor by Jayababu et al., 2019. This methodology encompassed establishing a p-n junction between p-type NiO and n-type ZnO. The study showcased that the synergistic effect of this resultant heterojunction, in conjunction with the chemical sensitization and catalytic properties of NiO, notably augmented the sensing efficacy of the ZnO/NiO sensor at room temperature. ZnO-MWCNT was also investigated for the detection excuted on of NH3 at RT (Vatandoust et al., 2021). It was shown that nanotubes fill the void between ZnO NPs and cause the ZnO surface to become rough, increasing the surface area available for gas testing. Recently, ZnO NPs were combined with carbon nanofibers (ZnO@CNF) to produce NH3 sensor working at RT (Fan et al., 2022). It was demonstrated that the working temperature of the ZnO@CNF gas sensor is significantly reduced from 325°C to 23°C compared to pure ZnO. 32 intelligence (AI) algorithms used for data processing are primarily responsible for the observed disruption. The primary objective of the E-nose concept is to mimic an animal's olfactory system to detect various substances within a complex mixture of gases, scents, odors, perfumes, etc. (Figure 4). An E-nose device consists of two essential parts: a sensor system and a pattern recognition component. A typical sensing system consists of an array of sensing components and corresponding transducers. Figure 4. Parallel description of animal olfactory system and artificial E-nose system Some of the commonly used commercial e-nose systems, such as the PEN3 developed by Airsense Analytics, The Cyranose® 320 produced by Sensingent, and the Fox (2000, 3000, 4000) instruments developed by Alpha-MOS, utilize electrochemical transduction. This involves converting the interaction between the sensitive layer and the target analyte into an electrical signal, which is then collected using analog or digital read-out devices. Therefore, this review will focus on electrochemical transduction as it provides reliable quantitative and qualitative detection and analysis. 33 An overview of the literature database revealed that significant efforts are being made to miniaturize the complete E-nose system in order to make such devices mobile and suitable for onsite applications. MOx are considered ideal candidates for miniaturization due to their high sensitivity per surface area. Technological advancements in fabrication of MOx layers enabled miniaturization to micro and nanoscale levels. Kang et al., 2020 have demonstrated a top-down lithography approach for fabrication of different MOx nanopattern channels (NiO, CuO, Cr2O3, SnO2, and WO3) on silicon wafer. Developed E-nose system was able to effectively differentiate seven hazardous analytes. Reported results offer a powerful tool for miniaturization of E-nose devices. Aiming to achieve low power consumption and RT operating conditions, Chen et al., 2018 developed an e-nose device with 3D SnO2 nanotube array, and with the designed setup they achieved high-sensitivity and successful discrimination of gas mixtures at RT, which yielded 1000 times lower power consumption. Rehman et al., 2020 presented an interesting approach for wireless e-nose devices based on Figaro TGS sensor array, for discrimination of gas mixtures and VOCs. Most significant advancement of MOx in the evolution of e-nose devices is expected to be found in the nexus between tailored material properties and further improvement of AI and machine learning algorithms for data analysis. In future endeavors, closer binding between E-nose and artificial intelligence technologies should be expected. Kiselev et al., 2018 published an interesting paper, describing functional instability of E-nose units over different time periods of exploitation. Through examination of the gathered data, authors discovered that subtle changes in the composition of the surrounding air had the greatest impact on the stability of device performance. The authors developed a novel strategy through an extra training technique that is shown to effectively control both the temporal changes in ambient and the drift of multisensor array 34 characteristics, even over extended periods of time, to overcome the discovered instabilities. Within the suggested framework, using the power of AI algorithms, more efficiency of MOx materials can be extracted, opening a new frontier for scientific, technological and market development. With the improvements in design of sensitive layers and pattern recognition systems, e-nose technology and devices expanded over the agricultural and food production fields. E-nose devices found application in monitoring of fruit, vegetables, grain products, dairy products, seafood products, fats, oils and beverages quality, authenticity, and other important parameters. Interesting application of the e-nose sensor array was reported by Ayari et al., 2018, where monitoring of the adulteration of margarine in cow ghee was performed. They used an array composed of commercial MQ sensors and TGS sensors, whereas for the data analysis they used principal component analysis (PCA) and artificial neural networks (ANN) methods. Based on the obtained results they were able to discriminate between the pure and counterfeit cow ghee samples. The freshness of post-harvest kiwifruit was predicted in the study by Du et al., 2019 using an E-nose with 10 MOx semiconductor (MOS) gas sensors. E-nose device has proven to be a powerful tool for the prediction of the postharvest kiwifruit ripeness through aroma volatiles. Transcinnamaldehyde, thymol, menthol, and vanillin were the four safe bioactive volatile terpenes and natural chemicals that were the subject of the study presented by Gouda et al., 2019 on the egg yolk volatile components. Gas chromatography/mass spectrometry (GC/MS) and headspace solid phase microextraction (HS-SPME) were used to examine the volatiles, and an E-nose with 18 sensors was used to distinguish between different fragrance patterns. To better comprehend the impacts of bio-active chemicals on