Nanobiopesticides in sustainable agriculture: developments, challenges, and perspectives

Xiaohong Pan *a, Xueping Guo a, Tianyun Zhai a, Dingyang Zhang a, Wenhua Rao ab, Fang Cao a and Xiong Guan *a
aState Key Laboratory of Ecological Pest Control for Fujian and Taiwan Crops, College of Plant Protection & Key Lab of Biopesticide and Chemical Biology, Ministry of Education, and Ministerial and Provincial Joint Innovation Centre for Safety Production of Cross-Strait Crops, Fujian Agriculture and Forestry University, Fuzhou 350002, P. R. China. E-mail:;; Fax: +86 591 83789258; Tel: +86 591 83789259
bInstitute of Plant protection, Fujian Academy of Agriculture Sciences, Fuzhou 350003, P. R. China

Received 23rd June 2022 , Accepted 13th November 2022

First published on 14th November 2022


Environment-friendly nanomaterials with biodegradable, responsive, and biocompatible properties have attracted considerable interest for exploring safe and efficient pesticides, and applying nanotechnology to develop new nanopesticide formulations would avoid the hazards of chemical pesticides and improve the efficacy of biopesticides. It can also be conducive to the development of less toxic biopesticides with increased stability of active ingredients, favorable biological safety, and enhanced activity on target pests. At present, there are comprehensive research papers, reviews, and books available on nanopesticides, but there are few reviews on nanobiopesticides. This review summarizes the main applications of nanotechnology in biopesticide formulation (such as nanoinsecticides, nanofungicides, nanobactericides, nanobioherbicides, and RNA pesticides), explores the possible uptake and transport mechanisms of nanobiopesticides in plants, analyzes its possible fate and impact on environment, and describes the challenges and possible risk of nanobiopesticides. Overall, this review provides a promising and comprehensive environmental perspective on the latest nanotechnology in the biopesticides field.

Environmental significance

Nanotechnology offers great opportunity to achieve more rational use of pesticides, and nanopesticides are considered to be one of the most important chemical pesticides innovations, which would largely enhance the bioactivity, achieve controlled release, increase the solubility, and prolong the duration. But the environmental behaviors of these novel agrochemicals are not fully characterized, and the lack of information of their effects on human and animal health have limited their rapid development. This review highlights the applications of nanotechnology in the agricultural fields and the application field of nanomaterials on biopesticides, summarizes the main progress of nanobiopesticides, and discusses the challenges of nanopesticides and restrictions in an actual environment. Further, this review is expected to provide a more comprehensive understanding of nanobiopesticides and promote its development, which is novel and interesting for readers in the environmental field.

1. Introduction

Nanotechnology, as “the next industrial revolution”, has been widely explored to improve agriculture. It is a promising and fascinating technology, which opens a new door for the next revolution in agriculture and agri-technology fields. Nanotechnology has shown promise for more sustainable and efficient agricultural systems to promote food security.1,2 In recent times, more intensive research and practices of nanotechnology in agriculture have been developed, where the applications can be categorized into nanopesticides, agricultural diagnostics, nanofertilizers, nanobiosensors, pollution management, sustainable agriculture, etc., (illustrated in Fig. 1a). IUPAC selected the “Ten Chemical Innovations That Will Change Our World” in 2019, and the nanopesticide ranks first.3 Applying nanotechnology to develop new nanopesticide formulations plays an important and effective role in plant pests and disease control to avoid the hazards of chemical pesticides and improve the efficacy of biopesticides.
image file: d2en00605g-f1.tif
Fig. 1 a) Applications of nanotechnology in agricultural sciences; it could achieve the controlled release of the active ingredient, increase the solubility, and exhibit the extension of duration, location targeting, and strong compatibility. b) The application limiting factors of biopesticides and nanobiopesticides based on nanotechnology.

Pesticides are chemicals that are applied to control pests and prevent plant diseases. They can be divided into insecticides, fungicides, bactericides, herbicides, and rodenticides according to their structure,4,5 but it is toxic to both humans and pests. Biopesticide formulations, which are ecofriendly pesticides, are alternatives to agrochemicals. Biopesticides can be obtained from different organisms, such as plants, bacteria, fungi, and nematodes.6,7

Biopesticides exhibit less toxicity, quick decomposition, low exposition characteristics, and can overcome the adverse effects (such as persistence, bioaccumulation, and toxicity) of chemical pesticides in agricultural activity. However, the low efficacy, short duration, inconsistent field performance, and high cost have generally limited the development of biopesticides, and biopesticides still only account for a small percentage of the global crop-protection market (around 5% market share with a value of about US$ 3 billion worldwide).8,9 The poor performance of pesticides/biopesticides has compelled the scientific community to discover new and cost-effective alternative strategies.10,11 Therefore, the introduction of nanomaterials in pesticides can effectively avoid the negative aspects of traditional agrochemicals or biologically-originated pesticides.10 Nanotechnology is conducive to the development of less toxic biopesticides with increased stability of the active ingredients, favorable biological safety, and enhanced activity on target pests (as illustrated in Fig. 1b).12–15

Currently, there are relatively comprehensive research papers, reviews, and books available on nanopesticides (194 results containing the word nanopesticide on WOS for the period from 1900 to October 2022), but there are few reviews on nanobiopesticides (with hardly 7 results containing the word nanobiopesticide in WOS). The present review summarizes the types and research progress of nanobiopesticides (mainly focusing on the application of nanotechnology in insecticides, fungicides, bactericides, herbicides, and novel RNA pesticides), explores the possible uptake and transport mechanisms of nanobiopesticides in plants, evaluates their possible impacts on environmental fate, discusses their future perspectives and challenges, and provides an in-depth understanding of the interactions among NPs, the environment (microorganisms, soils, plants), and humans that are still needed to develop a practical and effective strategy in nanobiopesticide applications.

