Nano-Biopesticides Today and Future Perspectives

biopesticides.

Preface

Opender Koul

Nanotechnology has revolutionized several fields of science like engineering, biotechnology, analytical chemistry, and, of course, agriculture. However, its use in crop protection is just in infancy. While nanotechnology and nanomaterials have been used successfully and safely in medical, environmental, and food processing sciences, their use in agriculture, especially for plant protection by biopesticides, is still a subject under exploration. Utilization of biopesticides and also biological nanomaterials has lots of role to play in pest control in order to become a significant component of organic agriculture. Various bioproducts have been studied and utilized worldwide for integrated pest management; however, strategies for the use of such biopesticides via nanoapplications on a larger scale has still long way to go.

A question that is frequently asked is why nanotechnology-based agriculture? The simple answer could be that the use of bioproducts via biotechnological approaches for pest management is significantly safe to enhance crop protection, which subsequently will help in producing more quality produce of better nutritional value. At the same time, harmful ecological consequences like spreading genetically engineered genes to indigenous plants, increasing toxicity, which may move through the food chain, disrupting nature’s system of pest control, creating new weeds or virus strains, loss of biodiversity, and insecticidal resistance cannot be summarily ignored. Hence, it is necessary to bring forth new innovative technology/methods to overcome these problems. One such novel technology is nanotechnology, which can play a significant role in enhancing the agricultural outputs. However, it is also important to study various aspects related to single or multiple nanoparticles (NPs) or NPs with chemical or biological or natural materials vis-à-vis the environmental impact before recommending for agriculture purposes. Furthermore, formulation methods, handling, and application technologies can also be devised for the better utilization of NPs in agriculture sector. Moreover, compared to commercially available insecticides, chemical and biogenic nanostructured selected metals can provide a cheap and reliable alternative for control of pests, and such studies may expand the frontiers for nanoparticle-based technologies in pest management.

The present volume has been compiled to provide latest insight into all the aspects mentioned here in order to discuss their role as nanobiopesticidal products for pest management. Chapter 1 introduces the subject with an emphasis on definitions and the role of nanotechnology and its use for biopesticide delivery, which is further substantiated in Chapter 2 by discussing the role of technology in crop protection, emphasizing on status and future trends. In addition to the crop protection by nanobiopesticides, they also play some role in nutrition of the plants, which is appropriately discussed in Chapter 3. One of the important components of this technology is the composition and preparation methods of nanobiopesticides, which has been comprehensively dealt with in Chapter 4. For the appropriate delivery of such products, the development of suitable formulations is highly significant, which signifies the parameters required to be studied and standardized. These aspects have been discussed and elaborated in Chapters 5–7 with some case studies provided in Chapter 9. Chapter 8, however, deals with the bioavailability and environmental safety of such nanoproducts.

In addition to the use of nanotechnology for the insecticidal chemicals, there are several studies that show the importance of such a technology having beneficial impact on bacterial (such as Bacillus thuringiensis) and viral (such as baculoviruses) biopesticides as discussed in Chapters 10 and 11. It was observed that Silver NPs have significant impact as insecticidal and microbial biopesticides. These aspects have been discussed comprehensively in Chapters 12–14. The use of nanotechnology for the management of weeds and other undesirable vegetation is in the very early stages of development. Application of this technology to develop practical and commercial bioherbicides is very much at the conceptualization stage and experimentation in field environments is practically nonexistent. However, overview of this is provided in Chapter 15, which deals with the potential for application of nanotechnology in bioherbicide development relying on examples from studies with other biopesticides prepared as nanoformulations to illustrate several possibilities. Patenting issues in the development of nanobiopesticides is a matter of concern and quite significant in order to have reliable and potential products in the market. This has been comprehensively discussed in Chapter 16. Finally, it is essential to know the overall state of the art and future opportunities for the use of nanobiopesticides in agriculture, and extensive details for this have been provided in the last chapter of the book.