the volatility of biological fatty media, their study revealed new information, describing how terpenes can shield egg yolk media from the unpleasant odor 35 production brought on by the lipid and protein breakdown. Liu et al., 2018 used an E-nose to track the progress of fungal contamination in peaches. Three common spoilage fungus, Botrytis cinerea, Monilinia fructicola, and Rhizopus stolonifer, were injected into peaches before they were kept for different amounts of time. Then, e-nose was used to examine the volatile chemicals produced in the fungal-inoculated peaches, growth information (colony counts) of the fungi and the findings were cross-compared. The findings demonstrated a correlation between variations in volatile chemicals and the total number and kind of fungus present in fungal-inoculated peaches. The primary components of E-nose reactions were terpenes and aromatic chemicals. The outcomes also demonstrated the potential of e-nose for application in differentiating between types of fungal contamination in peaches by exhibiting its excellent discriminating accuracy. Liu et al., 2019b, reported an innovative technique for a bionic E-nose based on a MOS sensor array and machine learning algorithms utilized to identify wine quality. Odor recognition makes it easier to distinguish between wines with various characteristics, such as production regions, vintage years, fermentation techniques, and varietals. Results show the value of the created E-nose, which, after choosing the best algorithm, may be used to differentiate between various wines based on their characteristics. Pirsa and Shamusi, 2019 reported research regarding the viability of changing the e-nose software to assess rice aging during storage with a MOx gas sensor. Using an E-nose device, the scent change of aromatic and non-aromatic rice was tracked throughout the storage process. The aromatic samples followed a predetermined schedule with discrete groupings that stood out on their own, demonstrating the lowering of aging indices. During the early phases of preservation, the volatile components in the aromatic rice experienced significant modifications. Unorganized clustering of the non-aromatic rice demonstrated its resilience since the scent molecules it contains 36 become less varied. The E-nose system coupled with advanced numerical techniques can be used to accurately manage rice aging. The market for E-noses is expected to expand significantly in the next decade. Increasing usage of e-nose in the food and beverage sector, which aids in enhancing the quality of consumable items, is one of the reasons driving the growth of this market. The expansion of this market might be hampered by several issues, such as the relatively high price of e-nose devices. However, e-nose technology has seen growing application in a number of industries, including environmental monitoring and military defense, thanks to global players' innovation and continual development efforts. At the moment, e-nose and expansion of its functions in healthcare and quality control services have opened up new potential for this sector. 2.4 Smart packaging The development of smart food packaging is increasingly important in modern lifestyle, playing a crucial role in reducing food waste (Motelica et al., 2020; Galstyan et al., 2018), reducing synthetic polymer waste through bio-based and biodegradable packaging (Salgado et al., 2021), and improving customer convenience in general. Smart packaging can protect food and extend its shelf life by modifying the atmosphere in a package, introducing antimicrobial or anti-oxidative properties, indicating spoilage, improving humidity and gas barrier properties, and monitoring storage conditions (Yousefi et al., 2019, Salgado et al., 2021). For this purpose, NMs based on transition MOx exploit their antimicrobial and photocatalytic properties to protect packed products from the negative effects of various microorganisms and may provide additional beneficial effects on the shelf life of packed food. The most commonly used oxides for this purpose are TiO2 and zinc dioxide (ZnO2). 37 The mechanism of TiO2 antimicrobial effect in nanocomposite films is explained in detail by Kubacka et al., 2014. It clearly indicates a great potential for this material to be implemented in smart food packaging, which was recognized by many researchers who employed different approaches toward development of TiO2 based smart packaging. Recent research shows high antimicrobial activity of cellulose based paper composite with TiO2. The results indicate outstanding antibacterial properties against escherichia coli (E. coli), moderate action against staphylococcus aureus (S. aureus), for composite paper with 8% of TiO2 NPs, and good scalability of process at low production cost (Maślana et al., 2021). Active nanocomposite packaging based on TiO2 and chitosan demonstrated better moisture barrier and mechanical properties than pure chitosan and efficient photo-degradation of ethylene for extended shelf-life (Kaewklin et al., 2018). Currently, an unconventional sort of smart packaging considers application of coating directly on a product, such as meat, cheese or a fruit. Fonseca et al. have developed gelatin-TiO2 coated expanded polyethylene foam nets deposited on the surface of a papaya fruit by a novel procedure. After 4 days in storage, coated fruit have demonstrated lower ethylene emission and respiration rate at the climacteric peak, better physical properties, better preservation of green peel, orange pulp, sweetness/acidity equilibrium and no fungal growth (de Matos Fonseca et al., 2021). TiO2 also finds an application in oxygen detection in the packages with modified atmosphere. The colorimetric printable sensor developed by Wei et al. based on TiO2 nanotubes showed quick response by color change in the presence of oxygen, and its unaffected by the natural light (Wen et al., 2018). The oxygen sensor was composed of hydroxyethyl cellulose, glycerin, methylene blue and TiO2 nanotubes, ball milled all together and deposited by screen-printing on a PET substrate. The indicator was UV activated before the use and showed a great contrast between referent and sensor exposed to oxygen in modified atmosphere packaging. 