2. The main categories of nanobiopesticides and their research progress

2.1 The common nanocarriers in biopesticides

Nanoparticles (NPs), which possess a small size and high specific surface area, show unusual and fascinating physicochemical properties in comparison to their bulk materials, such as specific chemical properties, physical strength, optical–electrical properties, thermal properties, magnetism, and biological activity.10,16,17 These novel properties of NPs impart enhanced beneficial characteristics and allow them to be converted from insoluble, poorly absorbed, and unstable biologically active substances into convenient deliverable substances.18,19 The main categories of nanomaterials are pure carbon nanostructures, inorganic nanomaterials, organic nanomaterials, and organic–inorganic hybrids according to their composition,20 and the most widely used NPs in agriculture are silver, copper, titanium, zinc, silica, gold, aluminum, iron, chitin NPs, chitosan, nanoclay, graphene NPs, multiwalled carbon nanotubes, and biopolymers.21–28

Nanobiopesticides are associated with optimistic innovative technologies of producing and utilizing biopesticides that fall in the nanoscale (1–100 nm).29 However, the nanocarriers used for medical, cosmetic, food, or agricultural applications generally have outer diameters much larger than 100 nm, although the internal functional features may be smaller than 100 nm.30 Therefore, nanopesticides may or may not fall within the definition of nanomaterials. Nanopesticides are used to describe any pesticide formulation that (i) intentionally include entities in the nm size range (up to 1000 nm), (ii) are designated with a “nano” prefix (e.g., nanohybrid, nanocomposite), and/or (iii) are claimed to exhibit novel properties associated with the small size of their components.30,31 Nanopesticide delivery has been classified into nanospheres, nanocapsules, nanocontainers, nanoemulsions, nanogels, liposomes, inorganic nanocarriers, etc. according to their forms,29 where the nanocapsules, nanogels, and micelles are the most popular shapes of NPs used in controlled-release biopesticide delivery.32 In general, the polymer- and clay-based nanomaterials are considered as biocompatible, cost-effective, and stimulus-responsive nanocarriers to encapsulate the active ingredients, and the active ingredients are mainly conventional pesticides, such as avermectin, atrazine, and glyphosate.2 Chitosan, cellulose, and polylactide are the most common natural polymers for developing nanocapsules, nanospheres, nano(hydro)gels, and nanomicelles for the active ingredients. Besides, mesoporous silica and montmorillonite are typical clay-based nanomaterials with high active ingredient encapsulation capacity, and some nanocomposites and two-dimensional (2D) nanomaterials with high specific surface areas have also been reported to facilitate the loading of active ingredients.2 Some of the reported NPs in biopesticide application are represented in Table 1 and Fig. 2. Overall, the advantages of nanopesticides are increased stability and bioavailability, enhanced adhesion to surfaces, controlled release of active ingredients, high targeting properties, and enhanced environmental safety.33–37

Table 1 Different types of NPs and their application in biopesticides
Nanoparticle Size (nm) Biopesticides Bioactivity effect against Ref.
Nano-Mg(OH)2 50–100 Bacillus thuringiensis Culex quinquefasciatus 57
Mg(OH)2 cross-nanosheets 712 Bacillus thuringiensis Helicoverpa armigera 59
Mesoporous silicon 5000/400 Bacillus thuringiensis Caenorhabditis elegans/Ancylostoma ceylanicum 60
Silica NPs 90.2 Bacillus thuringiensis Caenorhabditis elegans 64
Silver NPs 100–300 Bacillus thuringiensis Aedes aegypti 65
Mesoporous silica NPs 40 Bacillus thuringiensis Tuta absoluta 61
TiO2 33–44 Bacillus thuringiensis Ephestia kuehniella Zeller 66
Zinc oxide NPs 20 Bacillus thuringiensis Callosobruchus maculatus 67
Fe3O4 NPs 168 Bacillus thuringiensis Helicoverpa armigera 68
Amino acid-functionalized fluorescent nanocarriers 49 Bacillus thuringiensis Agrotis ypsilon 69
Graphene oxide 0.85 Bacillus thuringiensis Ephestia kuehniella Zeller 70
Lignin nanospheres 166–210 Avermectin 71
Polylactic acid 245.7 Avermectin Grapholitha molesta Busck 72
Poly-γ-glutamic acid and chitosan 56–61 Avermectin Pine wood nematodes 38
Carboxymethyl cellulose and rosin 167 Avermectin Plutella xylostella 56
MSNs-ss-starch nanoparticles 80.3 Avermectin Plutella xylostella larvae 62
Star polyamine (SPc) 108.1 Avermectin Green peach aphids 73
Layered double hydroxides (LDHs) 60–130 Avermectin 48
Poly(glycidyl methacrylate-co-acrylic acid) grafted hollow mesoporous silica 190.1 Abamectin Cnaphalocrocis medinalis larvae 63
Plant virus nanoparticle (PVN) 37.6 Abamectin Meloidogyne hapla root knot nematodes 55
Nanochitin 102–119.2 Abamectin Helicoverpa armigera 74
Mythimna separata
Zein 198 Neem oil Acanthoscelides obtectus, Bemisia tabaci, and Tetranychus urtica 75
Star polymer (SPc) 17.4–144.6 Eugenol Potato late blight 76
Silver nanoparticles 9.54–49.0 H. coronarium rhizomes extract Aedes aegypti 77
Carboxymethyl chitosan with ricinoleic acid (R–CM-chitosan) 200–500 Azadirachtin (Aza) 46
Starch nanoparticles (SNPs) 93–113 Essential oils (EOs): menthone Escherichia coli 78
Staphylococcus aureus
Cashew gum (CG) 27.7–432.7 Eucalyptus staigeriana essential oil (ESO) Listeria monocytogenes 79
Salmonella enteritidis
Agar or alginate or carrageenan 359–634 Zataria essential oil 80
Zein with sodium caseinate (SC)–chitosan hydrochloride (CHC) double layers 176.9–741.6 Thymol Staphylococcus aureus 39
Chitosan 82–165 Achillea millefolium essential oil (AEO) Tetranychus urticae 40
Poly-γ-glutamic acid (γ-PGA) and chitosan (CS) 56–61 Avermectin Caenorhabditis elegans 81
Chitosan derivate (CMC-g-RA) 215.2–960.1 Botanical insecticide capsaicin (Cap) 41
Chitosan nanoparticles 10–28 Metarhizium anisopliae Plutella xylostella 42
Spodoptera litura
Chitosan nanoparticles 20–60 Green tea oil Staphylococcus aureus 43
Escherichia coli
Chitosan 100–200 Chitin synthase2 gene Anopheles gambiae 44
Chitosan crosslinked to sodium tripolyphosphate <200 dsRNA Aedes aegypti 45
Star polycation (SPc) 146.1 Hemocytin (hem) dsRNA and botanical pesticide atrine Green peach aphids 82
Branched amphiphilic peptide capsules (BAPCs) 70–300 dsRNA Tribolium castaneum 83
Functionalized perylene diimides nanocarriers <200 dsHem Aphis glycines 84
Layered double hydroxide (LDH) 15–120 dsRNA Pepper mild mottle virus (PMMoV) and cucumber mosaic virus (CMV) 85
Nanoliposome 110 Bacterial crude extract Fusarium oxysporum 86
TiO2 and ZnO 50 and 67 Bio-agent Bacillus subtilus Podosphaera xanthii 87
ZnO synthesized by aqueous plant leaf extract of Terminalia bellerica 20–30 Alternaria brassicae 88
Herbicidal metabolites extracted from Fusarium oxysporum fungi 60–90 Ninidam theenjan 89
Nanoemulsion containing palm oil derivatives and Parthenium hysterophorus crude extract 140.1 Diodia ocimifolia 90
Mesoporous silica nanoparticles 80–180 Citridiol 91
Cellulose nanocrystals and silicon dioxide NPs 82.5 Emamectin benzoate Phenacoccus solenopsis 92
Porous hollow silica 80.0 Validamycin 93
Nanosized calcium carbonate 50–200 Validamycin Rhizoctonia solani 94
Amino-modified silica 52.5–315.4 Kasugamycin Escherichia coli 95