I received a tremendous response and support from all the authors for preparing their chapters in tune with the theme of the book, for which I express my gratitude to them. I am also thankful to Lindsay Lawrence and Prem Kumar Kaliamoorthi at Elsevier for the cooperation and help at various stages in the preparation of this volume.

I hope the book will prove useful to all those interested in promoting the cause of biopesticides and nanotechnology applications in both developed and developing countries, so that sustainability in the agricultural systems and crop protection for future generations is achieved.

Chapter 1

Nanobiopesticides: An introduction

Opender Koul    Insect Biopesticide Research Centre, Jalandhar, India

Abstract

Nanotechnology is recognized as one of the key strategies that can contribute to sustainable and competitive agriculture. Several studies have reported an enhancement in the efficacy of certain biological substances on pests, a decrease in toxicity toward humans and the environment, and a reduction of losses due to physical degradation with the encapsulation of these substances in nanoparticulate systems. Thus, nanotechnology could contribute to the development of less toxic biopesticides with favorable safety profiles, increased stability of the active agents, enhanced activity on target pests, and increased adoption by end users. Research has shown that the use of nanoparticles is effective in protecting plant products and plant oils from rapid degradation, allowing a prolonged effect on target pests. Because the polymers used in this kind of formulation are biodegradable, continuous delivery of the active agent with low environmental harm is achieved. Though studies on the risk assessment of nanomaterials vis-à-vis biopesticides toward agroecosystem components after their release into the environment is lacking, it is imperative to add risk-assessment protocols into the strategies based on nanotechnology. Overall, nanobiotechnology seems promising in the direction of formulations that can be used to improve the stability and efficacy of natural products. Such formulations can provide controlled release of the molecules at the site of action, minimize potential toxic effects on nontarget organisms, and prevent degradation of the active agent by microorganisms. While there is certainly industrial activity aimed in this direction, the technology is still far from proven, with major questions persisting around release rates, storage stability, and cost effectiveness. Use of engineered nanomaterials (ENMs) is a widely known phenomenon in nanotechnology. However, relevant toxicity endpoints for ENMs need to be identified and safety evaluations need to be conducted before their application strategies are employed. Safety assessments are not easy because the application of ENMs will be relative to different selected organisms that will depict the sensitivity to the potential toxic effects.

Keywords

Nanotechnology; Nanobiopesticides; Nanoencapsulation; Nanosensors; Sustainable agriculture; Engineered nanomaterials; Environment

Acknowledgments

I am thankful to Murray B. Isman, University of BC, Canada and Melanie Kah, University of Vienna, Austria for their critical reading of the earlier version of the chapter.

1.1 Introduction

The term nanotechnology was coined in 1974 by Norio Taniguichi of Tokyo Science University to describe semiconductor processes such as thin-film deposition that dealt with control on the order of nanometers. His definition still stands as the basic statement today: "Nanotechnology mainly consists of the processing of separation, consolidation, and deformation of materials by one atom or one molecule." Nanotechnology deals with materials at nanoscale levels (1–100 nm), whereby the properties of the matter change compared to the macrosize and thus enable unique applications. However, the definition of nanomaterials is really not a straightforward entity and may not be just a matter of size. The nanoscale can be applied to one or more dimensions and the form of the particles can be in aggregate, agglomerate, or nanostructured materials (Parisi et al., 2015). The available data suggest that about 90% of the nano-based products and patents have been developed in China, Germany, France, Japan, Switzerland, South Korea, and the United States (http://statnano.com/news/45648). In India, progress to date has been slow. However, according to the Planning Commission of India Report of 2011, India has created a nanomission with responsibility for setting nanoscience institutions, developing nanoscale systems, and establishing a regulatory framework for nanotechnology.

Overall applications of nanotechnology in agriculture can be categorized into several groups, such as:

•Seed science.

•Nanofertilizers for crop nutrition.

•Nanoherbicides for weed control.

•Nanopesticides/biopesticides.

•Water management.

•Nanoscale carriers.

•Biosensors to detect nutrients and contaminants and crop-monitoring decisions.

•Issues of agricultural engineering.