38 The potential of ZnO NPs has been recently reviewed by Kim et al., 2020. The review reports great potential of ZnO NM incorporated in smart food packaging, exhibiting strong biocidal properties and nontoxic behavior for humans. The review paper also explains the ZnO mechanism of photocatalytic effect and diversity of ZnO NP morphology. A great example of multifunctional ZnO based smart food packaging was developed by Pirsa and Shamusi, 2019. A newly developed cellulose-polypyrrole-ZnO film together with a chicken meat in a package was put under a test over time. The results showed a good antimicrobial and antioxidant protection of the meat product, prolonging good organoleptic properties. Also, electrical properties of the film had been related to storage conditions over time, making the film also an time-temperature indicator. A ZnO based bionanocomposite coating reported by Li et al., 2019a applied on bananas produced moderate protection of the fruit in a period of 7 days. The coating delayed ripening and improved overall postharvest quality and shelf life of the fruit. A suitable replacement for conventional synthetic polymer packages, based on zein-ZnO and ZnO: magnesium (Mg) QDs was reported by Schmitz et al., 2020. The composite films were transparent and homogenous. Hydrophobicity of the films was improved as well. An important feature of this active food package is seen in antimicrobial testing. Different amounts of ZnO fillers were tested, where best inhibition of S. Aureus was reported for sample with 44.8 wt% ZnO NPs in zein, while ZnO:Mg QDs were most efficient against E. Coli when less than 1 wt% of particles were added. ZnO NPs are used not only for antimicrobial purposes, but for improving mechanical properties as filler also. Chicken skin gelatin/tapioca starch composite with ZnO has been analyzed by Lee et al., 2020. It was found that tensile strength doubled with addition of 5% of ZnO, while elongation at break reduced. Water vapor permeability was also reduced, with a best result for the composite with 4% of ZnO. Antimicrobial properties were also tested against E. Coli and S. Aureus, showing good 39 improvement with increasing content of ZnO up to 5%. The application of ZnO NPs as modifiers of some standard synthetic polymers, like low density polyethylene, was also explored. This approach looks to improve a packaging material in a simple procedure, adding an antimicrobial effect of the packaging (Rokbani et al., 2019). Different processing conditions were explored toward obtaining stable ZnO coated packaging material, without detachment of ZnO over time. It was concluded that even after 8 months of storage the material maintained moderate antimicrobial properties toward E. Coli and S. Aureus. It was also found that such coated material may lose antimicrobial properties after washing with water. Semiconductor NMs based on MOx have made a breakthrough in food storage application as the so-called “photocatalytic refrigerators”. The source of the idea is drawn from excellent photocatalytic properties of these materials, that can be used for antibacterial purposes, for odor elimination or for ethylene decomposition. The incorporation of MOx into food packaging as an antimicrobial agent and nanosensors, as previously described, can transform standard packaging into advanced smart packaging. This technology not only helps preserve and maintain the freshness and quality of the food within, but also provides up-to-date information on the quality of the packaged food, enabling consumers to make informed decisions regarding purchase, storage, and consumption (Thirupathi Vasuki et al., 2023, Joshi et al., 2024). Smart packaging aligns with the broader trend of incorporating technology into various aspects of daily life, providing consumers with more information and control over the products they consume. This innovation represents a step forward in creating a more sustainable, efficient, and consumerfriendly food supply chain. 40 While the potential benefits of MOx-integrated packaging are substantial, ongoing research and collaboration across industries are essential to address any potential safety concerns. Adherence to regulatory guidelines is crucial to ensure that these technological advancements contribute positively to the food industry while maintaining consumer safety and confidence. 3. MOx NMs for agrochemical targeted delivery Common agricultural practices mainly rely on the use of agrochemicals, such as fertilizers and pesticides, to maintain sufficient crop yield. Fertilizers act as plant growth enhancers by increasing nutrient availability and aiding mineral delivery, while pesticides are employed to protect plants from pests and weeds (Dhankhar and Kumar, 2023). In recent decades, the rapid progress of science, technology, and industry has led to the widespread integration of artificial NMs in agrochemical formulations. Within this class of materials, MOx NMs stand out due to their unique properties. As shown in Figure 5, NMs used to promote crop production can be classified into two categories: nanofertilizers and nanopesticides. 41 Figure 5. Schematic representation of multifunctionality of MOx NPs and their application as Nanofertilizers and Nanopesticides in agricultural environments. The aim of this section is to bring such an important field of research closer to readers attention, and to provide more clarity in potential for further advancement of MOx NMs in crop production applications. 3.1. Nanofertilizers Conventional use of fertilizing agents such as urea, nitrate, or phosphate compounds accumulates extensive amounts of harmful chemicals. The staggering demand for fertilizer application was forecast to significantly increase with a growing population, leading to increased efforts for efficient management of pesticides and fertilizers (Xiang et al., 2020). One proposed solution is to find alternative technologies for pesticide and fertilizer deployment. Another solution is directed towards the development of rapid pathogens and pest detection (Buja et al, 2021). 