image file: d2en00605g-f2.tif
Fig. 2 Common nanocarrier types in biopesticide application, including chitosan NPs,38–45 carboxymethyl chitosan NPs,46 magnetic NPs,47 layered double hydroxides (LDHs),48 poly(lactic-co-glycolic acid) (PLGA) NPs,49,50 zein nanoparticles,51–54 plant virus NPs,55 carboxymethyl cellulose NPs,56 Mg(OH)2 nanoplatelets,57 boron nitride nanoplatelets,58 flowerlike nanosheets,59 and mesoporous silica.60–63

2.2 The application of nanotechnology to insecticides

Bacillus thuringiensis-based nanoinsecticides. Bacillus thuringiensis (Bt) is a microbial pesticide with a wide range of applications that has insecticidal activity against lepidopteran and coleopteran pests and has no toxicity to non-target organisms. However, Bt is easily affected by environmental factors, such as ultraviolet (UV) light, rainwater, and digestive enzymes, which lead to a decrease in its insecticidal duration and cannot meet biological pest control work. The application of nanotechnology in the preparation of Bt biopesticides can provide more efficient, stable, and environment-friendly Bt formulations.

Nanomaterials can improve the reflection and scattering of Bt preparations with respect to UV radiation and improve the environmental stability of Bt-active ingredients. For example, nano-Mg(OH)2 can efficiently adsorb the Bt mosquito-killing protein Cry11Aa and improve the UV stability of the protein, while improving the enzymatic hydrolysis of the protein in the midgut of the target pest process, promoting the destruction of midgut cells, and ultimately increasing the insecticidal activity of the protein on the pests.57,96 Bt chitinase was immobilized onto the surface-modified spherical nanosilica to prepare a silica–chitinase complex by electrostatic adsorption and covalent binding, and the obtained product exhibits high resistance to UV radiation.64 Bt mixed with different crystal forms of nano-TiO2 shows different anti-UV activity,66 which indicates that the UV resistance properties may be closely related to its morphology and crystal forms. Moreover, graphene oxide combined with olive oil on the Bt cell mixture showed synergistic UV protection effects,97 and UV reflective nanomaterials, nano-ZnO, nano-SiO2, and nano-TiO2, combined with Bt to form a microcapsule formulation with relatively long-lasting UV resistance.98

Rao et al. synthesized nano-Mg(OH)2 to absorb Cry1Ac protein and control the loss of Cry1Ac protein that can be induced by rainwater flushing, where the nano-Mg(OH)2–Cry1Ac mixture can be loaded on the groove of the cotton leaf, which could enhance the anti-rainwater washing ability and insecticidal activity compared to those of the pure protein.59 Wu et al. combined mesoporous silica with Bt Cry5B protein and the mesoporous silica loading not only protected the Cry5B protein from hydrolysis by mammalian pepsin but also improved the protein transmission in the worm and increased the control efficiency of the protein on the nematode.60 In addition, studies have shown that GM plants can secrete Bt Cry protein in their roots and other tissues, and the secreted protein can bind to nanoparticles in soil to form complexes with long-term activity. For instance, nano-SiO2 and Cry1Ab protein can be combined by electrostatic adsorption, where the electrostatic adsorption is based on the non-uniformity of the surface charge distribution of the Cry1Ab protein, while the conformation and insecticidal activity of Cry1Ab protein did not significantly change during the adsorption process.99,100 Montmorillonite and kaolin can prevent Cry1Aa protein from oligoaggregation, maintain protein conformational stability, and exhibit higher insecticidal activity.101,102 Therefore, the tight binding of soil nanoparticles is the key to the transgenic protein possessing a persistent insecticidal effect in the soil environment.

Moreover, nanomaterials can be used as carriers to prepare GM crops due to their efficient gene-delivering properties. Modified magnetic nano-Fe3O4 particles were used to adsorb Bt cry1Ac genes, and the prepared gene delivery tool could provide a fast and efficient solution for the preparation of GM cotton.68 Nanomesoporous silica was used as the cry1Ab gene carrier and was introduced into the tomato via injection, and the related gene could be highly expressed in the progeny tomato seeds.103 Meanwhile, the cry1Ab gene carried by mesoporous silica can also be expressed in tomato progeny by injecting the plant leaves.61 The resistance of Lepidoptera and other pests to Bt Cry protein is also an important concern. Amino acid-functionalized fluorescent nanocarriers can improve the penetration ability of the Bt Cry1Ab protein into the midgut cells of Agrotis ypsilon, which is independent of midgut receptors; thus, it can bypass the changes caused by the receptor changes.69 This strategy can improve the control effect of Bt-resistant pests, reduce the frequency of use of alternative chemical pesticides, and has a good promoting effect on the sustainable development of agriculture and environmental protection. In addition, the green synthesis of NPs based on Bt cell culture is an alternative to chemical and physical methods, where it not only reduces the content of toxic chemical raw materials required in the preparation process but also increases the insecticidal activity of the obtained products. The prepared nanosilver using the supernatant of the Bt culture has a synergistic effect on the control of Aedes aegypti.65 Nano-ZnO was synthesized by a Bt cell culture medium as the matrix for the control of storage pests, and the results showed that the insecticidal activity of the complex was significantly higher than that of the pure nano-ZnO and Bt preparations.67,104

