1Department of Botany, Ethnopharmacology and Algal Biotechnology Laboratory, School of Life sciences, Periyar University, Salem, Tamil Nadu, India;
2Department of Food Science and Biotechnology, College of Life Sciences, Sejong University, Seoul, South Korea;
3Department of Botany, Thiagarajar College, Madurai, Tamil Nadu, India
#Contributed equally as first author
Mycotoxins are poison that filamentous fungi generate under specific conditions. Mycotoxins in food and feed have a detrimental effect on both human and animal health, resulting in significant financial losses for agriculture sector. Despite the continuing advancement of traditional approaches, modern research trends favor novel alternatives. Therefore, it is crucial to prevent mycotoxin contamination, which has raised concerns around the globe. Recent advancements in the management of mycotoxin contamination have been possible by the application of promising new nanomaterials. Mycotoxins have negative impacts on human health, but nanotechnology methods appear to be viable, efficient, and affordable solutions. This review elucidates information on the incidence and toxicology of mycotoxins. Nanotechnology’s potential for removal of mycotoxins is mentioned briefly. Then, attention is directed on using newly developed nanomaterials to regulate mycotoxin contamination, such as testing, production, inhibition, adsorption, and removal of mycotoxins. The issues regarding the toxicity, incidence, and management of mycotoxins are tentatively presented along with potential prospects for using nanotechnology to remove mycotoxins from food and feed.
Key words: mycotoxin types, mycotoxin detection, nanomaterials, mycotoxin control, mycotoxin risk elimination
*Corresponding Authors: Balasubramanian Balamuralikrishnan, Department of Food Science and Biotechnology, College of Life Sciences, Sejong University, Seoul 05006, South Korea. Email: [email protected]; Arumugan Maruthupandian, Department of Botany, Ethnopharmacology and Algal Biotechnology Laboratory, School of Life Sciences, Periyar University, Salem-636 011, Tamil Nadu, India. Email: [email protected]
Received: 19 April 2024; Accepted: 16 July 2024; Published: 31 August 2024
© 2024 Codon Publications
This is an Open Access article distributed under the terms of the Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0). License (http://creativecommons.org/licenses/by-nc-sa/4.0/)
Mycotoxins are toxic substances that are synthesized by fungus under particular circumstances, which include elevated levels of moisture, presence of tainted or substandard crops, and inadequate agricultural techniques (Abdallah et al., 2024). These toxins are secondary metabolites and possess low molecular weight. Several studies have emphasized the synthesis of mycotoxins by filamentous fungus (Bennett, 1987; Horky et al., 2018). Nevertheless, the existence of filament on grains does not always imply the existence of mycotoxins. However, there is a potential for mycotoxin synthesis. It is crucial to acknowledge that the lack of molds on stored food and feed over an extended period does not guarantee that the grain is devoid of mycotoxins (Edwards, 2004; Simpson et al., 2001). Over 500 types of mycotoxins are documented and about 10,000 different varieties of fungus are identified.
It is conceived that over 1,000 additional species are yet to be discovered. No recognized systematic technique exists for detecting masked mycotoxins, thus making their identification an exceptional problem (Dallasta et al., 2015; Haque et al., 2020). Foods and feeds consisting of mycotoxins present a substantial global health risk due to their potential to harm humans and animals severely. This can result in various health issues, such as damage to the liver, heart, kidneys, gastrointestinal tract, and even the development of cancer, ultimately leading to death (Freire and Santana, 2018; Khaneghah et al., 2019).
In Malaysia, India, and Kenya, severe outbreaks of aflatoxicosis are observed that resulted in innumerable deaths of people (Yang et al., 2020a). The topic of mycotoxin risk is complex and needs attention from both agricultural technology industry and scientific community as a whole. Several types of fungi, such as Aspergillus, Fusarium, Claviceps, and Alternaria, produce mycotoxins. Aspergillus generates aflatoxins (AFT), ochratoxin A (OTA), trichothecenes (TCTs) and deoxynivalenol (DON) whereas Fusarium produces zearalenone (ZEN), fumonisins (FUMs) B1 and B2 as well as emerging mycotoxins, such fusaproliferin (FUs), moniliformin, beauvericin (BEA), and enniatins (ENNs). Meanwhile, Claviceps creates ergot alkaloids (EAs), while Alternaria produces altenuene, alternariol, alternariol methyl ether, altertoxin, and tenuazonic acid (Cunha et al., 2018). Certain mycotoxins are more prevalent than others, such as AFT, ZEA, OTA, FUM, PAT, and TCT. The mycotoxins mentioned in the study conducted by Haque et al. (2020) and Luo et al. (2018) are a significant cause for worry in both food sector and public health. The persistent and substantial issue of mycotoxin contamination of foods and feeds has prompted global outrage. Additionally, FUM has been known to cause toxic effects in livestock, which causes pneumothorax enlargement in pigs, hydrothorax, porcine respiratory edema syndrome, and equine leukoencephalomalacia (ELEM) in horses (Agriopoulou et al., 2020). This problem is unpredictable and uncontrollable and can crop up at any point in food production, such as pre-harvest, during harvest, drying, or storage. This can put consumers at risk of being directly exposed to mycotoxins through food products or indirectly through feed (Winter and Pereg, 2019).
Getting rid of mycotoxins during food production and processing can be difficult due to their resistance to chemical and physical treatments as well as thermal processes (Alshannaq and Yu, 2017; Marin et al., 2013). Besides, the presence of mycotoxins in the food and feed supply is a significant challenge in their removal, as they exhibit long-lasting toxicity (Laan et al., 2006; Luo et al., 2018). Numerous methods are available to control mycotoxin contamination, which primarily rely on two approaches—techniques for pre-harvesting protection and post-harvesting mycotoxin removal. These methods are studied and developed extensively (Ben Taheur, 2019). The most effective method for preventing mycotoxin production is through pre-harvest prevention strategies, such as implementing good agricultural and manufacturing practices. However, if mycotoxin contamination does occur, it becomes crucial to detect and detoxify them post-harvest. This was emphasized by Anfossi et al. (2016), Chauhan et al. (2016), and Jard et al. (2011). Proper management of crops is crucial in preventing the occurrence of mycotoxins. Negative factors that could affect the spread of mycotoxins during the growth period include drought, insect infestations, changes in temperature, and crop rotation, as stated by Osweiler (2000). According to Cheat and Oswald (2016), mycotoxins generated by mold have harmful effects on animals, such as poultry, being the most vulnerable, followed by pigs and ruminants. It is widely known that ruminants have a high ability to metabolize certain types of mycotoxins with an efficiency rate of almost 100% (Rodrigues, 2014). These mycotoxins are often lipophilic and are present in animal products. This can lead to health issues, such as the presence of AFL M1 in milk, which has been linked to serious health issues (Aslam et al., 2016).
Various adsorbents are used as nutritional supplements, resulting in recent developments in removal of mycotoxins from food and feed. Owing to their opposing polarity, the most often used fragments of clay are bentonites and zeolites (Dal Pozzo et al., 2016). A potential issue with clay absorbents is their propensity to bind to feed-borne vitamins and minerals. Mycotoxins are a notable problem discovered in many fields, such as veterinary sciences, mycology, plant science, analytical and applied chemistry, toxicology, food science, and agriculture.
Mycotoxin contamination has been reduced significantly due to the development of mycotoxin detection techniques. Numerous effective techniques have been developed since mycotoxins were first discovered in foods and feeds. These include ultra-performance liquid chromatography (UPLC), thin layer chromatography (TLC), quick strip screening tests, enzyme-linked immunosorbent serological assay (ELISA), gas chromatography (GC) combined with flame-ionization detection (FID) and electron-capture detection (ECD), and high-performance liquid chromatography (HPLC) coupled with diode array detection (DAD), ultraviolet light (UV), and fluorescence detection (FLD) (Alshannaq and Yu, 2017; Turner et al., 2015). However, mycotoxin testing is very challenging because of complex sample matrices and low-level mycotoxin contamination.
Recently, there have been a few prospects to improve significantly the performances of detection techniques because of the rapid growth of nanotechnology (Li et al., 2018; Lv et al., 2018; Zhang et al., 2019). According to Zhong (2009), nanomaterials are substances having a length of <100 nm in at least one dimension and created from both inorganic and organic substances. Different nanomaterials have proven to be useful in creating efficient methods for pre-treatment of samples and thus utilized as core of sensing techniques to detect mycotoxins accurately. This has led to significant improvements in detection techniques, including sensitivity, accuracy, and detection time (Goud et al., 2018; Yang et al., 2020a). Various strategies, including chemical, biological, and physical methods, are used effectively for eliminating mycotoxins (Agriopoulou et al., 2020; Luo et al., 2018). Recent advancements in nanomaterials have shown great potential in controlling mycotoxin contamination (Gonzalez-Jartín et al., 2019; Horky et al., 2018). These materials have been found to inhibit production, and absorb and detoxify mycotoxins. Nowadays, advanced nanomaterials are used widely to reduce mycotoxin contamination—a subject of growing interest. However, not many thorough evaluations are available on the application of nanoparticles (NPs) in preventing mycotoxin contamination. Hence, this article provides a comprehensive summary of how emerging nanomaterials are used to control mycotoxin contamination. Various applications include the use of nanomaterials for mycotoxin assay, inhibiting mycotoxin production, adsorbing mycotoxins, and eliminating mycotoxins. The information in this review offers new perspectives on controlling mycotoxins by using innovative nanomaterial-based methods.