48 3.2. Nanopesticides NM-based formulations outperform traditional pesticides and formulations due to their high efficacy, which is due to their high surface area, enhanced solubility, induction of systemic activity resulting from smaller particle size, improved agility, and low toxicity for the removal of organic solvents (Sasson et al., 2007). NPs have the potential to significantly improve the effectiveness and stability of enzymes, entire cells and other natural products employed as biopesticides. The objective of utilizing NMs in agriculture is to mitigate nutrient scarcity, amplify crop production, minimize the reliance on chemical plant defense, and lower manufacturing expenses to optimize productivity (Hyder et al., 2023). While low-volume, high-value applications are anticipated for NM-based preparations, nanostructured delivery systems will necessitate a targeted distribution strategy centered on exploiting the pest's habits and behavior. Jameel et al., 2020 created ZnO-NPs with a thiamethoxam nanocomposite and examined their synergistic effects on Spodoptera litura larvae. The larvae were fed castor leaves that had been treated with thiamethoxam as well as a mixture of ZnO-NPs and thiamethoxam (1090 mg/L). They found a 27% increase in larval mortality, as well as deformities in adults and pupae, delayed CuO/PEC 300 nm Fortunella margarita Swingle seed Increased seed germination. Leonardi et al., 2021 MnOx/FeOx 23.42 nm Corn The development of plants, with a specific focus on germination rates, root growth, and fresh weight in maize plantlets. de França Bettencourt et al., 2020 Fe3O4 ∼16 nm Legume seeds Increase of 88–366% of embryonic root growth in specific legume plants. Palchoudhury et al., 2018 γ-Fe2O3 S-Fe2O3 S* small 40-215nm 4-15 nm Soybeans γ-Fe2O3 improved growth and decreased the Fe and N inputs. SFe2O3 enhanced the growth, yield, and nutritional quality, and provided better delivery of Fe nutrition with a slower rate of Fe dissolution. Cao et al., 2022 49 emergence, and reduced fecundity. Experiments on the pulse beetle, Callosobruchus maculatus (C. maculatus), performed by Malaikozhundan and Vinodhini, revealed an attractive strategy using an environmentally friendly manufacturing process of Pongamia pinnata (P. pinnata) coated ZnO NPs (Pp-ZnO NPs). These NPs reduced the number of eggs deposited and the hatchability of C. maculatus in an inverse proportion to the dose. Following treatment with Pp-ZnO NPs reveals a substantial suppression in the larval, pupal, and overall development stages of C. maculatus was observed. Additionally, 25 g mL-1of polypropylene (Pp)-ZnO NPs are 100% fatal to C. maculatus, making them more effective in controlling the species. Pp-ZnO NPs are more competent in suppressing C. maculatus, inducing 100% mortality at a concentration of 25 g mL-1. The midgut activities of glutathione S-transferase, lipase, β-amylase, cysteine protease, and glucosidase in C. maculatus were reduced post-stimulation with Pp-ZnO NPs (Malaikozhundan and Vinodhini, 2018). The objective of the research presented by Ilkhechi et al., 2021 was to employ the sol-gel method to create ZnO, TiO2, and ZnO-TiO2 NPs with a weight ratio of 1 to 1 for Zn and Ti utilizing zinc acetate and titanium isopropoxide. Aspergillus flavus (A. flavus) was tested in vitro using antifungal activities such as minimum inhibitory concentration (MIC) and minimum fungicidal concentration (MFC) to assess NPs' morphological and physical properties. Although ZnO-TiO2 was more efficient against A. flavus than pristine TiO2 and ZnO, all the produced NPs at (50 g/ml) concentration inhibited fungal growth. Spurs growth was completely suppressed by TiO2 and ZnOTiO2 for 300 g/ml) concentration. Pure ZnO and TiO2 had pyramidal and spherical shape, respectively, whereas ZnO-TiO2 NPs had both spherical and pyramidal shapes on the surface with growing particles. A modest concentration (150 g/ml) of ZnO-TiO2 revealed increased reactive oxygen species (ROS) formation and oxidative stress induction as compared to TiO2 and ZnO 50 alone, leading to the fungicide's fungicide activity (Ilkhechi et al., 2021). In conclusion, the nanostructured ZnO-TiO2 composite can be employed as an antifungal medicine, however more study is required to comprehend how the NPs' antifungal mechanism differs from ROS-induced apoptosis. In their work, Kolenčík et al., 2019 discovered that ZnO NPs applied foliarly improve the quality of crop products, as the plant water stress index was lower after ZnO NP foliar application than in the control throughout the entire life cycle. According to the increased nutritional parameters of the foxtail millet grain, the plant's photosynthetic efficiency, transpiration, and enzyme activity have improved. By incorporating ZnO NPs, the oil content was enhanced by 34% and total proteins by 9.1%. Additionally, the seed yield and seed Zn accumulation exhibited a significant increase of 18.3% and 21.1%, respectively, compared to Bulk-Zinc sulfate (ZnSO4). On the other hand, no differences were observed between ZnO NPs foliarly applied treatments and the control in terms of the weights of dry seed heads and thousand grains of ZnO NPs. The reason behind this was the considerable decrease in zinc concentration, falling below the typically referenced 0.1% level that is known to have detrimental effects when Zn2+-corresponding metal-based fertilizers are applied to the leaves. Lakshmeesha et al., 2020, created high-purity, nano-sized (30-40 nm) hexagonal-shaped ZnO-NPs from aqueous leaf extract of Melia azedarach (MaZnO-NPs) in order to reduce antifungal activity. Characterization of the generated MaZnO-NPs was accomplished using UV-Vis spectroscopy, FTIR, XRD, SEM, and TEM. The