Nanotechnology in avermectin insecticides. Avermectin (AVM) plays a very important function as a bactericidal and an antiparasitic agent against nematodes and arthropods, and has been widely used for decades. However, the low solubility, high sensitivity, easy decomposition, and short efficacy duration of AVM limit its application. It has been proved that nanosilica could be a super nanocarrier to load and control the release of AVM. Liang et al. established a novel redox-α-amylase double-stimulus-responsive pesticide release system (AVM@MSNs-starch NPs, Fig. 3a), and the constructed compound could protect AVM from photodegradation and achieve the controlled release of the active ingredient with longer effectiveness.62 An efficient AVM nanodelivery system based on a star polyamine (SPc) was constructed by Yang et al., which could enhance the contact and stomach toxicity of AVM against green peach aphids, which reveals the wide applications in the agricultural field.73 Gao et al. designed a pH-responsive organic–inorganic hybrid nanomaterial by modifying HMSNs with high adhesion and wettability on rice leaves,63 which could significantly improve the photostability of AVM and exhibit the high release rate to achieve the high activity of Lepidoptera pests.
image file: d2en00605g-f3.tif
Fig. 3 a) Mesoporous organosilica nanovehicles used as nanocarriers of avermectin, adapted with permission from ref. 62, copyright 2020, Elsevier B.V. b) Boron nitride nanoplatelets for pH-responsive release and enhanced UV stability of avermectin, adapted with permission from ref. 58, copyright 2020, Elsevier B.V. c) Avermectin-loaded plant virus NPs, adapted with permission from ref. 55, copyright 2015, American Chemical Society. d) Preparation of AVM–chitosan/γ-PGA nanoparticles. Adapted with permission from ref. 110, copyright 2018, Elsevier B.V.

Moreover, scientists have prepared boron nitride interface-modified nanocarriers with 18.19% loading of AVM (Fig. 3b), where the presence of a PEG modification layer improves the dispersion of drug-carrying NPs in water and imparts an AVM pH-sensitive release signature, which could improve the AVM's adhesion performance and photostability on cucumber leaves.58 Zhao et al. used sodium dodecyl sulfate to modify AVM-layered double hydroxide nanohybrids, which achieved the well-controlled release of AVM, and it is expected to become a candidate material for water-dispersible controlled-release formulations.48 Song et al. constructed a pH-responsive release AVM nanopesticide based on 2D MXene (Ti3C2) nanomaterials with a maximum pesticide load of 81.44%, where the nanopesticide delivers high water solubility and good photostability, which could reduce pesticide dosage and spraying time.105

Lignin is a renewable resource of aromatic compounds in nature and is a widely found biopolymers around the world.106 The hydrophobic modification of lignin was carried out by the electrostatic self-assembly method to prepare microspheres with an AVM loading rate of 62.58 ± 0.06%, where the obtained microspheres also show good performance on the release control of AVM and resistance to photolysis.107 Liang et al. synthesized biomimetic mussel AVM NPs with a diameter of about 120 nm and an >50% adsorption rate of AVM (w/w), which showed good adhesion to crop leaves, excellent storage and light stability, and sustained-release ability.108 In addition, Guan et al. used raw materials to prepare AVM nanoemulsions that can be efficiently improve the photostability of AVM and provide strong target crop leaf adhesion and low residue.109 As a non-inhalant insecticide, AVM is difficult to be absorbed and transmitted by plants because it only has a small amount of osmotic absorption at the application site. Wang et al. prepared AVM/glycine methyl ester-modified polysuccinimide NPs (AVM@PGA) by self-assembly, where the release of AVM has obvious pH sensitivity, and the anti-UV photolysis ability of AVM is greatly improved.34 In addition, AVM@PGA can also regulate the transmission and distribution of AVM in plants, which has a good effect on the prevention of plant pests.

In addition to poor UV light stability and low water solubility, AVM's poor fluidity in soil can also affect its nematode performance due to the limited protected areas around the plant growth roots. Cao et al. encapsulated AVM in red trilobite necrosis virus to manipulate the physicochemical properties of the soil of AVM (Fig. 3c), and it was found that PVNAVM expanded the treatment range of root-knot nematodes in the soil and improved its insect resistance activity against nematodes compared to the free AVM molecular treatment.55 A simple electrostatic interaction method was reported to encapsulate AVM within NPs composed of poly-γ-glutamic acid (γ-PGA) and chitosan (CS), which achieved high water dispersibility, anti-photolysis, high nematicidal activity, and controlled-release multifunctional nanocarrier of pesticides (Fig. 3d).81 All this research on different types of nanoencapsulation technologies of AVM provides references for the preparation of more efficient, stable, and environment-friendly AVM formulations.

Nanobotanical insecticide. Botanical pesticides are a branch of the biopesticide family, and have advantages of low residues and toxicity, no bioaccumulation, and are environment friendly.111 The secondary metabolites produced by plants, such as alkaloids, flavonoids, terpenoids, and volatile oils,112 are used in the development and utilization of botanical pesticides.113,114 However, there are problems such as difficulty in formulation, poor stability, and easy decomposition due to their special sources and complex components, which affect the efficacy of active ingredients.113 The application of nanotechnology has helped to solve these problems of botanical pesticides in agricultural application to a large extent (Fig. 4).115 Nanoemulsions have been developed to improve the chemical stability, hydrophilicity, and environmental durability of botanical pesticides.116 Nanoemulsions based on plant essential oils have broad applications in insecticides and have good insecticidal activity against various agricultural pests.117–120 For example, Iqbal et al. developed a stable neem oil-based nanoemulsion (NE) formulation with bio-inspired adjuvant of Cymbopogon citratus and Prosopis juliflora with long-term storage stability that showed significant insecticidal activity against Bemisia tabaci in eggplant (91.24%) by reducing the surface tension and contact angle.121 Wuryantini et al. compared the efficacy of tobacco plant-derived insecticide nanoemulsion and crude extract and found that the nanoemulsion had better control effect on Citrus aphids than the crude extract,122 indicating that the use of nanoagents has broad prospects in improving the utilization of active ingredients of plant-derived pesticides.
image file: d2en00605g-f4.tif
Fig. 4 Application of nanotechnology for botanical pesticides. The nanobotanical pesticide products mainly contain nanoparticles, nanoemulsions, nanocapsules, microcapsules, and microemulsions. Also, the performances of traditionally botanical pesticides could be effectively improved by nanotechnology.