Aflatoxins, which are highly toxic mycotoxins, are primarily produced by Aspergillus spp., such as parasiticus and flavus. They are considered as the most prevalent mycotoxins (Luo et al., 2018; Xue et al., 2019). It has been reported that there are now more than 20 types of AFT molecules (Table 1). The difurocoumarolactone group is the most significant subgroup, which includes aflatoxin G2 (AFG2) and aflatoxin G1 (AFG1), and the difurocoumarocyclopentenone group, which consists of aflatoxin M1 (AFM1), aflatoxin M2 (AFM2), AFB1, and AFB2 (Ismail et al., 2018). It is inevitable for AFG1, AFG2, AFB1, and AFB2 to be present in both food and feed. Of all these varieties, AFB1, AFB2, AFG1, and AFG2 are found commonly; AFB1 is the most dangerous aflatoxin, followed by AFG1, AFB2, and AFG2. It must be remembered that AFM1 and AFM2, formed from AFB1 and AFB2, respectively, are hydroxylated through metabolites (Esan et al., 2024). It is common to find both AFM1 and AFM2 in some animal products, including dairy products and egg yolks, as well as the flesh of animals that eat feed containing aflatoxins (Kumar et al., 2017). Of all the mycotoxins, AFTs are believed to be most potent. Owing to their interaction with proteins, enzymes, RNA, and DNA, they lead to liver disorders (Da Silva et al., 2023). AFTs are also known for their chronic hepatocarcinogenic, teratogenic, mutagenic, and toxicologic effects (Enyiukwu et al., 2014). According to Luo et al. (2018), of all the AFTs, AFB1 is considered as the efficacious and most common carcinogen found in nature. There is a growing body of evidence linking persistent anthrax poisoning to hepatic tumor or malignancy of the liver. Acute cases of aflatoxicosis are reported globally, including India, China, Kenya, and Malaysia. Symptoms include gastrointestinal discomfort, nausea, edema, and in serious circumstances death (Haque et al., 2020; Liew and Mohd-Redzwan, 2018). The AFTs are most commonly found in different nuts, such as peanuts, walnuts, almonds, pistachios, cashews, pecans, and Brazil nuts as well as cereals, such as barley, oats, wheat, rice, and corn. AFTs can also be present in food products made from these items, such as cornflakes, pasta, flour, bread, and breakfast food. Other sources of AFTs include dried fruits, animal products, spices, edible vegetable oils, wines, cottonseed, herbs, animal tissues, milk curd, eggs, and meat (Agriopoulou et al., 2020; Luo et al., 2018). Food items with low AFT levels are easier to find at small-scale farms with limited storage period; however, utilizing bags makes little difference in reducing AFT levels (Fang et al., 2022).
Table 1. Occurrences, sources, and their effects on various types of mycotoxins.
Mycotoxins | Structure | Fungi source | Occurrences | Health issues | IARC classification | References |
---|---|---|---|---|---|---|
Aflatoxins (G1, G2, M1, M2, B1, and B2) | Aspergillus flavus, A. pseudotamarii, A. bombycis, A. nomius, Emericella stellata, E. olivicola, and E. venezulensis | Rice, cereals, spices, nuts, and milk | Carcinogenic, mutagenic, immunosuppressive, hepatoxic, and teratogenic | Group 1 | Wu and Santella, 2012 | |
Zearalenone (ZEN) | Fusarium crookwellense, F. equiseti, F. graminearum, F. cerealis, F. incarnatum,and F. culmorum | Soybeans, sorghum, barley, oats, rice, and wheat | Genotoxicity, carcinogenicity, prolapse of vagina, and immunotoxicity | Group 3 | Sadrabadi et al., 2016 | |
Ochratoxins (OTA,OTC, and OTB ) | Penicillium verrucosum, Aspergillus auricomus, A. glaucus, Neopetromyces muricatus, A. fonsecaeus, Penicillium carbonarius, Aspergillus niger,and P. cyclopium | Dried vine fruit, wheat, wine, rye, raisins, grape juice, and coffee | Carcinogenic, neurotoxic, protein synthesis inhibition, immunodepressant, and mutagenic | Group 2B | De Girolamo et al., 2020 | |
Patulin (PAT) | Byssochlamys sp., Pencillium patulum, P. expansum,and P. crustosum | Pears, apricots, peaches, cherries, apples, ans olives | Pulmonary congestion, convulsions, edema, embryo toxicity, dyspnea, and pulmonary edema | Group 3 | Omotayo et al., 2019 | |
Fumonisins (FB3, FB1, and FB2) | Fusarium anthophilum, Alternaria alternate,F. moniliforme, F. napiforme, F. nygamai, and F. dlamini | Milk, corn-based products, asparagus, maize, and rice | Cytotoxicity, immunodepressant immunotoxic, apoptosis, and pulmonary edema | Group 2B | Cortinovis et al., 2013 | |
Trichothecenes (T-2, DON, and HT-2) | Cephalosporium sp., Trichoderma sp., Myrothecium sp., Stachybotrys sp., and Phomopsis sp. | Cereals | Oral lesions, leukocytosis, anorexia, infertility, diarrhea, and hemorrhage | – | Alshannaq and Yu, 2017 | |
Citrinin (CIT) | Penicillium expansum, P. citrinum, P. redicicola,and P. verrucosum | Spices, sake, stored grains, red pigments, and cheese | Immunotoxic, hepatotoxic, reproductive toxicity, and embryo toxic | – | Haque et al., 2020 | |
Ergot alkaloids | Neotyphodium coenophialum, Claviceps fusiformis, C. africanana, and C. paspali | Grass, millet, oats, wheat, and triticale | Gangrenous form, edema of the legs, paraesthesias, neurotoxicity, nausea, blindness, and vomiting | – | Topi et al., 2017 |
IARC: International Agency of Research on Cancer.
Zearalenone is primarily developed by different Fusarium species, such as Fusarium culmorum, F. equiseti, F. graminearum, F. crookwellense, and F. semitectum. This macrocyclic β-resorcyclic acid lactone was first mentioned by Bhatnagar et al. (2002) later on Tola and Kebede (2016). The ZEN-producing fungi typically thrive in storage environments having high humidity, excessive moisture, and temperate weather conditions (Luo et al., 2018). ZEN is classified as an estrogenic mycotoxin because of its resemblance to natural estrogens. This leads to a noticeable estrogenic impact on both animals and humans (Alshannaq and Yu, 2017). ZEN’s biological decomposition has been studied and is determined to be superior to physical and chemical methods. The biological breakdown of ZEN is effectively carried out by enzymes lactonase, peroxidase, and laccase (Zhang et al., 2023). In particular, females that are exposed to ZEN may have an estrogenic impact that triggers the early onset of puberty (Massart et al., 2008). Additionally, the use of ZEN may result in toxicity because of its ability to stimulate the generation of reactive oxygen species (ROS; El Golli Bennour et al., 2009). Furthermore, ZEN demonstrates stable characteristics if exposed to typical cooking temperatures, although it may be partially removed in high temperature environments (Castelo et al., 1998). ZEN is reported to found in several countries, including Germany, Philippines, China, Japan, Croatia, Iran, Thailand, and Egypt (Agriopoulou et al., 2020; Munkvold, 2017). ZEN is frequently discovered in rye, sorghum, maize, corn, wheat, and barley. Maize stands out among these crops for having a higher ZEN infection rate (Hussein and Brasel, 2001). It is worth mentioning that ZEN contamination of substances takes place concurrently with other pollutants, such as OTA, DON, FB1, and AFB1 (Luo et al., 2018). The majority of studies have included high-dose, short-term exposure in animals, neglecting the subtle chronic effects of low-dose, long-term exposure to toxins, more similar to human exposure (Han et al., 2022).
There are three categories of secondary metabolites known as ochratoxins (OTs), namely ochratoxin C (OTC), ochratoxin B (OTB), and ochratoxin A (OTA). Aspergillus and penicillium are the main producers of these metabolites. OTB is a less toxic than OTA because it does not contain chlorine. It is often be found in feeds and foods beside OTA (Udovicki et al., 2018). According to Haque et al. (2020), OTC is classified as an ethyl ester form of OTA.
According to Agriopoulou et al. (2020) and Alhamoud et al. (2019), OTA is the most hazardous and prevalent of the three types of OTs that pollute foods and feeds. It is reported that OTA can damage both liver and kidneys. Additionally, studies have shown that OTA may cause birth defects, neurological damage, cancer, genetic damage, and damage to the immune system (Mantle, 2002; Pitt, 2000). It can obstruct the production of adequate protein by hindering the hepatic and renal systems’ hydroxylase to phenylalanine activities because of its similarity to crucial amino acid phenylalanine. It is worth mentioning that OTA can hinder the creation of both RNA and DNA (Alshannaq and Yu, 2017). According to Agriopoulou et al. (2020), various food items, such as dried vine fruits, meat species, cereals, milk, alcoholic beverages (e.g. beer and wine), cocoa, coffee, and chocolate, are found to contain OTA. According to Eskola et al. (2019), cereals have the highest total exposure to OTA, accounting to approximately 60%.