•Animal sciences.

•Fisheries and aquaculture.

As per the data available, crops are attacked by about 67,000 species of organisms, and among these insects and mites are the major taxa. The global agricultural production losses due to these pests have been estimated at 10%–16% (Bradshaw et al., 2016). Obviously, different approaches have been used to overcome these losses and the use of nanotechnology for this purpose is gaining momentum due to the potential of this technology in the effective delivery of products. As this book discusses nanobiopesticides in general, therefore, the application of nanomaterials in agriculture is the focus that aims to reduce applications of plant protection products, minimize nutrient losses in fertilization, and increase yields through optimized nutrient management. This implies that while reduction in the pesticide load is inevitable, crop health and vigor cannot be ignored where the use of biofertilizers becomes an equally important component within the pest management system. Nanotechnology tools such as nanoparticles and nanocapsules are being used for the detection and treatment of crop diseases, the enhancement of nutrient absorption by plants, active ingredient delivery, and the exploration of plant breeding and genetic transformations. The potential of nanotechnology in agriculture is large but a few issues remain to be addressed, such as increasing the scale of production processes and lowering costs as well as risk-assessment issues. In this respect, particularly attractive are nanoparticles derived from biopolymers such as proteins and carbohydrates with a low impact on human health and the environment. For instance, the potential of starch-based nanoparticles as nontoxic and sustainable delivery systems for agrochemicals and biostimulants is being extensively investigated. Nanomaterials and nanostructures with unique chemical, physical, and mechanical properties—for example, electrochemically active carbon nanotubes, nanofibers, and fullerenes—have been recently developed and applied for highly sensitive biochemical sensors. These nanosensors (Mishra et al., 2017; Parisi et al., 2015) also have relevant implications for applications in agriculture, in particular for soil analysis, easy biochemical sensing and control, water management and delivery, detection of crop pathogens, and pesticide and nutrient delivery. Nanosensors can also be used for the interpretation of nutrient operations, disease protection, and the sustenance of crop stature (Kaushal and Wani, 2017).

However, on the whole, agro-nanotech innovative products are experiencing commercial constraints due to production costs and the requirement of high volumes of products under field conditions, thus making agricultural applications still a marginal sector for nanotechnology.

1.2 Potential of Nanotechnology

The potential of nanotechnology in terms of its agricultural applications is significantly high; however, there are some key issues that need to be addressed (Fraceto et al., 2016). The foremost issue is application under field conditions, that is, to develop efficient crop production products. Second is the development of sustainable and clean technology. Third is the commercial viability, that is, having cost-effective technologies that are effective. The fourth issue is the fate of nanoproducts and their risk assessment. Last but not least would be the issue of regulation vis-à-vis use in the field and the socioeconomic aspects. However, two applications have played a very significant role in agriculture.

1.Nanoencapsulation.

2.Nanosensors.

Nanoencapsulation plays a vital role in the protection of the environment by reducing leaching and the evaporation of harmful substances as well as its specific potential for pesticide/biopesticide delivery. This is because such nanoencapsulated products would reduce the dosage of pesticides and become environmentally friendly for crop protection (Nuruzzaman et al., 2016) as well as being obtained in different forms (Fig. 1.1). The worldwide consumption of pesticides is about two million tonnes per year, of which 45% is used in Europe alone, 25% is consumed in the United States and 30% in the rest of the world. Careless and haphazard pesticide use increases pathogen and pest resistance, reduces soil biodiversity, kills useful soil microbes, causes biomagnification of pesticides and pollinator decline, and destroys the natural habitat of beneficial organisms such as birds. Therefore, uses and benefits of nanoencapsulation in insect pest management via formulations of nanomaterial-based pesticides and insecticides, increase in agricultural productivity using nanoparticle-encapsulated fertilizers for slow and sustained release of nutrients and water could play a significant role.

Fig. 1.1 Nanoencapsulated materials within a shell give different forms as shown.