Incorporating polymers into botanical pesticide formulations to form nanospheres or nanocapsules can reduce the loss of active ingredients and achieve controlled release.123 The microencapsulation of essential oils can improve the oxidative stability, thermal stability, shelf life, and biological activity of oils,86,124 and it can also control the volatility and release properties of essential oils.125 Feng et al. synthesized an amphiphilic carboxymethyl chitosan with ricinoleic acid (R–CM-chitosan) to be used as a carrier for the botanical pesticide azadirachtin (Aza), where the formed Aza/R–CM-chitosan water dispersion on the nanoscale level had a better controlled release activity.46 González et al. found that the incorporation of geranium or bergamot essential oil into a solid controlled-release nanoformulation could prevent its rapid evaporation and degradation and enhance its stability and insecticidal activities through contact and ingestion.126

Moreover, plant polyphenols are embedded in or adsorbed on the surface of nanoparticles to produce polyphenol particles, which have stronger activity in terms of solubility, antioxidant stability, and wider application range. Three plant compounds (geraniol, eugenol, and cinnamaldehyde) were encapsulated in zein NPs,127 where the nanoencapsulation provided protection against the degradation of the compounds during storage and resulted in reduced toxicity to non-target organisms, while also showing superiority to the emulsifying compound in terms of repellent and insecticidal activity. In all, the application of nanotechnology in botanical insecticides can improve their chemical stability, hydrophilicity, environmental durability, and insecticidal activity.

2.3 Nanotechnology in fungicides

Plant pathogens can infect the plant tissue at different stages of crop growth,128 and phytopathogenic fungi are a type of plant pathogen that can cause great economic losses worldwide.129 Nanotechnology can offer ecofriendly and green alternatives for plant disease control, and the use of nanotechnology to develop safe antifungal agents is of great significance.129–134 Nanobiofungicides are fungicides formulated at the nanometer size with novel properties and can be designated as nanohybrids or nanocomposites.135,136 It has been reported that microorganisms (including bacteria, fungi, actinomyces, yeast, and algae) and plants are able to synthesize nanofungicides,137–139 and the biosynthesis of nanofungicides has been recognized as an efficient and green method.140

Silver NPs can be synthesized by a biological method using Bacillus amyloliquefaciens as a new source, and in vitro studies have revealed that biosynthesized AgNPs exhibit good antifungal effects on Fusarium solani and Fusarium oxysporium, which indicates that the low-cost and ecofriendly nanobiofungicide can be a promising alternative to traditional chemical fungicides.141 A novel nanobiofungicide encapsulated in nanoscale liposome particles with high antifungal activity against Fusarium spp. was reported, which was synthesized by ethanol crude extract from plant growth-promoting bacteria.142 The co-effect of bioagent Bacillus subtilus, -TiO2, and nano-ZnO was investigated against powdery mildew disease caused by Podosphaera xanthii, and the result indicated that the combination of B. subtilus and nano-ZnO treatment could significantly reduce the symptoms and severity of P. xanthii by reducing electrolyte leakage and elevating the ROS levels.87 Phytofabricated ZnO NPs were synthesized using the aqueous plant leaf extract of Terminalia bellerica, and it has shown significant antifungal potential against blight disease/leaf spot disease.88 Moreover, ZnO NPs and ZnO-based nanobiohybrids have been synthesized by a chemical route and green synthesis from garlic extract, respectively, and it was found that the nanobiohybrids exhibited a fungal inhibition of 72.4%, while the inhibition of the chemically-synthesized ZnO NPs was 87.1%. In addition, ZnO-based and phytofabricated ZnO NPs have also been reported as nanofungicides to manage plant pathogens.88,143 All these studies suggest that the biosynthesis of nanobiofungicides is cheaper and more environmentally sustainable and stable than using chemical synthesis methods.

Chitin/chitosan-based stimulus responsive nanopreparations can release active nanopesticides more accurately and effectively and adopt targeted delivery or controlled-release mechanism. Nanochitin has good ability to inhibit mycelial growth, a strong ability to inhibit conidial formation, and increase disease control efficiency when applied as a seed-coating agent and/or when mixed with chemical fungicide.38 Zhou et al. reported that nanochitin can help with seed germination, plant growth promotion, and fungicide efficacy in inhibiting tobacco root rot.144 Saharan et al. synthesized chitosan-copper nanocomposites and showed excellent antifungal activity in tomato, where it has also been proved to be an important growth promoter in different crops.145 Dananjaya et al. studied the antifungal activity of chitosan–silver nanocomposites on Fusarium oxysporum species complexes, and the results showed that chitosan–silver nanocomposites caused obvious damage to the surface of mycelium and increased membrane permeability and, sometimes, cell disintegration.146 Oleoyl–chitosan nanocomposites were tested on pathogenic fungi (Verticillium dahlia), which showed that the oleoyl–chitosan nanoparticles dramatically decreased the mycelium growth.147 All these findings show that chitin/chitosan could be used as excellent nanocarriers.

Moreover, porous hollow silica NPs were prepared as the controlled delivery system of validamycin to enhance the activity and reduce the toxicity compared to free validamycin, and it was shown that the release rate of validamycin is mainly related to the pH and temperature of the dissolution medium.93 Nanosized calcium carbonate was used as a carrier to load with the biopesticide validamycin, where the composite exhibited high loading efficiency, sustained-release performance, and good environmental compatibility, and it displayed better germicidal efficacy against Rhizoctonia solani compared to conventional validamycin.94 Similarly, the dual-functionalized pesticide nanocapsules (loaded with validamycin and thifluzamide) exhibited good foliar spread to reduce the loss of pesticide on leaves, and it had a clear synergistic effect between the two active ingredients.148 A nanoconjugate derived from kasugamycin with amino-modified silica was developed by Ding et al., and it was found that the kasuga-silica can effectively protect kasugamycin against photodegradation and the release rate of kasugamycin was dependent on the temperature, pH, and particle size.95 Overall, the application of nanotechnology in the fungicide could effectively improve the performance of biopesticides to a large extent.115