Aptamers and aptasensors are used to find mycotoxins in food. However, when these sensors are used to detect mycotoxins in a complicated food matrix, their setup has to be optimized. Detoxification employing organic extract, ozone, and cold plasma therapy was also discovered to be a successful treatment. Thus, development of poisonous fungi can be restrained due to biocontrol and detoxication techniques (Ganesan et al., 2022).
Patulin (PAT) is a polyketide mycotoxin which is primarily produced by a number of aspergillus and penicillium species, including Penicillium patulum, Aspergillus clavatus, P. griseofulvum, P. crustosum, P. leucopus, P. urticae, and P. expansum (Agriopoulou et al., 2020; Luo et al., 2018). According to Walravens et al. (2014), of all the species, P. expansum is known to be the most frequent producer of PAT. So far, studies have shown that PAT can cause various long-term health issues, such as damage to the liver and kidneys, mutagenicity, neurotoxicity, teratogenicity, genotoxicity, and carcinogenesis. In addition, it can also cause immediate health difficulties such as gastrointestinal issues, hemorrhage, nausea, ulceration, and vomiting (Zhong et al., 2018). It has been found that PAT is present in apple-processing products, vegetables, and fruits. It has been also discovered in other fruits, such as grapes, pears, oranges, and their processed variants (Agriopoulou et al., 2020). During production of fruit juices, PAT is transferred without being removed from rotten fruits (Romero Bernal et al., 2019). Furthermore, according to a Chinese law, the European Union (EU), and the US Food and Drug Administration (FDA), the maximum allowed limit of PAT in apple and fruit juices is 50 g/L/kg (Vidal et al., 2019). PAT detoxification in apple-based products requires further research on the fermentation-related PAT degradation process by Saccharomyces cerevisiae (brewer’s yeast or baker’s yeast) and development of debris from the degradation . S. cerevisiae CICC 31084 was effective at harmful PAT (Yang et al., 2023).
Fusarium toxins, also known as fumonisins, are primarily generated by the fungus Fusarium proliferatum and F. verticillioides. According to Rheeder et al. (2002), fumonisins are produced under wet and warm environmental conditions. The classic physical and chemical techniques used for removal of mycotoxins have various blockades, such as an unstable effect, significant nutritional loss, influence on the palatability of feed, and difficulties in mass manufacturing. Nevertheless, there are many ways to stop FUMs from getting into the food supply (Qu et al., 2022). In addition, Aspergillus niger (A. niger) has been shown to create FUMs on grapes and raisins (Mogensen et al., 2010). At present, more than 28 different types of FUMs have been identified and classified into four groups: fumonisin B (FB), fumonisin C (FC), fumonisin A (FA), and fumonisin P (FP). Among these, FBs (such as FB2, FB3, and FB1) are most prevalent in nature, with FB1 being the most frequently detected FUM with highest concentration, and it is also known to be the primary cancer-causing agent in humans (Alberts et al., 2016; Luo et al., 2018). FUMs are toxic to animals, causing equine horse leukoencephalomalacia as well as pulmonary edema syndrome and hydrothorax and thorax expanding in pigs (Agriopoulou et al., 2020). Additionally, studies have reported a correlation between the consumption of maize kernels contaminated with FUMs and neural tube defects and higher incidences of cancer of the esophagus in humans (Haque et al., 2020).
Trichothecenes are produced by many fungus species, such as fusarium, trichoderma, stachybotrys, cephalosporium, verticimonosporium, trichothecium and myrothecium (Udovicki et al., 2018). Presently, more than 200 TCT variants have been identified and are categorized into four groups: A, B, C, and D (Da Silva et al., 2023). Examples of A type variants include HT-2 toxin, neosolaniol (NEO), diacetoxyscirpenol (DAS), and T-2 Toxin. B type variants include DON, fusarenon-X (FX), and nivalenol (NIV), among others. According to Ferrigo et al. (2016), A-type TCTs are considered as the most toxic group, compared to type B analogues. As stated by Luo et al. (2018) and Haque et al. (2020), A-type variants have toxic effects that result in necrotic lesions, myelotoxicity, hematotoxicity, and a slowdown in growth at contact location. These also cause vomiting, hemorrhage, and diarrhea. These toxins are primarily found in cereals, such as maize, rice, barley, rye, oats, and wheat. Similarly, these have been discovered in soybeans, sunflower seeds, peanuts, bananas, potatoes, beer, certain cereal-based noodles, breakfast cereals, and bread (Alshannaq nd Yu, 2017).
Citrinin (CIT) is a secondary benzopyran metabolite that is mostly produced by Penicillium expansum, Aspergillus spp., and Monascus spp. CIT is nephrotoxic and genotoxic, affecting both humans and animals. In order to effectively control toxins at various phases of production and processing, adequate Hazard Analysis Critical Control Point (HACCP) plans, good manufacturing practices (GMPs) and good agricultural practices (GAPs) are necessary. Additionally, a number of biological, physical, and chemical techniques are used to reduce CIT formation and contamination and destroy it, thus preventing it from entering the food chain (Kamle et al., 2022). It has been reported that CIT is linked to both pig kidney disease and yellowed rice illness. According to Edite Bezerra da Rocha et al. (2014) and Haque et al. (2020), CIT and OTA together hindered RNA synthesis in the kidneys of mice. In addition, contact with CIT can have cancer-causing effects, as noted by Luo et al. (2018). Stored cereal grains and barley are found to be an excellent setting for growth of the fungus that causes CIT. Additionally, CIT has been discovered in marred beans, dairy products, rice, pomaceous fruits, fruit juices, wheat, nuts, rye, and spices (Haque et al., 2020; Tanaka et al., 2007).
A lethal alkaloid combination, known as ergot alkaloids, is mostly found in the sclerotias (a compact black or purple mass of hardened fungal mycelium containing food reserves) of Claviceps and Neotyphodium species (Grusie et al., 2018; Haque et al., 2020). According to Grusie et al. (2018), the most frequent EAs identified concurrently in contaminated foods are ergocornine, ergocristine, ergocryptine, ergosine, ergometrine, and ergotamine. Accordingly, EA toxicity causes paroxysm, mirage, agalactia, feverishness, and incineration in humans, and hypersensitivity, cramps, decreased productivity, internal hemorrhage, suppression of lactation, miscarriage, diarrhea, and corrosion in livestock (Grusie et al., 2018; Haque et al., 2020; Hulvova et al., 2013). The current investigation discovered that whereas concentrations of EAs found in pelleted grain-based matrices may be higher than in mash feeds of comparable composition, pelleting did not worsen the detrimental physiological effects of ergot. Related heat and pressure of pelleting could make it simpler to extract EAs for tests (Stanford et al., 2022). According to Topi et al. (2017), EAs are typically found in various grains, such barley, rye, triticale, oats, wheat, and millets. The highest proportion of fungal contamination among these cereals is observed in rye, as reported by Tittlemier et al. (2015).
The utilization of core-shell NPs for mycotoxin detection in particular involves the association of core-shell NPs with aptamers or the use of antibodies for the advancement of biosensors. As shown, different NPs with core shells were created and used in pre-treatment of samples, lateral flow immunoassay (LFIA), chemiluminescence sensors, electrochemical analysis, fluorescence, and surface-enhanced Raman spectroscopy (SERS) detection. This has made possible to detect important mycotoxins, such as AFs, OTA, DON, and ZEN, with extreme sensitivity and selectivity. Notably, every strategy offers benefits of its own. (Zhai et al., 2023).
For accuracy, several analytical methods, such as ELISA, HPLC, and TLC, are available and used frequently for the precise measurement of mycotoxins (Anfossi et al., 2016; Chauhan et al., 2016). Mycotoxins, for instance, are easily distinguished using TLC because of their varying migration velocities over an absorbent material layer (Hussain et al., 2021). By contrast, HPLC separates mycotoxins in mobile phase and measures their amount by means of fluorescence or UV detection (Pandey et al., 2021). The ELISA uses mycotoxin-specific antibodies to detect and quantify mycotoxin levels (Zhan et al., 2021). The present research concentrated on increasing detection limit, time consumption, sample consumption, and convenience of use (Berthiller et al., 2017; Guo et al., 2015; Sadhasivam et al., 2017; Selvaraj et al., 2015). This is because early detection is necessary to safeguard health.
According to practice, NPs are used in two distinct ways in detection systems (Rai et al., 2015; Rhouati et al., 2017). Direct interaction between NPs and identified chemical occurs at the receptor level. This system needs sufficient repeatability and specificity. NPs develop to improve signal to the detector’s transducer. Rai et al. (2015) have provided an overview of these technologies. The cited study summarized potential methods for immobilizing biomolecules and concluded that mycotoxins involved more investigation into the development of nano biosensors with increased rigidity and toughness. Because of their maximum surface-to-volume ratios, NPs are advantageous in this situation because they can bind larger amounts of mycotoxins (Gontero et al., 2017).