Nanosensors (Kaushal and Wani, 2017) are analytical devices with at least one sensing dimension no greater than 100 nm that are fabricated for monitoring physicochemical properties in places otherwise difficult to reach. Nanotubes, nanowires, nanoparticles, or nanocrystals are often used to optimize the signal transduction derived by sensing elements in response to exposure to biological and chemical analytes having a similar size. Nanosensors help farmers maintain their crops with precise control while reporting the timely needs of plants. Thus, it will be necessary to address research efforts toward the development of nanosensors to aid decision making in crop monitoring, offer accurate analysis of nutrients and pesticides in soil, or for maximizing the efficiency of water use for smart agriculture. Nanosensors also find applications in fast, sensitive, and cost-effective detection of different targets to ensure food quality, safety, freshness, authenticity, and traceability along the entire food supply chain. Surely, nanosensors represent an emerging technology challenging the assessment of food quality and safety as well as being able to provide smart monitoring of food components.

Many intelligent packaging materials involve nanosensors as monitoring systems to measure physical parameters (humidity, pH, temperature, light exposure), to reveal gas mixtures (e.g., oxygen and carbon dioxide), to detect pathogens and toxins, or to control freshness (e.g., ethanol, lactic acid, acetic acid) and decomposition (e.g., putrescine, cadaverine). Crop growth and field conditions such as moisture level, soil fertility, temperature, crop nutrient status, insects, plant diseases, weeds, etc., can be monitored through advancements in nanotechnology. This real-time monitoring is done by employing networks of wireless nanosensors across cultivated fields, providing essential data for agronomic intelligence processes such as optimal time of planting and harvesting crops. More precise water delivery systems are likely to be developed in the near future. The factors critical for their development include water storage, in situ water holding capacity, water distribution near roots, the water absorption efficiency of plants, encapsulated water released on demand, and interaction with field intelligence through distributed nanosensor systems.

Overall, the applications of nanotechnology vis-à-vis the role of biopesticides in crop protection are many-fold (Fig. 1.2) and have a tremendous scope in agriculture.

Fig. 1.2 Applications of nanotechnology in agriculture.

1.3 Nanotechnology and Sustainable Agriculture

The use of new technologies to obtain sustainable agricultural growth is undoubtedly a must and the evidence suggests that nanotechnology can play a significant role in achieving this goal. In fact, the idea is to reduce the amount of chemicals applied, minimize nutrient losses in fertilization, and increase yield through pest and nutrient management. How can this be achieved? Foremost is the use of specific nanotools for the control of rapid disease diagnostics, enhancing the capacity of plants to absorb nutrients, and the delivery of products to control of a variety of pests. The significant interests in using nanotechnology in agriculture include specific applications such as nanofertilizers and nanopesticides/nanobiopesticides to increase crop productivity without soil and water contamination while protecting against several insects and microbial diseases. The question can be asked, why nano? The answer is that two key factors account for the special properties of nanomaterials: their quantum effects and their structure.

Their tiny structure means they have a greater relative surface area than other materials and this can alter or improve properties such as strength and electrical characteristics or reactivity. This ultimate technology possesses several unique plasmonic, electronic association, and optical properties that are related to the quantum confinement effects; the alteration of the electronic energy levels may appear due to the surface area in relation to volume ratio.

In modern agriculture, sustainable production and efficiency are unimaginable without the use of agrochemicals such as pesticides, fertilizers, etc. Nanomaterials not only directly catalyze degradation of waste and toxic materials but also improve the efficiency of microorganisms in the degradation of waste and toxic materials. Bioremediation uses living organisms to break down or remove toxins and harmful substances from agricultural soil and water. In particular, some other terms are also generally used such as bioremediation (beneficial microbes), phytoremediation (plants), and mycoremediation (fungi and mushrooms). Thus, with bioremediation, heavy metals can be removed from soil and water environmentally and efficiently by microorganisms (Dixit et al., 2015). On the whole, it is obvious that revolutionary advances can be envisaged during the next decade where convergence between nanotechnology and crop production and crop protection will occur that, according to Diallo and Brinker (2011), would lead to:

•Reengineering of crops, animals, and microbes at the genetic and cellular level.