2.4 Nanobactericides

At present, there are also many explorations of nanotechnology in the bactericides field. Liang et al. prepared ZnO@ZIF-8 nanospheres with the core–shell structure by the in situ growth method and used it to load berberine with efficient synergistic bactericidal effect, which could induce reactive oxygen species (ROS) generation, cause bacterial DNA damage, cytoplasm leakage and, membrane permeability changes (Fig. 5a).149 Peppermint oil and green tea oil were encapsulated in chitosan NPs by emulsification–ionic gelation technique; it was found that nanoencapsulation maintained the stability of the total phenolic contents in both EOs, and the antioxidant and antibacterial activity (against Staphylococcus aureus and Escherichia coli) was significantly improved for peppermint oil and green tea oil, respectively (Fig. 5b).43 Leimann et al. found that microencapsulation of lemongrass oil with polyvinyl alcohol (PVA) could protect the oil from spoilage and maintain its antibacterial activity.150 Du et al. compounded Zn2+ particles into chitosan solution, which showed a significant improvement of the antibacterial activity of the composites with increasing Zn2+ concentration.151 The fabricated CuNP composite nanogel showed high controllability of Pseudomonas syringae on tobacco and safety compared to the commercial bactericide thiodiazole copper.152 All these studies indicated that nanotechnology can improve the antibacterial activity of traditional biopesticides.
image file: d2en00605g-f5.tif
Fig. 5 a) Illustration of the synthesis of Ber@ZnO-Z nanospheres and their applications in the synergistic control of bacterial wilt disease of tomato. Adapted with permission from ref. 149. Copyright 2022, American Chemical Society. b) Nanoencapsulation of essential oils by the emulsification–ionic gelation method. Adapted with permission from ref. 43. Copyright 2019, Elsevier B.V.

Moreover, pure nanomaterials also show high antibacterial activity, and the use of nanomaterials as active ingredients for crop protection is also a very important field of research. Silver, zinc, and copper nanoparticles are most reported in agricultural practices as the antibacterial agent.153 Silver chloride NPs was also biosynthesized by Rhizospheric bacteria and exhibited high antibacterial activity against Ralstonia solanacearum;154 the green synthesized Ag NPs exhibited long-term antimicrobial properties and attenuated toxicity to plants compared with chemically synthesized Ag NPs,155 which suggested that the green synthesized Ag NPs could be used as potential nanopesticide or nanoscale growth regulator in agriculture. ZnO nanomaterials also showed high antibacterial activity (against Xanthomonas citri) without phototoxicity.156 It was found that the shape of the NP significantly influences the antibacterial activity of spherical CuO NPs and nanosheets of CuO, and both NPs could damage the bacterial membrane and DNA.157 Moreover, the biosynthesized magnesium oxide NPs could be used as effective antibacterial agents against rice pathogen Acidovorax oryzae, indicating that MgO NPs could be used to formulate a potent nanopesticide.158

2.5 Bioherbicides and nanotechnology

Agricultural weed is a kind of plant adapted to the agricultural environment, which directly and indirectly interferes with crop production and causes great economic losses worldwide.159 The control of weeds mainly depends on herbicides and includes chemical herbicides and biological herbicides (industrially produced by microorganisms, plants, and animals or their tissues and metabolites).160–162 However, in practical application, the herbicide utilization rate is low due to man-made or environmental factors, which also causes a series of problems to the environment, increasingly serious damage to the ecological environment, thus significantly affecting the sustainable development of agriculture.163 The application of nanomaterials and technology in the field of pesticides can change the physical and chemical properties of pesticides, fully improve the utilization rate of pesticides, reduce pesticide residues, and reduce environmental pollution.164–166

Bioherbicides are natural products that can be used for weed control,167 which show a short residual period in the environment and less pollution and adverse effects on soil, water, and non-target organisms.161,168 However, the relatively short half-life reduces the weed control effect in the field scale, and the complicated and expensive preparations restrict the development of biological herbicides.169 Therefore, it is necessary to develop suitable protective bioherbicide active substances to optimize their deployment and effect in the field.169 However, few reports have focused on the combination of biological herbicides and nanotechnology, where research on biological herbicides has great potential for innovation and development. At present, the nanoformulation technology that has attracted considerable attention is the nanocapsule. Taban et al. studied the herbicidal activity of different concentrations of nanocapsule mint essential oil, and it was found that the nanocapsule herbicide had a considerable herbicidal activity on weeds and a mild effect on non-target crops.86 Some NPs (i.e., alginate, chitosan, nanoclay, and lipids) with special chemical properties can be used as bioherbicide carriers to control the release of active components, thus reducing the loss of active components and improving the utilization rate of bioherbicides.115,163 The herbicide metabolites were extracted from the free supernatant of Fusarium oxysporum isolated from soil and coated with chitosan NPs, and it was found that chitosan NPs could be used as the carrier of F. oxysporum herbicide, which showed good herbicidal activity against weeds.89 In addition, the nanoemulsion system can also be used as another way of effectively delivering biological herbicides, where the NPs are evenly dispersed on the surface of leaves, enhance the permeability of the active ingredients in weed leaves, and thus show better control effects on weeds.90 It is believed that nanobiological herbicides that combine biological herbicides with green, inexpensive nanomaterials will play an important role in reducing environmental pollution and the sustainable and healthy development of agriculture (Fig. 6), but it is necessary to consider the compatibility of NPs with other biological agents and their specificity to plant hosts under field conditions to limit or avoid further damage to the environment and human health.168,170

image file: d2en00605g-f6.tif
Fig. 6 Nanotechnology application in bioherbicides that could potentially enhance the solubility, mobility, and durability, and reduce the toxicity.

2.6 Nanotechnology application in other types of biopesticides

RNA biopesticides use RNA interference (RNAi) to inhibit important gene expression in target organisms, leading to the developmental retardation or death of harmful organisms, thus achieving the purpose of pest control. The traditional delivery system for RNA pesticides is usually influenced by various external factors that can lead to low efficiency and hinder its application in modern agriculture. In recent years, nanodelivery system-based RNA pesticides have drawn increasing attention in the development of green and sustainable agriculture (Fig. 7). Compared to traditional delivery strategies, the nanocarrier-mediated RNAi delivery system has several advantages such as high efficiency, low dose, and slow release. RNAi is considered a safe pest control strategy due to its high sequence specificity.171
image file: d2en00605g-f7.tif
Fig. 7 Schematic representation of a nanoparticle-mediated double-stranded RNA/small interfering RNA (dsRNA/siRNA) delivery system. Adapted with permission from ref. 171. Copyright 2020, John Wiley & Sons Australia, Ltd on behalf of Institute of Zoology, Chinese Academy of Sciences.