Over the past 10 years, research on nanomaterials had concentrated on metal NPs, polymers, quantum dots (QDs), super paramagnetic NPs, and carbon nanotubes (CNTs). Additionally, the usage of NPs enables diverse surface ornamentation from functional groups, including COOH, CH3, NH2, and OH as well as numerous alterations with the help of appropriate ligands. The immune detection of mycotoxins is emphasized in the present research. A fast-evolving method that includes NPs (such as sensitivity) and antibodies (such as specificity) is the lateral flow immuno chromatographic test. The threshold of diagnosis for several mycotoxins is between 0.1 and 10,000 mg/mL using gold NPs of QDs (Xie et al., 2015). For detecting AFL B1, immuno electrodes based on bismuth oxide nanorods were developed (Solanki et al., 2017) (Figure 1). The third-generation immunosensors function by direct electron transfer of analytes to electrodes and has quick response (15 s), hypersensitivity (1.132 A/mg/dL), wide linear spectrum (1–70 mg/dL), and minimal detection threshold (8.715 mg/dL) (Zhang et al., 2004).
Figure 1. Various immunodetection systems. (A) A signal-amplifying electrosensor that relies on the interaction of antibody along with mycotoxin. (B) A lateral simple immunoassay for the visual identification of mycotoxins.
Recently, ready-to-use immuno chromatographic test strips with detection threshold of 0.05 and 0.1 mg/mL were suggested for the concurrent identification of T2 toxin and ZEA. Magnetic NPs with an antibody label are used for instant pre-treatment to obtain perfect sensitivity and quick testing (Petrakova et al., 2017). Aptasensors for the simultaneous detection of AFL B1 and OTA A using surface-added Raman scattering are developed using silver(Ag)@gold(Au) core-shell NPs. Plasmonic interaction at the intersection of gold core and Ag shell is the primary source of stable and quantifiable signals in Raman scattering aptasensors (Zhao et al., 2015b).
Multiplex detection in one step of several mycotoxins has been the subject of recent research. This streamlines the whole analysis, regardless of whether it is needed for a device in the form of a strip or another shape (Sun et al., 2016). In order to identify 20 mycotoxins, Kong et al. (2016) created semi-quantitative and quantitative multi-immuno chromatographic strips using gold NPs as a marker. The capacity to interpret results with a naked eye is its benefit. According to the estimates made by Kong et al. (2016), the sight detection thresholds for FUMs, DONs, AFs, ZEAs, and T2s were different. Sensitivity and reliability are not sufficient for detection. Owing to the fact that plant enzymes alter the structure of mycotoxin derivatives, it is difficult to identify these using standard analytical methods (Berthiller et al., 2013).
As a successful pre-treatment step of masked derivates, enzyme or acid hydrolysis is frequently used prior to mycotoxin testing (Goryacheva and De Saegar, 2012). Mass spectroscopy could also reveal covered up mycotoxins (Aqai et al., 2011; Huybrechts et al., 2015; Nakagawa et al., 2011). Initially, a summary of categorization, the frequency and toxicity traits of prevalent mycotoxins, was provided. Then, after providing description of molecularly imprinted polymer (MIP) composites and an overview of those composites, overly concentrated enhances the functioning of NPs in relation to popular subcategories of sensors based on MIP, including quartz crystal microbalance, electrochemical, chromatography, surface-added Raman scattering, and surface plasmon resonance (SPR) (Mukunzi et al., 2022). NPs might help with mycotoxin separation or detection as well as the emergence of a proof-of-concept tool for locating unidentified updated masked mycotoxins, which is still a significant difficulty. Small peptides are used to extract and clean up mycotoxins in mycotoxin testing, enhancing delicacy with repeatability of conventional monitoring of equipment. Past techniques have a tough time in detecting mycotoxins in food and food products in real time. However, antigen–antibody-based immunoassays can do this. Despite the fact that tiny peptides can be anti-immune complex peptides, competitive antigens, coating antigens, simplifying antibody preparation, or avoiding the use of toxin standards have a crucial role in mycotoxin detection. Additionally, these strategies have flaws, such as the requirement to employ mycotoxin standards and to consider the complexity and difficulty of creating anti-toxin antibodies (Zhao et al., 2022).
For the purification and monitoring of harmful substances in foods, which include aromatic hydrocarbons that are polycyclic (Li et al., 2018), fluoroquinolones mycotoxins (Wen et al., 2020; Yang et al., 2020b) and others nanomaterials, particularly magnetic NPs (MNPs), are used in conjunction using different analyses platforms (e.g. LC-MS/MS and HPLC) (Liu et al., 2020; Zhao et al., 2017b). This study compared the efficacy of ELISA and HPLC-fluorescence techniques for detecting FUM in maize, and found the accuracy of both techniques (as evaluated by trueness and accuracy), with HPLC utilized as a confirmatory method. In our investigation, all performance metrics, including recovery and repeatability data, fulfilled the EU standards for the acceptability of analytical procedures for detection and quantification of FUMs (Sokolovic, 2022). Karami-Osboo et al. (2015) used HPLC-UV to analyze DON, with a limit of detection (LOD) of 45 g/kg and a limit of quantitation (LOQ) of 150 g/kg in wheat flour by utilizing Fe3O4 MNPs as a cleaning reagent for extraction of mycotoxins. To extract AFB1, AFB2, AFG1, and AFG2 from samples of nuts and cereals, Fe3O4 MNPs were also utilized (Karami-Osboo and Mirabolfathi, 2017). These samples were then combined with HPLC equipped with a fluorescence detector to detect AFTs. Notably, Guo et al. (2015) used UHPLC-MS/MS in conjunction with magnetic multi-walled carbon nanotubes (m-MWCNTs), magnetic solid-phase extraction (MSPE), to purify and identify TCTs type A, such as NEO, HT-2 toxin, DAS, and T-2 toxin (Dong et al., 2016) (Figure 2). Used m-MWCNTs as sorbents founded on the same technique for the extraction and detection of ZEN and its derivatives in corns (Han et al., 2017). Additional magnetic NPs are used for HPLC-based mycotoxin testing (Capriotti et al., 2019), including Co3O4@C@ MIP (Wu et al., 2018), metal-organic framework (MOF), magnetic nanographene (Durmus et al., 2020; Huang et al., 2019), magnetic zeolitic imidazolate frameworks (ZIFs; Gao et al., 2019), and Fe3O4/rGO. Despite the fact that HPLC-based tests have demonstrated excellent empathy, excellent precision, and strong dependability to detect mycotoxins, they are labor-intensive, time-consuming, and difficult, particularly dependent on costly instruments and professional operators (Goud et al., 2019; Zhang et al., 2020).
Figure 2. Flowcharts of magnetic solid-phase extraction (MSPE) method.
According to Niu et al. (2019) and Xue et al. (2019), the basis for immunoassays is the interaction of antibodies with antigens and signal molecules for labeling the contact, and can be recognized from the results of its detection through naked eye and straightforward analytical instruments. Owing to the highly focused detection association of antibody with antigen, immunoassays have been the most widely used detection method for fast analysis in a non-laboratory scenario (Bu et al., 2020; Niu et al., 2019). Owing to its benefits of chemical stability, simple synthesis, and inexpensiveness gold (Au) NPs are frequently employed for mycotoxin detection. In addition, a number of new substances have been researched, showing promise for improving signals. The development of manufactured vibrant NPs for multiplex immunoassay analyte detection (Adunphatcharaphon et al., 2022). Amazingly, the utilization of immunoassays has been benefited greatly from the progress of nanotechnology.