•Nanobiosensors for identification of pathogens, toxins, and bacteria in foods.

•Identification systems for tracking animal and plant materials from origination to consumption.

•Development of nanotechnology-based foods with lower calories and with less fat, salt, and sugar while retaining flavor and texture.

•Integrated systems for sensing, monitoring, and active response intervention for plant and animal production.

•Smart field systems to detect, locate, report, and direct application of water.

•Precision and controlled release of fertilizers and pesticides.

•Development of plants that exhibit drought resistance and tolerance to salt and excess moisture.

•Nanoscale films for food packaging and contact materials that extend shelf life, retain quality, and reduce cooling requirements.

1.4 Biopesticides and Nanotechnology

During the last few decades, the role of biopesticides in crop protection has gained momentum as alternatives to synthetic pesticides. There are comprehensive research papers, reviews, and books available on the subject (Atwa, 2014; Isman and Grieneisen, 2014; Koul, 2005, 2016; Koul and Dhaliwal, 2002). Recently, new substances have been reported in the literature as promising compounds for use as biopesticides, including strains of the fungus Talaromyces flavus SAY-Y-94-01, extracts of the plant Clitoria ternatea (butterfly pea), products of the fungus Trichoderma harzianum, products of the bacterium Bacillus thuringiensis var. tenebrionis strain Xd3 (Btt-Xd3), the alkaloid compound oxymatrine, fermentation products of the bacterium Lactobacillus casei strain LPT-111, stilbenes accumulated in grape canes, and olive mill wastes (Damalas and Koutroubas, 2018). However, biopesticides have not yet reached the desired level of application in order to overtake chemical pesticides. There are several problems in terms of the stability, field applications, and delivery systems. Overall, biopesticides currently comprise a small share of the total global crop protection market, with a value of about $3 billion worldwide that accounts for just 5% of the total crop protection market. Fewer biopesticide-active substances are registered in the European Union (EU) than in the United States, India, Brazil, or China, due to long and complex registration processes in the EU that follow the model for the registration of conventional pesticides (Damalas and Koutroubas, 2018). To overcome some specific problems of stability and delivery, nanotechnologies can improve the application strategies of biopesticides to facilitate their commercialization; however, from a regulatory perspective, adding nano to biopesticides will not ease the registration process because the toxicity of nanomaterials will further add to the regulatory costs.

Enhancement of the efficacy of biopesticides and a reduction of losses due to physical degradation (e.g., volatilization and leaching), using nanotechnologies has been the subject of several recent studies (Bakry et al., 2016; De Oliveira et al., 2014; Giongo et al., 2016). Thus, nanotechnology could contribute to the development of less toxic biopesticides with favorable safety profiles, increased stability of active agents, enhanced activity on target pests, and increased adoption by end users (Agrawal and Rathore, 2014; Khot et al., 2012; Prasad et al., 2014). Future research must target ways of circumventing the risk factors associated with nanoparticle usage because the current comprehensive knowledge of risk assessment factors and further toxicity of nanoparticles toward agroecosystem components after their release into the environment is lacking (Mishra et al., 2017). Overall, nanobiotechnology seems promising in the direction of formulations that can be used to improve the stability and efficacy of natural products (Ghormade et al., 2011; Perlatti et al., 2013). Such formulations can provide controlled release of the molecules at the site of action, minimize potential toxic effects on nontarget organisms, and prevent degradation of the active agent by microorganisms (Durán and Marcato, 2013; Gogos et al., 2012). While there is certainly industrial activity aimed in this direction, the technology is still far from proven, with major questions persisting around release rates, storage stability, and cost effectiveness (Damalas and Koutroubas, 2018).