In general, the siRNA, miRNA, and piRNA pathways would be the RNAi pathways in insects,172 but double-stranded RNA (dsRNA) may be restricted or limited to the xylem vessels and plant vascular system. At present, a novel delivery strategy based on nanocarriers can overcome the cell wall barriers of plants and accurately deliver DNA or RNA into the plant, leading to transient or stable transformation.173 A perylene imide nanocarriers-mediated dsRNA delivery system was developed on Aphis glycines, where the interference efficiency of the nanocomplex on the target gene reached 95.4% and the population inhibition effect was 80.5%.84 Moreover, a star polycation-based gene and drug co-delivery system was constructed to deliver hemocytin (hem) dsRNA and botanical pesticide matrine against green peach aphids, and it was found that the matrine/star polycation/dshem complex could overcome the short life disadvantage of dshem an slow-acting properties of matrine simultaneously.82 Guanidine-containing polymers were developed to protect dsRNA against nucleolytic degradation in alkaline intestinal environments, where they can effectively interfere with the essential gene chitin synthase B, and the mortality rate of Spodoptera exigua increased from 16% to 53% by the polymer-protected dsRNA treatment.174 dsRNA loaded on layered double hydroxide (LDH) clay nanosheets (formation of BioClay) can provide sustained-release performance, where dsRNA can be detected on sprayed leaves even 30 days after application, and the BioClay could achieve a 76% antiviral efficiency on being sprayed on Arabidopsis thaliana leaves.85 The smaller and cheaper soybean phosphatidylcholine (SPc) was selected as the nanocarrier to effectively penetrate the body wall of the soybean aphid through topical application and spraying, with a high mortality up to 81.67% and 78.50%, respectively.172

Although RNA pesticides have been a breakthrough in the fields of pest control and plant protection, the instability, high cost, and short life of dsRNA seriously constrain their commercial application.82 Meanwhile, the dsRNA delivery efficiency is often low, and it is difficult to produce sufficient amounts of stable dsRNA in traditional transgenesis because of the plant RNAi machinery.171 Hence, more in-depth studies on nanodelivery system-based RNA pesticides must be conducted before the broad usage of nanodelivery system-based RNA pesticides.171 For instance, cheap raw materials have been used in the synthesis process of NPs to overcome the high production cost of nanoparticle-based RNA pesticides, where the common commercial chemical pentaerythritol is used as the star initiator to reduce the production costs.175 Meanwhile, the potential risk and biocompatibility of nanodelivery system-based RNA pesticides should be assessed before their application,176,177 and the non-target effects and insect resistance to RNA pesticides should be considered.178

3. The uptake and transport of nanobiopesticides in plants

In recent years, many studies have focused on the construction of smart controlled-release nanopesticide formulations and biological activity evaluation.179 The uptake, transport, and distribution of nanopesticides in plants are not fully understood, and the phytotoxicity and genotoxicity caused by NPs are rarely considered.180–183 Indeed, understanding the interaction behavior between nanopesticides and plants is helpful for designing new nanocarrier systems for desired applications,184 and it is also conducive to revealing their biocumulative effects and biological safety to provide guidance for the safe use of nanopesticides.185–187

The efficient deposition and strong adhesion of pesticides on the foliage surface are key factors in minimizing pesticide loss and improving the utilization efficiency.179 NPs are easily adsorbed or aggregated on plant epidermis by electrostatic adsorption, mechanical adhesion, and hydrophobic affinity due to their large specific surface area and high surface reactivity.188 The interaction between nanopesticides and plants mainly includes three steps: (ref. 20 and 189) (1) NPs are deposited or adsorbed on the surface of plants (roots, stems, and leaves); (2) NPs permeate into the cuticle and epidermis, and then migrate to the vascular tissues by means of symplasts or exoplasms; (3) NPs are transported to other parts of the plant through the vascular tissue (illustrated in Fig. 8). Although similar features exist in roots (an epidermis with stomata, mesophyll, and vascular tissue) and leaves (trichomes, cuticular folds, and wax crystals), the different morphological characteristics of roots leaves would lead to different barriers for NPs entry.20 Meanwhile, the accumulation and transport of NPs also depend on nanoparticle shape, application method, and nature of plant tissues, and the translocation of NPs from leaf to root was achieved by the phloem transport mechanism.190

image file: d2en00605g-f8.tif
Fig. 8 Schematic diagrams of the uptake and transport process of NPs in plants. The NPs could deposit or adsorb on the surface of plants (roots, stems and leaves); or permeate into cuticle and epidermis, and then migrate to vascular tissues by means of symplasts or exoplasms; or transported to other parts of the plant through the vascular tissue.

More details on the uptake, transport, and fate of NPs in plants could be seen in Su et al.'s20 and Schwab et al.'s reviews,191 and most reports focus on the delivery of the nanopesticide. Currently, the transport of avermectin-based nanobiopesticides has attracted some attention. Yu et al. have developed three types of functionalized abamectin poly(lactic acid) (Abam-PLA) NPs with different adhesion abilities to cucumber foliage, where the adhesion of Abam-PLA NPs to the foliage surface mainly depends on the surface functional groups of NPs and was easily regulated by varying the functional groups.179 Liang et al. have developed avermectin NPs with a particle size of 120 nm using a copolymer (styrene and methacrylic acid) as the avermectin carrier and polycatechol as the adhesive group on the surface. The interaction force between NPs and the surface of cucumber and broccoli foliages is mainly derived from the hydrogen bond, which highly enhanced the adhesive performance on the foliage surface.81 Moreover, multifunctional avermectin/polysuccinimide with glycine methyl ester nanoparticles (AVM–PGA) were prepared,34 where AVM could be detected in stems and all leaves after treatment with AVM–PGA, whereas only few AVM molecules could be detected in treated rice leaves for free-form AVM. The PGA nanocarriers could improve the uptake and transportation of AVM in rice, and could also interact with the plant amino acid transporter to enhance their cellular uptake and phloem loading.192 The above reports implied that nanocarriers can improve the uptake and transport characteristics of nonsystemic AVM biopesticide. In addition, novel Au NPs conjugated with D-glucose (Glc) and rotenone (R) nanopesticide were designed, and it was found that R–Au NPs–Glc could be actively transported into tobacco BY-2 cells by hexose transporters dependent on an energy-dependent process. Glc was found to be a promising ligand for the uptake and delivery of nanopesticides.193

In the future, exploring the interactions between nanopesticides and plants should not be limited to the migration path mechanism but also the dynamic digestion, residual behavior, and toxicology of nanopesticides in plants. To understand the differences in the morphological and physiological characteristics of plants before and after the NP treatment, identifying the key factors in determining the penetration process of NPs into plants, and selecting suitable nanosizes and carriers to reduce the residue and improve the utilization rate of pesticide would be helpful for the development of green and efficient nanopesticides.