Different nanomaterials, such as covalent organic frameworks (COFs), magnetic particles, silicon NPs, upconversion NPs (UCNPs), QDs, metal nanomaterials, carbon nanomaterials, and MOFs, have drawn growing attention due to their distinctive properties, such as strong fluorescence, variable diameters, improved surface reactivity, and superior electrical 2conductivity. These materials have also been widely used for boosting immunoassay spectacles, particularly sensitivity (Alhamoud et al., 2019; Li et al., 2020; Su et al., 2019). Two novel immunoassay systems (APN-ELISA and PN-ELISA) for OTA detection were created by using nanobodies as coated antibody and the phage-displayed peptidomimetic and ALP-tagged peptidomimetic fusion as a competing antigen. The operation of recognizing APN-ELISA and PN-ELISA was equivalent to or even superior to mimotope-based immunoassays used for OTA (Yang et al., 2023). Additionally, a wide range of opportunities for nanomaterial-based immunoassays in determining the presence of mycotoxins have been realized (Chen et al., 2020; Liu et al., 2020; Rai et al., 2015; Wang et al., 2016; Xue et al., 2019). Nanomaterials have played a crucial role in these nanomaterials-based immunoassays, which immobilize biomolecules and alter electron transport by lowering or increasing of its producing signals (Xue et al., 2019). The noticeable enhancing of signal in immunoassays is caused by the utilization of nanomaterials having a surface that is naturally nanoscale-sized and can provide conducive biocompatible environment for the immobilization of biomolecules. Some NPs, such MNPs, MOFs, AgNPs, COFs, and Au NPs, have wide surfaces and strong biocompatibility, which make them useful for binding biomolecules such as cysteamine, antibodies, and enzymes as well as acting as electroactive indicator carriers (Sharma et al., 2010; Xue et al., 2019). As an illustration, MOFs, AgNPs, MNPs, and Au NPs have been utilized to immobilize enzymes, and synthetic materials of NPs and enzymes investigate act as signal indicates for immunoassays signal amplification (Goud et al., 2018; Xue et al., 2019). Au NPs, QDs, and UCNPs are the examples of nanomaterials with exceptional optical properties that could be used for signaling mycotoxin immunoassay categorization (Jiang et al., 2020; Xue et al., 2019). Particularly, silver/gold (Ag/Au) NPs are worthy of enhancing information in mycotoxin immunoassays (Xue et al., 2019). Recently, a novel SERS-based subsequent-generation immunosensor targeting and additionally determining six mycotoxins (T-2 toxin, ZEN, FB1, OTA, DON, and AFB1) in maize employed Raman reporter molecules (4-mercaptobenzoic acid [MBA] and 5,5-dithiobis-2-nitrobenzoic acid [DTNB]) to modify Au@Ag core-shell NPs for SERS nanoprobes.
T-2 toxin, ZEN, FB1, DON, OTA, and AFB1 could be recognized using the recommended SERS-based flowing laterally immunosensor with LODs = 8.6, 0.96, 0.11, 0.26, 15.7, and 6.2 mg/mL, respectively (Zhang et al., 2020; Figure 3). In order to keep enhancing the degree of specificity in the immunoassays of mycotoxins, emerging nanomaterials with enzyme-like catalytic activity (specifically nanozyme) can be further investigated as catalytic labels that substitute enzymes for signal generation/amplification of immunoassays in future investigations (Niu et al., 2019; Zhang et al., 2019, 2020). Furthermore, despite the fact that the use of nanomaterials-based immunoassays for mycotoxin detection is common, the superior antibodies utilized in these procedures still have certain inherent limitations, such as expensiveness, complicated preparation, and time-consuming. As a possible substitute for antibodies, several molecular recognition components, such as aptamers and MIPs, have been created as biosensors for identification of mycotoxins.
Figure 3. Representation of a multiplex SERS-based lateral circulation of immunosensor for mycotoxin analysis.
Aptamers are a subset of molecular recognition elements having unique reactions with a variety of analytes. These are formed from molecules of peptides or nucleic acid. Aptamers are widely used in the creation of aptasensors because to their recognition selectivity toward numerous analytes (Goud et al., 2018; Sharma et al., 2015). Different nanomaterials, such as carbon-based nanomaterials, magnetic NPs, metal oxide NPs, UC NPs, COFs, MOFs, and noble metal NPs (such as graphene and CNTs), fit together into aptasensors to produce new aptasensors based on nanomaterials (Sharma et al., 2015; Xue et al., 2019). Furthermore, the detection of mycotoxins has been extensively caused by these aptasensors based on nanomaterials (Goud et al., 2019; Luo et al., 2020; Zhu et al., 2020).
Nanomaterials play a few key roles, such as alternative to enzyme labels (Bulbul et al., 2015; Tian et al., 2020) fluorescence quencher, immobilization support signal creation, signal amplification, etc., in aptasensors based on nanomaterials for mycotoxin screening (Goud et al., 2018; Sun et al., 2018). Developing nanozymes in the construction of aptasensors for mycotoxin assay (Goud et al., 2019; Rhouati et al., 2017) has outlined the application of smart sensors that utilize nanomaterials in mycotoxin testing. Advanced nanozymes have been employed effectively in the aptasensing of mycotoxins as signal generation/amplification labels (Chatterjee et al., 2020; Tian et al., 2019). Aptasensor with colorimetry for identifying ZEN was constructed by employing ZEN aptamer and Au NPs with peroxidase-mimicking activity (Lin et al., 2024). Although clustered regularly interspaced short palindromic repeats and CRISPR-associated protein 9 (CRISPR/CAS 9) technology has been implemented in a number of aptasensor scaffolds and has significantly increased their efficacy, there are still some significant technological issues that need to be resolved. Breakthroughs may potentially result by putting together cutting-edge computational modeling and algorithms, anti-matrix interference materials, user-friendly portable diagnostic equipment, the Cas-aptamer-based sensor which can detect a wide range of biological processes (Suliman Maashi, 2023). ZEN could be linearly detected with the suggested aptasensor of 10–250 mg/mL with a 10-mg/mL LOD as reported by Sun et al. (2018). Similar to this, a new colorimetric aptasensor was built on aptamer-controlled MnCo2O4 nanozyme activity for OTA testing. A low LOD of 0.08 mg/mL allowed for the selective detection of OTA in maize samples using the existing aptasensor (Huang et al., 2018).
Recently, a new colorimetric aptamer biosensor was created to detect simultaneously OTA and AFB1 in agricultural products. Thymolphthalein (TP)-GO and Fe3O4/GO were combined, utilizing AFB1 aptamer, to provide a platform to carry out AFB1 testing. The platform separation took place with AFB1 present. Owing to the production of TP when alkaline conditions are present, the solution took a dark blue hue following the magnetic separation of Fe3O4/GO. Similar to this, another platform was created by combining Fe3O4@Au and Au NPs using complimentary OTA aptamer strands. Owing to the presence of OTA, platforms made of Fe3O4@Au crumbled, allowing Fe3O4@Au to separate magnetically. When the base material 3,3',5,5'-tetramethylbenzidine (TMB) is catalyzed by Au NPs exhibiting enzyme-like activity, a distinct color change takes place. AFB1 was exponentially detected between 5 mg/mL and 250 mg/mL using designed aptamer biosensors, while OTA was identified linearly between 0.5 mg/mL and 80 mg/mL (Zhu et al., 2020). Despite nanomaterial-based aptasensors having already been used widely in mycotoxin testing, their commercial success is significantly hindered by intricate designs and expensive amplification processes of aptamer. Likewise, for the recognition of small molecules, nanomaterial-based aptasensors require a lot of energy and produce nonspecific interactions, which limit to some extent the scope of their application.
Molecularly imprinted polymer, an exceptional biomimetic substance, is commonly employed as a recognition component for biosensors with regard to the antibody–antigen understanding concept in conjunction with antibodies and aptamers (Alhamoud et al., 2019; Cieplak and Kutner, 2016). The MIPs have emerged as an effective substitute for antibodies for producing sensors and have achieved major advancements in the application of mycotoxin testing because of benefits, such as potential applications, high specificity, quick binding kinetics, easy preparation, good stability, and low cost in harsh environments (Alhamoud et al., 2019; Pacheco et al., 2015).
Based on its manner of detection or immobilized biorecognition element, biosensors can be categorized as follows. First, a biosensor’s transducer type-optical, electrochemical, thermal, or mass-based-can determine its detecting methodwith respect to the biorecognition element technique, mycotoxin sensing methods concentrate on immunosensors or aptasensors, which use antibodies or aptamers as biorecognition elements. The used MIPs are novel synthetic biorecognition elements. A particular analyte must be recognized and associated by a biorecognition element, regardless of the molecular structure of a bioreceptor. Analyte contact (and potential binding) and the biological recognition event (transduction) combine to produce a proportionate signal that is amplified and transformed via a transducer to calculate analyte concentration (Meira et al., 2023).
The capacity of NPs for signal production and amplification is successfully linked with particular recognition features of MIPs to further enhance the features of mycotoxin detectors based on MIPs (Xue et al., 2019). MIP’s deficiency in conductivity and electrocatalytic activity makes it difficult to be used in practical applications. Because improved affinity and binding kinetics are made possible, conventional MIPs make task simpler when attached to a transducer surface. A potent tool for their usage in the field of sensing has been developed by the manufacture of nano-sized MIPs for mycotoxins analysis, either solely or in conjunction with NPs. As a result, scientists are urged to use both new and NPs at hand to expand the applications of MIP composite materials. The two main factors that contribute to this are the predominance of serological testing in diagnosis and the technical difficulties that traditional molecular imprinting must overcome (Mukunzi et al., 2022). Numerous nanomaterials, such as MOFs, QDs, CNTs, and metal NPs, have been used in developing MIP-based sensors for detecting mycotoxins (Bagheri et al., 2018; Goud et al., 2018). A novel electrochemical sensor to identify OTA was created by modifying multi-walled CNTs with glassy carbon electrode and MIP. OTA could be detected directly in the range of 0.050–1.0 M using the existing glassy carbon electrode (GCE)/MIP/MWCNT with an LOD of 0.0041 M and an LOQ of 0.014 M by Pacheco et al. (2015). Another work used chitosan (CS) composites with Ru(bpy)32+-doped silica NPs (Ru@SiO2 NPs), Au NPs, and MIP-modified GCE to effectively construct a novel MIP-based electrochemical luminescence (MIP-ECL) sensor for the ultrasensitive identification of FB1. Ru@SiO2 NPs were used as ECL luminophores in the suggested ECL sensor, while Au NPs functioned as intensifying ECL with a localized surface plasmon resonance (LSPR) source. According to Zhang et al. (2017a), the developed MIP-ECL sensor allowed for the identification of FB1 with a wide range of 0.001–100 mg/mL with an LOD of 0.35 mg/mL. In particular, revolutionary AgNPs@ZnMOF nanozymes’ exceptional peroxidase-mimicking catalytic activity and MIP’s exclusive recognition ability, Bag herietal were integrated succeeded in developing a new, highly effective nanozymes-based MIP fluorescence sensor to identify PAT, which ranged from 0.1 to 10 mol/L with a minimal LOD of 0.06 mol/L (Bagheri et al., 2018). Contrary to a popular belief regarding MIPs that there is a potential recognition component for sensor development, they lack the inherent bioreceptors like antibodies aqueous environment selectivity (Ashley et al., 2017; Figure 4).