Since the development of nanotechnology, the nanoform of SiO2 materials has gained interest for a wide variety of applications. Surface charge-modified hydrophobic amorphous SiO2 NPs have qualified for approval as a novel form of nanobiopesticides for horticultural and crop plants (Barik et al., 2008). In fact, nanopesticides of biological origin (i.e., bionanopesticides) could be fabricated using any metal such as Ag, Cu, SiO2, or ZnO with broad-spectrum pest management efficacy. However, extensive research and a spectra of various field studies are required to fully understand interactions between nanoparticles, microorganisms, soils, plants, and humans (Lade et al., 2017). I would like to point to a very recent study in India where a group of scientists have now shown it possible to substantially enhance the efficacy of such biocontrol agents by converting them into nanoparticles. Researchers at the University of Agricultural Sciences at Raichur in Karnataka have developed a new technique to do so. They have converted the secretion of a bacterium, Photorhabdus luminescens, into nanoparticles and found that its efficacy improved significantly (Kulkarni et al., 2017). A multistage process involving culturing, centrifugation, ultrasonic-assisted atomizing, and hot air-assisted vacuum has been used to obtain the product in the form of a dry powder. Cellular secretions of P. luminescens have been used as a pesticide against a wide range of insects. The bacterium lives within the body of a nematode called Heterorhabditis in a symbiotic relationship with the nematode. It secretes an array of toxins and enzymes. The secretions have a wide range of insecticidal actions against both sucking and chewing arthropod pests of agricultural crops.

The nano form of this biocontrol agent has been tested against two sucking pests of cotton, Tetranychus macfarlanei and Aphis gossypii. This study suggests that high mortality coupled with quick action emphasises the potential of nanotechnology in enhancing the pathogenicity of a microbial pesticide. It was found that a very low concentration of nanoparticulated secretion could kill pests relative to the unprocessed secretion. This means farmers need very small quantities of biopesticide in its nano form.

Nanoencapsulation of volatile compounds is an important tool that can be used to overcome the lack of stability of these compounds. The preparation and characterization of chitosan nanoparticles functionalized with β-cyclodextrin containing carvacrol and linalool have been recently documented to show extended stable toxicity. Biological activity against Helicoverpa armigera (corn earworm) and Tetranychus urticae (spider mite) were prevalent. In addition, repellent activity and reduction in oviposition were also observed for the mites (Campos et al., 2018). This suggests that nanocarriers could play a very important role in associating complex plant extracts or individual phytochemicals. The advantages could be enhanced bioactivity due to controlled release as well as increased activity against the pest. This has been emphasized in studies with medicinal plant extracts vis-a-vis the physicochemical characterization of the nanostructured delivery systems containing these complex matrices (Zorzi et al., 2015).

Nanotechnology also has a potential key role in the development of nanoherbicides. This has become necessary because the synthetic herbicide load needs to be reduced due to the pervasive problem of herbicide-resistant weeds caused by overuse of herbicides on herbicide-resistant transgenic crops on a global scale. Therefore, while the development of bioherbicides to control weeds is inevitable (Duke et al., 2014; Hershenhorn et al., 2016), the nano products for efficient delivery will be helpful in enhancing the bioefficacy of such products. For example, in a recent study, the agro (nano) technology for presowing treatment of rice seeds with environmentally sound, physiologically active, polyfunctional multicomponent complex (nano) chips with herbicide activity has been developed. These (nano) chips are based on natural minerals and polysaccharide derivatives from local raw material resources: modified vermiculite, sodium salt of carboxymethyl cellulose, and plant protection strategies (like herbicide and a biopesticide-AgroHit elicitor) (Voropaeva et al., 2014). These studies suggest about a twofold increase in crop yield along with significant weed growth inhibition. There are several such studies available in the scientific literature; these will be comprehensively dealt with in Chapter 15 of this book.