nanocomposite was shown to be far more powerful than the synthetic fungicidal drug Amphotericin B, as evidenced by dose-dependent inhibition of cladosporium cladosporioides (C. cladosporioides) and Fusarium oxysporum (F. oxysporum) growth. MIC and MFC values for MaZnO-NPs nanocomposite were 81.67 and 178.3 mg/mL, and 51 93.33 and 208.3 mg/mL, while synthetic fungicidal agent Amphotericin B exhibited a MIC and MFC values of 203.3 and 326.7 mg/mL and 236.7 and 381.7 mg/mL against C. cladosporioides and F. oxysporum, respectively. Malaikozhundan and Vinodhini, 2018 presented a green synthesis of P. pinnata leaf extract coated ZnO NPs (Pp-ZnO NPs) as an insect pest control agent. X-ray spectroscopy revealed hexagonal wurtzite structures in Pp-ZnO NPs with particle diameters of 21.3 nm. Pp-ZnO NPs were investigated for pesticidal activity against the pulse beetle, C. maculatus and shown to lower fecundity (eggs laid), pupal, and total development duration in a dose-dependent manner. At 25 g/mL, nanocomposite caused 100% mortality, while decreasing mid-gut α-amylase, α-glucosidase, β-glucosidase, cysteine protease, glutathione S-transferase, and lipase activity in C. maculatus. Manzoor et al., 2023 synthesized CuO NPs from A. indica leaves via green synthesis. CuO NPs with sizes ranging from 20 to 80 nm were discovered using TEM and SEM pictures. Synthesized CuO NPs demonstrated strong antibacterial activities against microorganisms, inhibiting pathogen activity by breaking cell walls and inhibiting fungal spore generation on jujube fruit. As a result of CuO NPs, ROS are produced, DNA is disrupted, and bacterial proteins are denatured, all of which inhibit the growth of bacteria. The approach described may be well-suited for applications in the biomedical, pharmaceutical, and agricultural fields. Table 3 reports some of the recent applications of nanopesticide based on MOx in plant protection. TABLE 3. Different types of MOx nanopesticides, their sizes, target, and following effects in plant protection. Nanopesticide Size (nm) Target Effect Reference 52 Thiamethoxam/ ZnO-NPs 5 and 0.5 μm Spodoptera litura larvae Increase of 27% in larval mortality, deformities in fullgrown and pupae, abeyant emergence, and attenuated fecundity. Jameel et al., 2020 Pp-ZnO NPs (P. pinnata coated ZnO NPs) 21.3 nm Callosobruchus maculatus Delayed the overall development and suppression of C. maculatus. Malaikozh undan and Vinodhini, 2018 ZnO NPs, TiO2 NPs, ZnO-TiO2 NPs, 33.21 nm 17.68 nm ZnO = 19.25 nm TiO2 = 8.36 nm Aspergillus flavus Suppressed fungal growth. Ilkhechi et al., 2021 ZnO NPs 20 nm Setaria italica L. (foxtail millet grains) Plants revealed inequalities in millet grain oil and total nitrogen content nutritional parameters. Kolenčík et al., 2019 MaZnO-NPs 30-40 nm Soybean Inhibited the growth of C. cladosporioides and F. oxysporum. Lakshmees ha et al., 2020 Co3O4NPs 34.9 nm Rice plants Inhibition of growth and biofilm formation of Xanthomonas oryzae pv. oryzae. Ogunyemi et al., 2023 CuO NPs - Wheat (Triticum aestivum) Inhibition of root growth. Xu et al., 2023 CuO NPs 29 - 45 nm Spodoptera frugiperda High larvicidal and antifeedant activity - reduced the number of larval hemocytes. Rahman et al., 2022 CuO NPs 20 - 80 nm Ziziphus jujuba fruit Antibacterial, antifungal, and antioxidant properties. Manzoor et al., 2023 ZnO NPs 20–30 nm Wheat Reduced Cd accretion in wheat grains. Rizwan et al., 2019 In summary, MOx NPs have a high surface area-to-volume ratio, which enables them to disperse and be absorbed more effectively in plants. This improves the delivery of nutrients and helps in controlling pests. The small size of these nanoparticles also makes it easier for them to penetrate plant cells, thereby enhancing nutrient absorption and promoting growth. As a result, there is an increase in crop yields and the quality of produce is improved. On the other hand, nanofertilizers 53 make use of MOx NPs to deliver nutrients directly to plant roots, enhancing nutrient uptake and utilization. This leads to stronger and healthier plants that are more resistant to diseases and environmental stress. However, there is still a lot to explore in this research field, and several promising directions for future investigation can be identified. Among these is the potential of MOx NMs for mitigating the negative effects of drought stress on plant growth. Certain nanoparticles such as ZnO, Si NPs can improve water retention in soil, promote water uptake by plants, and reduce the impact of drought on crop yield and may also be used to develop smart delivery systems for water and nutrients to plants during periods of water scarcity (Raza et al., 2023, Muhammad et al., 2022) . Research in this area aims to develop innovative solutions for sustainable agriculture, mitigating the impact of drought on crop yields. 4. NMs for agricultural environment 4.1 Agricultural wastewater treatment Nowadays, the number and concentration of different pesticides in surface, ground and wastewater are significantly increasing, because of the great development of the agrochemical industry (Radović et al., 2015; Barbosa et al., 2016). Many of them do not decompose into simpler, less dangerous compounds, but accumulate in the environment and transform into even more dangerous forms (Reddy and Kim, 2015). The reason for this behavior is the fact that most pesticides are resistant to chemical and natural photochemical and biological degradations (Ajiboye et al., 2020). Keeping in mind all the above, the creation and implementation of effective techniques for the treatment of polluted water are crucial jobs. Various processes have been tested to reduce the concentration and potential health risk of pesticides (Reddy and Kim, 2015). Traditional methods (adsorption, nanofiltration, reverse osmosis, chemical treatments, and various 54 biological processes) have several disadvantages, e.g. adsorption transfers the pollutant only from one phase to another, chemical oxidation can lead to incomplete degradation