Figure 4. The method of (A) MIL-101@MIPs synthesis; (B) extraction and purification (Huang et al., 2019).
Antibacterial NPs have been developed for the past 10 years as a remedy for harmful bacteria’s drug resistance. Their capacity to combat the production of mycotoxin has been hampered by the distinctions between bacteria and fungus. Bacteria have only one cell, but the majority of fungus has several cells. Additionally, bacteria have three different forms whereas fungi have a variety of shapes that can result in the production of mycelium. Owing to all these variations, fungi are more resilient and antibiotic-resistant (Sureka et al., 2014). It is now feasible to utilize antifungal medications that are very effective, thanks to the development of antifungal nanomaterials and introduction of nanotechnology. The generation of mycotoxin is now inhibited by the use of several nanomaterials (Hassanzadeh Davarani et al., 2018; Roque et al., 2017). Antifungal NPs, which are simple to make on a big scale, could be used in practice to avoid the occurrence of mycotoxins. Recent scientific studies, summarized in Table 2, claim that the antifungal approach is divided into two different paths. In general, there are two types of nanomaterial-based antifungal strategies: those that encapsulate antifungal compounds into polymeric nanomaterials and release them when the right conditions (such as the presence of enzymes, higher temperature, and pH variation) are available, and those that directly depend on nanomaterials to prevent the growth of fungi. First, a polymeric nanocage is used to enclose an antifungal substance whereas cargo release from nanopolymers is possible at right conditions (enzymes existence, pH shift, or a higher temperature); the instability in air is perhaps the method’s biggest drawback. Second, the impact of inhibition is only achieved by NPs. This technique primarily utilizes stable, quick-acting, and environment-friendly metal NPs. The creation of nanobiocomposites from plants, microbials, and animal sources that exhibit reduced toxicity and enhance their primary properties is another benefit of green synthesis (Adelere and lateef, 2016). Various nanogels have been used, as described previously (Beyki et al., 2014; Khalili et al., 2015), to encapsulate antifungal drugs against fungus. Enhancement in antifungal activity is achieved by encapsulating Thyme essential oil and Mentha piperita essential oil in nanogel chitosan–benzoic acid and nanogel chitosan–cinnamic acid, respectively (Beyki et al., 2014; Khalili et al., 2015). Additionally, because of their exceptional antibacterial abilities and metal NPs with a high surface area–volume ratio, these NPs have been regarded as one of the best antifungal agents (Abd-Elsalam et al., 2017). Other NPs that have been reported to be effective against fungi include magnesium oxide (MgO) NPs, zinc oxide (ZnO) NPs, nitrogen-doped titanium oxide–palladium oxide (TiON/PdO) NPs, and N- and F-co-doped TiO2 NPs as stated by Abd-Elsalam et al. (2017) (Figure 5). As reported by Abd-Elsalam et al. (2017), preventing mycotoxin-producing fungi from expanding is possible by ZnO NPs.
Table 2. Synthesized nanoparticles used for antifungal activity.
Type of nanoparticles | Fungal species | Dose concentration | Zone size | References |
---|---|---|---|---|
Silver | Alternaria flavus | 5 μg/mL | 4.5nm | Zhao et al., 2017a |
Alumina nanoparticle,Ag-doped titan oxide | Fusarium oxysporium | 400 mg/L | 200nm | Shenashen et al., 2017 |
Chitosan silver nanocomposites | Fusarium oxysporum | 100 μg/mL | 370nm | Dananjaya et al., 2017 |
Copper | Penicillium digitatum | 20 and 60 μg/mL | NA | Khamis et al., 2017 |
Sliver | Candida parapsilosis | 0.01 mmol/mL and 0.02 mmol/mL |
22mm and 27mm | Hawar et al., 2022 |
Selenium | Fusarium mangifera | 300 μg/mL | 14mm | Shahbaz et al., 2023 |
Iron oxide | Pencilliumchrysogenum | 0.5 mg/mL | 28.67±1.53 mm | Praveen et al., 2018 |
Silver | Phaseolina | 1,000 μg/mL | 13 mm | Vijayabharathi et al., 2018 |
Iron oxide | Cladosporium herbarum | 75 μg/mL | 40 mm | Henam et al., 2019 |
Selenium | Solani | 1mM | 45mm | Hashem et al., 2021 |
MgO and FeO | Alternaria alternata | 0.5 mg/mL | 16.33±1.15 mmand 15.66±0.57 mm | Koka et al., 2019 |
ZnO and Fe-doped ZnO | Niger | 40 μL | 13 mm and 18 mm | Ferin Fathima et al., 2020 |
Silver | Alternaria sp. | 100 μL | 21.6 ± 1.5 mm | Win et al., 2020 |
Silver | Rhizopus stolonifer | 0.1, 0.2, and0.5 mg/mL | 90 mm | Moreno-vargas et al., 2023 |
ZnO–CuO | Fusariumoxysporum | 1,000 μg/mL | 22.8 ± 0.76 mm | Gaber et al., 2023 |
Figure 5. (A) Experimenting with N- and F-co-doped TiO2 NPs’ antifungal activity and chemical structure. (B) Suggested mechanism of N- and F-co-doped TiO2 NPs’ antifungal activity. Under visible light irradiation, the labeled NP produces hydroxyl radicals (OH) at the surface of fungal cell wall. The fungal cell wall’s glucan and chitin layers react with this radical, degrading the cell wall and causing cell death.
The biosynthesized Ag NPs show exceptional capabilities for suppressing four mycotoxigenic fungus strains, such as A. ochraceus, Fusarium solani (F. solani), A. flavus, and A. alternata. Notably, Zhao et al. (2017b) evaluated the results of Ag NPs on the suppression of AFT formation and Luo et al. appropriately synthesized Ag NPs for the suppression of A. flavus growth with a common width of 4.5 nm. Fusarium oxysporum fungus development in vegetables, such as tomatoes, and fruits could be entirely stopped by visible light irradiation (Mukherjee et al., 2020). The treatment of Fusarium head blight (FHB) could be benefited from the combination of Ag NPs and DON-reducing fungicides, which may also be employed to create fungicidal formulations. Therefore, future research is required to assess Ag NPs’ antibacterial properties in a realistic agricultural setting (Jian et al., 2022). Ag NPs interfere with intracellular structures, alter transcription throughout the genome, and disrupt the integrity of fungal cell wall and cell membrane to impede their development. However, Ag NPs inhibit the UvKmt6-mediated H3K27me3 alteration, which suggests that Ag NPs and mycotoxin-reducing fungicides could be used in tandem to reduce rice false smut disease. These findings aid in understanding Ag NPs’ usage and potential drawbacks in the governance of plant fungal infection (Wen et al., 2023).
The maximum zone of inhibition against Penicillium chrysogenum (P. chrysogenum) with iron oxide (FeO) NPs was 28.67 ± 1.53 mm at 0.5 mg/mL (Praveen et al., 2018). The green-synthesized Ag NPs have a considerable antifungal impact on the plant pathogen Candida parapsilosis at a concentration of 0.01–0.02 mmol/mL with the maximium zone of inhibition being 22–27 mm (Hawar et al., 2022). The highest level of antifungal activity was demonstrated by selenium (Se) NPs at a concentration of 300 μg/mL and an inhibitory zone of 14 mm (Shahbaz et al., 2023). According to Vijayabharathi et al. (2018), synthesized Ag NPs inhibited Macrophomina phaseolina (M. phaseolina) with a high zone of inhibition of 13 mm at 1,000 μg/mL. With a concentration of 75 μg/mL and a size range of 40 mm, Fe2O3 NPs appear to have more antifungal action against Cladosporium herbarum (Henam et al., 2019). In contrast, 1 mM of Se NPs produced an inhibitory zone of 45 mm and exhibited the greatest antifungal action against Rhizoctonia solani (R. solani) (Hashem et al., 2021). In contrast to other fungal species, green MgO and FeO NPs demonstrated antifungal activity toward the fungus disease Alternaria alternata. Both MgO and FeO NPs exhibit greatest inhibitory efficacy at a concentration of 0.5 mg/mL, compared to other concentrations. The largest size range is 15.66–0.57 mm and 16.33 × 1.15 mm (Koka et al., 2019). ZnO- and Fe-doped ZnO NPs suppressed A. niger’s antifungal activity with a high zone of inhibition of 13–18 mm at 40 μL (Ferin Fathima et al., 2020). At a concentration of 100 μL in the zone range of 21.6 ± 1.5 mm, Alternaria sp. showed the highest antifungal activity in green production of Ag NPs (Win et al., 2020).