4. Future perspectives and challenges of nanobiopesticides

Nanotechnology and new nanomaterials are gaining popularity at the forefront of agricultural industry,194 where numerous publications are focused on the development of nanoformulated pesticides and more commercial products are available in global markets. Although several agrochemical companies (such as Syngenta, Bayer, Monsanto, BASF, and Dow AgroScience) have developed a large number of patents on nanopesticides,195,196 there are still very few types of nanopesticides that have reached the market, except nanoemulsions. The new nanoformulations must compete with existing conventional chemical pesticides with excellent control performance and economic feasibility; some pesticides with high efficacy and a safe environmental profile are already available in the market. For example, plant EOs and neem seed extracts (i.e., azadirachtin) botanical insecticides have been commercialized,197 and NSPW-L30SS, CLARIVA®, SIVANTO® prime, and Nimbecidine EC (0.03% azadirachtin) were developed by agrochemical companies.153

Previous studies have indicated that nanomaterials such as carbon nanotubes and nanosilver can produce acute toxicity in fish, even affect their reproduction, and cause negative effects on algae and other aquatic organisms.198,199 Therefore, the selection of non-toxic, biocompatible, and easily-degradable nanomaterials as the carriers is very important to for the development of nanoformulations,200,201 and it is necessary to intensify the application of nanotechnology in agriculture by developing more stable and safer nanoformulations of biopesticide products. The “green” synthesis of stable nanoformulations of biopesticides with prolonged insecticidal and antimicrobial effects have a promising future, and the biosynthesis of nanoscale materials from a variety of nanoencapsulated biocidal essential oils, enzymes, plant extracts, or biological extract could be a smart alternative.194 The environmental fate of nanobiopesticide formulations should also raise researchers' concerns despite their positive benefits compared to conventional biopesticides, and the potential toxicity of NPs in different crops and the effect on the plant's metabolic activity should also be considered.32,202

Nanobiopesticides can be absorbed, accumulated, and transmitted by the roots and leaves of plants, which is beneficial to the entry of pesticides into the plant and effectively controls of sucking pests and plant diseases. Root absorption is the main pathway for NPs to enter the plants, and the absorbed NPs may be transported upward to the aboveground part of the plants by transpiration,203,204 which makes it possible to control aboveground pests by applying pesticides underground. However, the uptake, bioavailability, and toxicity of nanobiopesticides mainly depend on the particle number, particle stability, and particle size distribution,181 and understanding whether the transport characteristic of nanobiopesticides leads to residues in plants should attract enough attention.204 More studies should be conducted on leaf-targeted bioaccumulation and dose biotransformation mechanisms of nanodelivery to develop specific risk assessment guidelines for nanobiopesticides in the future.

In addition, most reported nanobiopesticides are synthesized at the laboratory level currently, and it is difficult to synthesize high stability nanobiopesticides in large quantities in the preparation process as the preparation process is too complex and sophisticated for industrialization.205 As a result, there are no obvious advantages of equipment investment and production cost of nanobiopesticides when compared with conventional pesticide formulations. Therefore, the development of large-scale standardized preparation of nanobiopesticides is an important research issue, and it is urgent for researchers to develop simple and renewable methods to fabricate nanomaterials to be applied in agriculture fields.4

As for the controlled release of active ingredients nanoformulation, its efficacy and other performance tests must be evaluated over a longer period of time.206,207 As a result, standards for nanoscale preparations and environmental risk assessment criteria should be established to provide basis for new nanopesticide registration, and more field validation trials are needed to evaluate the potential hazards, non-target effects, and resistance of nanobiopesticides by humans and impacts on environmental health.176,208 Moreover, the acceptance of nanopesticides by consumers is low; thus, it seems that nanoparticle-based biopesticides still need more time for an in-depth study to evaluate their safety and increase their acceptance by consumers, and experts and educators should establish more research plans and developmental initiatives to increase the possible interests of customers.

5. Conclusion

Nanotechnology promises a breakthrough in improving the efficacy and safety through the nanoformulation of traditional pesticides/biopesticides, and it is one of the most promising solutions to the real-time challenges in agricultural activity. The development of nanoformulations would promote nanobiopesticide use in agriculture over the next decade. In this review, the potential uses of NPs are briefly illustrated, and the application strategies of nanotechnology in various biopesticides with current and future scenarios are discussed. The uptake and transport of nanobiopesticides in plants are evaluated, and the field evaluations, regulations, and risks involved in nanobiopesticide use are discussed. We believe more governments, universities, industries, and the public should be focused on the nanobiopesticide, and nanotechnology applications in agriculture, which can be successful under greater scientific and sophisticated design.

Author contributions

All the authors contributed to this review. Xiaohong Pan proposed the conceptualization, modified the structures of this review and made subsequent modifications. Xueping Guo wrote the original draft of botanical pesticide, and participated in specifically visualization presentation. Tianyun Zhai wrote the original draft of avermectin and nano chitin/chitosan. Dingyang Zhang wrote the original draft of nanobioherbicides, and participated in references proofreading. Wenhua Rao and Fang Cao wrote the original draft of Bt nanobiopesticide and nanobiofungicides. Xiong Guan acquired the funding and supervised the writing.

Conflicts of interest

There are no conflicts to declare.


This work was supported by the Natural Science Foundation of Fujian Province, China (2020 J01522), Fujian Agriculture and Forestry University Construction Project for Technological Innovation and Service System of Tea Industry Chain (K1520005A03), and the Special Fund for Scientific and Technological Innovation of Fujian Agriculture and Forestry University (CXZX2019005S and CXZX2020024A).


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