of pesticides, and in the case of biological treatments the main disadvantages are poor reaction rates, sludge removal and the need for strict control of suitable pH and temperature (Dong et al., 2015; Ong et al., 2018). Therefore, great attention is paid to Advanced Oxidation Processes (AOPs) that are employed for purification of water systems contaminated with pesticides. Among different AOPs, the central place is occupied by the processes of heterogeneous photocatalysis with the use of MOx NMs as photocatalysts. Namely, photocatalysts participate in and accelerate the chemical transformation of the substrate, but remain unchanged at the end of the photocatalytic process. Most photocatalysts are semiconductors, which are characterized by a suitable bangap (Dalrymple et al., 2007). Figure 6 shows an overview of publications for the last six years, which are based on the application of NMs in the removal of pesticides. In general, it is evident that there are more publications on this subject. Different semiconductor materials are used as photocatalysts in heterogeneous photocatalysis such as TiO2, ZnO, SnO2, ZnS, WO3, cadmium sulfide (CdS), cadmium selenide (CdSe), gallium arsenide (GaAs), gallium phosphide (GaP), etc. and among all mentioned, TiO2 and ZnO are the most frequently used ones (Etacheri et al., 2015; Ribeiro et al., 2015). 55 Figure 6. Number of articles published in 2018–2023, related to application of NMs in pesticides removal with “photocatal*”, “removal”, “ZnO”, “TiO2”, and “pesticide*” as a searching keywords (available online on Scopus). TiO2 has been the most studied photocatalyst because of its low production cost and chemical stability as well as its ability to induce reductive and oxidative reactions (Dong et al., 2015; Ong et al., 2018). According to published works in the last period, special emphasis is placed on the modification and immobilization of TiO2 to improve pesticide removal efficiency. Namely, Yu et al., 2015 investigated removal of pentachlorophenol using a photocatalyst made of Ag NPs mounted on anatase TiO2 nanotubes. Their findings point that Ag/TiO2 showed significant visiblelight absorption which indicates the possibility for the sunlight driven photocatalytic degradation of pentachlorophenol. The enhancement of photocatalytic activity can be attributed to the strong localized surface plasmon resonance of the Ag NPs and the intimate contact between Ag NPs and anatase TiO2 nanotubes, which favors the separation of photo-generated charge carriers. Through sol–gel synthesis, Achamo and Yadav, 2016 prepared nanosize Ag–N–P-tridoped TiO2. A synergetic effect of tridoping TiO2 enhanced its photocatalytic activity and thereby enhanced its 0 10 20 30 40 50 60 70 2018 2019 2020 2021 2022 2023 Number of publications Year TiO ZnO All MOx 2 56 ability to remove 4-nitrophenol from aqueous solutions. Obtained degradation of 4-nitrophenol using Ag–N–P tridoped can be explained by two effects, minimization of electron–hole recombination by the doped Ag and extension of the photoabsorption in the visible region by doped N and P. Also, An et al., 2016 investigated carbon-doped TiO2 catalysts supported by zeolite in the removal of 18 pesticides and pharmaceuticals and their findings showed that TiO2 can effectively degrade investigated substrates in water. Photodegradation efficiency is a consequence of carbon-doped TiO2 loading on zeolites which could block their micropores and reduce their surface areas and micropore number. Besides, the activity of carbon-doped TiO2 depends also on the photodegradable characteristics of the pollutants, since the zeolite support connects photolytic pollutants and carbon-doped TiO2 for energy and/or electron transfer. Further, Khavar et al., 2018 investigated synthesis by ultrasonic-hydrothermal technique of In,S co-doped TiO2 with reduced graphene oxide and its application in the removal of atrazine. Results showed complete degradation and 95.5% mineralization of atrazine within only 20 min. The enhanced photocatalytic activity of the prepared NM is explained by the synergistic effect of dopants contributing to improved visible light absorption and decreased recombination rate of the charge carriers. Besides, Abdelhaleem and Chu, 2019 studied application of a hybrid process for degradation of CBF through peroxymonosulfate activation and Fe(III) impregnated N-doped TiO2 photocatalyst. Applied process exhibited about 90% of total organic carbon reduction which can be ascribed to the generation of more reactive radicals through peroxymonosulfate activation by Fe (III). The efficiency of TiO2 for the degradation of mesotrione has also been improved by Merkulov et al., 2020 by using different Au NPs. Mesotrione can be efficiently eliminated from water by the modified TiO2 and the reason for this catalytic performance might be the band gap energy, as in the case of Au modified TiO2 it is shifted towards the lower values, hence there was efficacious 57 use of visible light. Finčur et al., 2021 studied the efficiency of TiO2, ZnO, and MgO (prepared by sol–gel method) in degradation of two antibiotics and two herbicides exposed to UV/simulated sunlight. Obtained results showed that TiO2 proved to be the most efficient nanopowder under both irradiations. Besides, Ivetić et al., 2021 investigated the removal efficiency of organic water pollutants (pesticides quinmerac and tembotrione, and pharmaceuticals metoprolol, amitriptyline, ciprofloxacin, and ceftriaxone) from water by adsorption and photocatalysis using titanium/molybdenum/mixed-oxides. Findings indicated that for all substrates, UV light had a better removal efficiency than simulated sunlight, which can be correlated to UV-Vis reflectivity results and estimated values of the catalysts’ optical absorption thresholds that just reach the Vis region, so when the reaction system is exposed to simulated sunlight, there is a smaller number of photons from the UV part of the spectrum, and thus, a smaller number of highly reactive species