Two fungus species, Rhizopus stolonifer and F. solani, were used in the manufacture of Ag NPs to study the antifungal activity as a function of time and concentration. According to Moreno-Vargas et al. (2023), the greatest zone was strongest in the 120 h of testigo, at 0.1, 0.2, and 0.5 mg/mL, which demonstrated a 90-mm zone of inhibition. When compared to other produced NPs, zinc oxide–copper oxide (ZnO–CuO) NPs had the strongest antifungal activity, but the starting materials (zinc. AQnacetate, copper acetate, and cross flow filtration) had no effect. Additionally, ZnO–CuO NPs demonstrated good antifungal efficacy against F. oxysporum, with an inhibition zone of 22.8 ± 0.76 mm at a dose of 1,000 μg/mL (Gaber et al., 2023). Interestingly, photocatalytic and antifungal activity and disinfection mechanism of PdO NPs against F. graminearum macroconidia was investigated in visible light. The PdO NPs were able to adsorb significantly on the outer layer of F. graminearum macroconidium due to opposing surface charges of macroconidium and PdO NPs, thus facilitating the photocatalytic disinfection of macroconidia. The antifungal effect of PdO NPs on F. graminearum macroconidia could be due to the ability of ROS to destroy cell walls and membranes (Zhang et al., 2013) (Figure 6).
Figure 6. Palladium-modified nitrogen-doped titanium oxide (TiON/PdO) photocatalyst’s antifungal efficacy and mechanism against agricultural pathogenic F. graminearum (Zhang et al., 2013).
Emerging nanomaterials have shown tremendous potential because of their extensive surface area (Ramadan et al., 2020; Santana-Mayor et al., 2020). Mycotoxins have diverse structural compositions, which result in a range of physical and chemical characteristics. Although mycotoxins may often be classified as either nonpolar or polar molecules, certain mycotoxins are reportedly intermediate in nature. TCT is a polar mycotoxin whereas ZEN is nonpolar, and both FUMs and AFTs are reportedly very polar (Horky et al., 2018; Stroka and Maragos, 2016). Nanomaterials respond to a variety of mycotoxins because of former’s polar and nonpolar behavior and adjust their characteristics to a variety of physicochemical conditions.
Numerous NPs, such as magnetic Fe3O4 modifiers, chitosan polymeric NPs, and carbon nanomaterials, are used extensively in mycotoxin adsorption (Horky et al., 2018; Ramadan et al., 2020). According to Horky et al. (2018), because of colloidal stability in different pH values, large surface area per weight, inherent inertness, superior adsorptive capability, and high stability, carbon nanomaterials (e.g. CNTs, nanodiamonds, and magnetic graphene) are currently used extensively to adsorb mycotoxins. The chemical structures that enable surface functionalization and provide a binding affinity to various mycotoxins are present in nanodiamonds, such as hydroxylation, carboxylation, and hydrogenation (Shoala, 2020). Horky et al. (2018) calculated the absorption capabilities of nanodiamonds for OTA and AFB1, which were approximately 10 g/mg and 5 g/mg, respectively. The CNTs with single or many walls are also used extensively in the process of adsorption of mycotoxins, such as AFTs, TCTs, and ZEN because of their adsorption capabilities (Horky et al., 2018; Shoala, 2020). There are reports of several mycotoxins being adsorbed by chitosan NPs simultaneously. For AFB1, OTA, FUM1, and ZEN, glutaraldehyde-crosslinked chitosan demonstrated exceedingly encouraging adsorption capability. However, DON and T-2 are not clearly adsorbed by glutaraldehyde-crosslinked chitosan (30%) (Zhao et al., 2015b). According to Luo et al. (2017), a nontoxic chitosan-coated Fe3O4 NP was effectively created with juice-pH for incorporating PAT-simulated environment. The chitosan-coated Fe3O4 NP demonstrated efficient adsorption for PAT with an optimum capacity of 6.67 mg/g for adsorption, and featured excellent adsorption characteristics such as low toxicity and good magnetic properties (Luo et al., 2017). Furthermore, a study created MIP-coated magnetic NPs (MIP-MNPs) for identification, quick adsorption, outstanding absorbing capacity, and excellent selectivity of OTA (Turan and ¸Sahin, 2016). In order to remove PAT from apple juice, Sun et al. (2020) created a new and powerful adsorbent with a magnetic molecular imprint (i.e. Fe3O4@SiO2@CS-GO@MIP). Additionally, Fe3O4@SiO2@CSGO@MIP demonstrated that PAT had a maximum adsorption capacity of 7.11 mg/g and could be removed within 24 h, removing more than 90% of the substance (Sun et al., 2022).
A study revealed that synthetic mesoporous silica nanoparticles (MSNs) with a larger Brunauer, Emmett and Teller (BET) technique surface area and a variety of morphologies, measuring 39.97 × 7.85 nm, adsorb up to 70% of AFB1 in aqueous environment within 15 min. MSNs exhibit great blood biocompatibility (with no hemolytic activity) and have no effect on the survival of 3-day transfer inoculum 3 × 105 (NIH3T3) cells in vitro. We further verified that AFB1-induced cytotoxicity in NIH3T3 cells in vitro was reduced by MSNs. Silanol groups and small size, porosity, and large surface area of mesopores could be responsible for MSN’s effective AFB1 adsorption. The polarity and size of AFB1, in addition to its physical and chemical characteristics, had a role in how well it bounds to MSNs (Savi et al., 2023).
Mycotoxin detoxification is seen as a never-ending process in the food sector. The removal of mycotoxins has been the subject of numerous strategies, including the chemical ones (such as ammonization, chemical agents, and ozonation), physical ones (such as irradiation, thermal processes, adsorption, cold plasma, UV, sorting, and microwave heating), and biological ones (such as microorganism and enzymes) (Figure 7) (Pankaj et al., 2018; Sun et al., 2019). However, the methods used to remove mycotoxins from the body have significant drawbacks. For instance, chemical techniques can result in residual issues, mycotoxin adsorption might result in secondary contamination, and biological approaches might be constrained by demanding environmental conditions, a protracted growing time, and expensive costs (Sun et al., 2019).
Figure 7. Removal of mycotoxins by nanomaterials using physical, chemical, and biological techniques.
Ammonization: Under very alkaline conditions, the amide bond of OTA undergoes hydrolysis to form non-toxic OTα and phenylalanine. This process is reversible. During the initial phases of investigation, ammonization emerged as a prevailing approach for detoxifying OTA. This approach exhibits detoxifying properties on different crops polluted with OTA, such as corn and wheat, without resulting in the generation and buildup of harmful breakdown byproducts (Ding et al., 2023). Ammoniating wheat at high pressure (60 psi) and normal temperature lowers the concentration of mycotoxins by 79% (Samuel et al., 2021). Similarly, treating contaminated cocoa shells with a 2% potassium carbonate solution at 90°C for 10 min could reduce 83% of OTA (Samuel et al., 2021).
Ozonation: Ozone is generated from the atmosphere or from a gas mixture containing oxygen and an energy source, such as corona discharge, UV light, or electrolysis. The corona discharge technology is extensively employed in several industries. This process involves the passage of oxygen or air across gaps between two electrodes (ground and dielectric) that are separated by energetic dielectric materials. During this process, oxygen is separated into oxygen atoms, which then mix with oxygen molecules to produce ozone (Pandiselvam et al., 2017). Ozone has a potential to impact the integrity and permeability of cell membranes, resulting in the leaking of cell contents. In addition, it interacts with proteins, such as DNA and RNA, and interferes with the structure of nucleic acids, resulting in the demise of cells. (An et al., 2024) Alternatively, ozone can chemically break down C8-C9 double bond by acting as an electrophile, resulting in the formation of primary ozonides. These ozonides can then degrade into smaller ozonated compounds, including aldehydes, ketones, and organic acids.
Irradiation: OTA was eliminated by irradiating infected corn with γ-rays. It demonstrated that extremely reactive radicals of γ-rays could damage OTA molecules’ ability to form double bonds with aromatic rings. Dosage of radiation is a crucial determinant impacting the process (Ding et al., 2023). The research conducted by Khalil et al. (2021) investigated the impact of γ-rays on the removal efficiency of OTA in both dry form and various aqueous solutions. The findings revealed that OTA in aqueous solutions was readily degraded by γ-rays whereas OTA in dry form exhibited lower susceptibility to degradation. These results suggest that γ-rays may not be an optimal approach for degrading OTA in grains.