formed. However, an excellent outcome was observed for ciprofloxacin eradication (80%) by employing a synergic adsorption/photocatalytic method. Many attempts are aimed at immobilization of TiO2 on appropriate carriers. Assalin et al., 2016 describes application of immobilized TiO2 using a flat panel photoreactor in the treatment of agricultural waste containing methyl parathion. Results showed that almost total mineralization of the insecticide was achieved after 90 min of the process. Khan et al., 2017 published the findings of the photocatalytic performance of a sol-gel nanostructured S-doped TiO2 film for lindane removal with addition of peroxymonosulfate. Obtained results showed that addition of peroxymonosulfate significantly improved lindane removal from water which was potentially due to the dual role of peroxymonosulfate (as electron acceptor, thereby reducing the rate of electronhole recombination and as an efficient source of sulfate anion and hydroxyl radicals). Fiorenza et al., 2020 reported that the 2,4-dichlorophenoxyacetic acid and imidacloprid photodegradation 64 % chromium metal reduction was 81.17%, 55.83%, 53.33%, and 38.17%, respectively. In comparison with control and zinc sulfate treatments, zinc NPs resulted in the highest seed germination, root and plant increase. In their study, Song et al., 2019 showed that 100 mg/kg of SiO2, TiO2, ZnS, and MoS2 NMs had the capacity to minimize hazardous heavy metal buildup in cucumber plants. The findings revealed that MoS2 NMs influenced the accumulation of the majority of heavy metals. However, NMs with a large surface area and binding sites may also combine with cations such as K+, Ca2+, and Fe3+, lowering plant absorption of macroand micronutrients, which has a detrimental influence on plant development. Cucumber leaves' Si concentration rose in the presence of MoS2, possibly promoting resistance to attacks. During a 4-week incubation period, none of the evaluated NMs had an effect on cucumber plant biomass. 5. Market barriers and Risk assessment MOx NMs in the agri-food chain bring tremendous opportunities for both industry and consumers. However, there are several obstacles that need to be considered in order for NM technology to be adopted in the agri-food industry. These barriers encompass various aspects that are interconnected, including concerns surrounding nanotoxicity, safety, and regulatory harmonization. Although extensive research has been conducted on MOx NPs such as ZnO and TiO2, there have been conflicting findings regarding their potential toxicity. Significant uncertainty remains regarding their impact on human health and the environment, necessitating a clear risk assessment strategy (Sengul et al., 2020). The contamination of food products with NPs may occur at different stages of the food supply chain, starting from the use of NPs in pesticides for crop production and 65 water purification techniques, to their involvement in nanosensing or packaging, which could result in their migration into food products. The foundation for evaluating the risk of MOx NMs used in agriculture and food packaging lies in conducting physicochemical characterization. The safety of NMs is influenced by factors such as size, shape, surface charge, surface area, purity, stability, concentration, and agglomeration state, which can vary throughout their life cycle across the entire food supply chain. Furthermore, it is essential to assess the "exposure risk" posed by NMs. These materials can enter the human body through three different pathways: inhalation (respiratory tracts), ingestion (digestive tracts), and skin contact (blood vessels). In the case of incorporating MOx in packaging, it is crucial to evaluate the potential migration of nanostructures into the food. Lastly, it is important to identify and characterize specific hazards such as genotoxicity and cytotoxicity (Buzea et al., 2007). Since nanotechnology was introduced in the agrifood sector, efforts were made worldwide to regulate the production and use of NMs through legislation, recommendations, and guidelines. For example, in the US, guidelines were established for risk assessments of NMs, such as the Final Guidance for Industry issued by the Food and Drug Administration (FDA) in 2014. In Europe, the European Food Safety Authority (EFSA) has developed a new guidance for the risk assessment of NMs in various food-related areas, covering everything from the initial characterization of the materials to their impact on human health. However, assessing the toxicity of NMs remains challenging due to discrepancies in the available database of physicochemical and toxicological studies. An example that highlights the limited knowledge on the toxicity of NMs is the case of TiO2 (E 171) in recent years. Although this substance has been approved as a food additive in the European Union (EU), the safety of its usage was re-evaluated by the Panel on Food Additives and Nutrient Sources added to Food (EFSA ANS) in 2016. The panel concluded that further research 66 is needed to address gaps in knowledge regarding the potential effects of TiO2 NPs on the reproductive system, in order to establish an Acceptable Daily Intake. Concerns were also raised about the characterization of the material used as a food additive, particularly regarding the particle size and distribution of TiO2. The French Agency for Food, Environment, and Occupational Health Safety (ANSES) conducted a review of the risks associated with exposure to the food additive, which confirmed the uncertainties and data gaps previously identified by the EFSA. In the same year, the Netherlands Food and Consumer Product Safety Authority (NVWA) also provided an opinion on the potential health effects of TiO2 as a food additive, emphasizing the need to consider both immunotoxicological and reprotoxicological effects. This example illustrates how legislation has been reviewed for one of the most commonly used and well-known NMs, which is often described as a safe material. However, this becomes even more challenging when dealing with new nanoformulations, as each type of MOx NM has unique characteristics that require a thorough evaluation on a case-by-case basis. The limited information provided by current toxicology methodologies is a major problem and can pose significant difficulties for risk assessors. Traditional 2D static cultures and expensive animal studies are inadequate to provide meaningful insights into the toxicity of NMs on human tissues and organs. In vitro models using 2D static cell cultures do not adequately replicate the complex interactions between cells and their surrounding matrices, as well as the continuous fluid and blood circulation observed in native human organs. As a result, these models are inherently inaccurate for toxicity studies. Likewise, animal models fail to capture precise molecular mechanisms due to differences in physiological responses between animals and humans. However, recent advancements in tissue engineering and 3D cell culture offer promising alternatives for assessing NP toxicity, bridging the gap between preclinical models and human systems. One such alternative is the use of 67 MicroPhysiological Systems (MPS), also known as Organ-On-a-Chip (OoC) platforms. These microfluidic systems cultivate human tissues in a 3D environment, providing biomimetic platforms that are more physiologically relevant compared to conventional models. Nowadays, various OoC models were developed, including those for the skin, intestine, liver, kidney, and lung, and their utility in assessing the toxicity of Metal and MOx NPs has already been considered (Lu and Radisic, 2021, Ashammakhi et al., 2019). For example, Zhang et al. (2018) developed a biomimetic 3D lung-on-a-chip to evaluate the pulmonary toxicity of ZnO and TiO2 NPs. This study simultaneously analyzed cellular morphology, junction protein expression, ROS generation, and apoptosis of epithelial and endothelial cells exposed to NPs. More recently, a lung-on-a-chip platform using a physiologically relevant flow rate was employed to investigate the toxicity of ZnO (Arathi et al., 2022). Moreover, in a study conducted by Ahn et al. in 2018, a Heart-On-Chip platform was developed using Mussel-inspired 3D fiber scaffolds to address the toxicity of engineered TiO2 and Ag NPs. It was discovered that engineered NPs cause a reduction in the contractile function of cardiac tissues due to structural damage to the tissue architecture. Another example of assessing nanotoxicity in 3D cardiac tissue was described by Lu et al. in 2021. Using their 3D heart model, they observed that CuO NPs induce electrical and contractile dysfunction through the generation of ROS, while SiO2 leads to the secretion of pro-inflammatory cytokines. A 3D Epidermal Model has also been developed to investigate the toxic mechanisms of silver NPs in studies conducted by Chen et al. in 2019 and Wills et al. in 2015. Additionally, Yin et al. in 2019 developed a 3D human placenta-on-a-chip model to monitor NP exposure at the placental barrier. Furthermore, Li et al. in 2019b created a 3D microfluidic hepatocyte platform for evaluating the hepatotoxicity of Fe3O4 NPs, revealing that cumulative exposure to magnetic NPs via the 3D hepatocyte chip results in 68 significant damage to hepatocytes. The introduction of advanced OoC technology could improve the assessment of nanotoxicity for new nanoformulations by providing more relevant human data. Combining OoC technology with AI and in silico computational models, as suggested by Halder et al. in 2020, could potentially offer more predictive models for nanotoxicity assessment with a high correlation between in vitro and in vivo results, thus facilitating the development of new MOxbased nanoformulations that have a positive impact in the agri-food sector. 5. Concluding remarks The potential of MOx NPs for beneficiary changes in agriculture, food, and the environment has been highlighted through state-of-the-art research on their utilization in crop growth, water and soil remediation, and food quality control. In agricultural production, MOx NMs in the formulation of nanopesticides and fertilizers have the potential to increase crop growth efficiency compared to conventional formulations while also providing solutions for wastewater treatment and soil remediation. In the food sector, the possibility to efficiently incorporate MOx NMs within packaging offers benefits like increasing food shelf life, protecting products, and providing information on product quality through food safety sensors. However, as with all new technologies, the potential benefits of MOx NMs must be balanced against risks, as concerns about their hazardous effects on human health and the environment persist. Humans may be exposed to MOx NPs in food through migration from packaging films and their accumulation in edible plant portions. This is why commercial applications in real farmlands and food chains are still in the early stage. Therefore, a proper nanosafety assessment is urgently needed. Toxicological assessment of NPs on human health relies mainly on in vivo data from animal studies, which do not reflect human 69 physiology and are difficult to implement due to the diversity in types of MOx NM. In parallel, there is still a lack of predictive in-vitro platforms as the standard 2D cell culture assays fail to mimic human physiology. Acknowledgment The work described in this article has been conducted within the project MicroLabAptaSens. This project has received funding from the Science Fund of the Republic of Serbia, within the IDEAS programme under grant agreement No 7750276. This research was supported in part by the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska–Curie Grant Agreement No. 872662 (IPANEMA) and through ANTARES project that has received funding from the European Union's Horizon 2020 research and innovation programme under grant agreement SGA-CSA. No. 739570 under FPA No. 664387. 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