Adsorption: Adsorption is a significant method for eliminating OTA by physical means. The process involves combining adsorption material with OTA to form a molecule that prevents the mycotoxin from being absorbed in the body through the gastrointestinal system. This combination is then removed by excretion (Quintela et al., 2013). The utility model offers the benefits of cost-effectiveness, a straightforward approach, and great efficiency. Physical adsorption is a surface process that occurs due to attractive forces prevalent between molecules, such as van der Waals forces and electrostatic interactions. In the case of OTA, these forces are between the negative charge of OTA and the positive charge of adsorbent. The phenolic hydroxyl groups of molecules engage in interactions with hydrophobic materials. The adsorption effect is influenced by several parameters, such as pore size, surface charge quantity, charge distribution, and specific surface area of adsorbent (Ding et al., 2023).
Cold plasma: Cold plasma is a phase of matter that exists beside solid, liquid, and gaseous phases. Cold plasma has the ability to efficiently break down and decrease the development of mycotoxins in both food and feed (Loi et al., 2023). Cold plasma technology operates by producing reactive chemicals, such as O2, O3, OH, NO, and NO2, which dismantle the structure of OTA and alleviate oxidative stress. This process leads to alteration or breakdown of OTA (Mohammadi et al., 2021). Cold plasma offers the benefit of rapid and effective degradation of OTA. However, its application is rather restricted due to the requirement of specialized equipment, resulting in its occasional use for degradation of toxins (An et al., 2024).
Microorganisms: Distinct processes by which microorganisms might lessen mycotoxin contamination include biotransformation (Piotrowska, 2021) and adsorption to cell walls, as discussed in Section 5.2 ‘Atoxigenic Aspergillus strains’. Various genera of filamentous fungi (such as Pleurotus, Armillariella, Armoracia, Trametes, Rhizopus, Trichoderma, Clonostachys, Cladosporium, and Aspergillus), yeasts (such as Saccharomyces, Pichia, Candida, Kluyveromyces, Yarrowia, Rhodotorula, and Rhodosporidium), and bacteria (such as Bacillus, Metschnikowia, Komagataella, Streptomyces, Rhodococcus, Pseudomonas, Pediococcus, Lactiplantibacillus, Enterobacter, Cupriavidus, and Brevibacterium) are capable of performing the biotransformation of AFs (Nahle et al., 2022).
Enzymes: Traditionally, enzymatic degradation is considered as specific. However, this is not the case for these particular enzymes. Their ability to break down AFs is dependent on their strong oxidative capacity, which is not limited to AFs alone as substrates. Laccases and peroxidases can synergistically interact with redox mediators, thereby expanding the range of substrates that these enzymes can act upon (Loi et al., 2023). When examined in protein and carbohydrate-rich diets, these enzymes have been demonstrated found to facilitate the creation of crosslinks and significantly alter the nutritional, technical, and rheological characteristics of foods. Modifications of some foods have been shown to enhance their nutritional and technical features (Loi et al., 2020). Therefore, it is important to conduct a meticulous examination for each specific situation to utilize these enzymes successfully.
The advantages of as a technique for progressive oxidation, photocatalytic degradation recently demonstrated significant potential for mycotoxin detoxification as a result of their low cost, environmental friendliness, ease of minimal pressure and temperature fluctuations, absence of secondary pollutants, and operation (Bai et al., 2017; Jamil et al., 2017). Amazingly, cutting-edge nanomaterials have become a popular research topic in mycotoxin detoxification sector and have played a significant role in the photocatalytic destruction of mycotoxins (Wu et al., 2020; Zhou et al., 2020). In order to prevent food contamination, a detailed examination of the mechanisms of detoxification and their capacity to preserve nutritional and organoleptic qualities, as well as toxicity assessments of the leftover components, is necessary (Hamad et al., 2022). While photocatalytic technology is mostly used to degrade AFB1 and DON in the aqueous phase, usage of photocatalysts on food infected by fungi is still in its early stage. The application of photocatalytic technology for detoxification of mycotoxins will be expanded if new or more photocatalysts are found to destroy efficiently other species of mycotoxins. Future research will pay close attention to the routes and toxicities of the byproducts of mycotoxin destruction in food samples by photocatalysts as well as changes in food quality and nutrition. Finally, widespread usage of photocatalytic technology can successfully remove mycotoxin contamination from agro-foods (Jing et al., 2023).
To date, numerous nanomaterials, such as titanium dioxide (TiO2), UCNP@TiO2, graphene/ZnO hybrids, g-C3N4, WO3/RGO/g-C3N4, and Fe2O3, are used in the photocatalytic destruction of mycotoxins, (Bai et al., 2017; Zhou et al., 2020). According to Sun et al. (2019), a straightforward hydrothermal technique was used to create an AFB1 photocatalytic degradation using an activated carbon and TiO2-based catalyst (AC/TiO2). Owing to the enhanced visible light intensity and higher surface area of AC/TiO2 composites, when exposed to UV-Vis light, 98% of degrading efficiency of material toward AFB1 could be achieved., which was greater than the degradation efficiency of bare TiO2 (76%) (Sun et al., 2019). Surprisingly, Wang et al. (2018) created a new photocatalyst (NaYF4:Yb,Tm@TiO2 composite; UCNP@TiO2) for the near-infrared (NIR) light-induced photocatalytic breakdown of DON (Zhou et al., 2020). Their team recently used UCNP@TiO2 to photocatalyze the degradation of DON under UV-Vis light and was able to identify three DON products because of deterioration (Wu et al., 2020). Additionally, TiO2 NPs were used to accelerate PAT breakdown in apple juice exposed to UV light. PAT in apple juice could be broken down to a limit of <10 mg/L using TiO2 NPs in 180 min (Douanla, 2019).
A number of cutting-edge mycotoxin analysis and control technologies depend on nanomaterials, which have been the subject of ongoing research and development throughout the last decade. Although much of ground is covered, still several major problems need fixing:
More innovative nanomaterials with new characteristics and multifunctionality should be found. Multifunctional composite nanomaterials could be created by mixing NPs with diverse properties. These NPs may enable more colorful detection and control tactics and perhaps entity integration. Nanomaterials could be used for detection, removal, and detoxification, reducing time and money, boosting detection effectiveness, and monitoring the detoxification process.
Safety and use of nanomaterials must be assessed. Nanomaterials have been employed widely in antifungal, mycotoxin absorption, and degradation; however, mycotoxin pollution control is a new phenomenon. Unknown health effects of nanomaterials could limit their usage for the sake of food safety. Nanomaterials used for mycotoxin control may be transferred to food by contact, which is their main drawback. Nanomaterial safety and applicability must be evaluated using applicable models or methods before their generalization and commercialization.
Nanomaterials, functional nucleic acids, biomimetic materials, and gene editing (CRISPR-Cas, clustered regularly interspaced short palindromic repeats and associated proteins) technology are needed to advance molecular biotechnology. These identification components greatly accelerate sensitive and selective detecting technologies. Because aptamers against AFB1 and OTA are well developed, several sensors are created using the same. Organic nanotechnology and biorecognition molecules help identify mycotoxins for control.
Computing technology integrates NPs to a greater extent. Most of the nanomaterial-based mycotoxin detection methods are still confined to laboratories because they require bulky and expensive apparatus to capture optical and electrochemical signals; this limits the manufacture of miniaturized commercial devices. More work must be done to combine nanomaterials with intelligent and information technology with automated spectrum processing and chemometric algorithms, such as portable and user-friendly Raman spectrometers.
Numerous articles are written on detection and control of mycotoxin contamination based on nanomaterials, which has become a prominent area of research in recent years. These techniques excel in three key areas: sensitivity, efficiency, and practicability. To ensure food safety, this study compiled the latest findings on the use of nanomaterials to build various measurements and control techniques to control mycotoxins, including methods to limit fungal development and absorption and degradation of mycotoxins. Specifically, distinct characteristics, intended usage, and suitability of each nanomaterial for each detection or control method are detailed and examined extensively. With the ongoing development and research in the field of nanomaterials, it is expected that this contribute more to ensuring the safety of food processing and production, as well as human health, by helping to create sophisticated and creative methods for detecting and controlling mycotoxins and other factors that pose a threat to human wellness. Researchers in the fields of nanotechnology and food science are expected to work together in the future to utilize multifunctional nanomaterials that inhibit the growth of mycotoxins discovered in food and feed.
Author contributions for this research article are as follows. Lavanya Ganesan: methodology, data curation, writing original draft, and investigation; Balasubramanian Balamuralikrishnan: conceptualization, writing original draft, selected bibliographic sources, visualization, and writing-review and editing; Sri Kalpana: formal analysis and selected bibliographic sources; Viji Maluventhen: formal analysis, editing, and selected bibliographic sources; Arumugam Maruthupandian: conceptualization and writing review and editing. All the authors revised and approved the final manuscript.
The data sets utilized and/or analyzed in this work are available on reasonable request.
No external funding was received for conducting this study.
Authors are thankful to their respective universities and institutes for their support.
The authors stated that they had no conflict of interest to declare. The authors had no known competing financial interests or personal relationships that had influenced this paper.
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