Diseases caused by bacteria, fungi, nematodes, and viruses are of major concern in agriculture where billions of dollars are lost due to damage in various crops. It has been estimated that about $600 million per year is spent on fungicides (Gonzalez-Fernandez et al., 2010). Mycotoxins alone impact about 25% of food crops globally (Patel et al., 2014). Obviously, novel approaches to control diseases are inevitable and the use of nanotechnology is one of them. The use of nanomaterials to suppress crop diseases in order to enhance crop yields has been widely studied (Servin et al., 2015). Navarro et al. (2008) suggested that high surface area nanoscale materials could more effectively retain nutrients and serve as a longer-term and more stable nutrient reservoir to plants. What seems to be a point of consideration is that effective nanomaterials may require plant micronutrients as well to raise the potential of the products and the growth of the crop through nutritional benefits. However, it is important to establish the efficacy of nanomaterials through additives/carriers as well as the use of nanoparticles themselves (Naderi and Danesh-Shahraki, 2013). The studies available suggest that the production of nanoenabled pesticides and fertilizers with greater solubility, more stable dispersal, decreased persistence, and greater target specificity is required (Rai et al., 2012) to have potential products for use under field conditions. It is, therefore, obvious that the role of nanotechnology in disease management by biopesticides or plant nutrition by biofertilizers is of great importance; this will be dealt with in subsequent chapters of the book.

There are some concerns too, regarding the potentially hazardous effects of nanobiopesticides on soil, human health, and the environment. While nano products may show potential bioefficacy, there could be hazardous interactions of nano-based pesticides with soil. Apart from nanoparticles, the particular plant species carrying peculiar photochemicals may play a crucial role in nanoparticle formulations as well. There are some plant extracts that have been exploited for insecticidal activity such as Catharanthus roseus L., Datura metal L., Cardiospermum halicacabum L., Argemone mexicana L., Calotropis procera L., Azadirachta indica A. Juss, Oscimum sanctum L., Oscimum canum L., and Citrus sinensis L. that have been tested for the development of effective nanoparticles. However, not all of them show enhanced activity. For example, in the case of neem, not all the nanoformulations obtained showed insect control efficacy and none showed a high residual effect, indicating that there was little or no liberation of active ingredients from the nanoparticles (Giongo et al., 2016). Therefore, studies are needed to improve the release rate of the compounds by the polymers.

1.5 Engineered Nanobiopesticides

The use of engineered nanomaterials (ENMs) is a widely known phenomenon in nanotechnology and can be categorized, as shown in Fig. 1.3. A vast variety of new materials is being developed. Screening ENMs by means of in vitro studies has been suggested by many as a fast approach to distinguish between low and high toxicity ENMs (Nel et al., 2006; Service, 2008; Shaw et al., 2008). Various chemical and physical methods have been developed to obtain nanomaterials, specifically the ecofriendly products such as biosynthesis of nanomaterials from plant extracts (Mittal et al., 2013). The traditional methods of synthesis often rely on chemical reduction in a liquid phase, as this enables greater control over structure and yield (Charitidis et al., 2014). Common reducing agents include citric acid, hydroxylamine, cellulose, hydrogen peroxide, sodium carbonate, and sodium hydroxide. Stabilizing agents are frequently added to promote dispersion and uniform particle size distribution; common stabilizers are polyvinyl alcohol and sodium polyacrylate. Detailed chemical reduction methods have been reported for Ag (Guzma´n et al., 2009), Au (Akbarzadeh et al., 2009), and Pt (Charitidis et al., 2014), among others. Metal oxide nanoparticle synthesis such as ZnO, CeO2, TiO2, CuO, and Al2O3 typically relies on vapor phase-based techniques (Comini, 2013). Hydrothermal techniques are seeing increasing use due to greater control of product properties and purity. A number of physical techniques can also be used for nanomaterial synthesis, with common approaches being laser ablation, chemical vapor deposition (CVD), sonochemical reduction, supercritical fluids, and gamma radiation (Charitidis et al., 2014). For carbon, fullerenes are often synthesized by arc-discharge or gas-combustion methods (Swihart, 2003), whereas carbon nanotubes are produced by CVD through the decomposition of gaseous hydrocarbon. Notably, a major shortcoming of CVD is related to product purity, which is inversely related to yield (Lai and Zhang, 2011). Given the sensitivity of many crops to heavy metals and solvents common to these synthesis protocols and the potential for food contamination from these constituents, it is clearly important to consider and recognize the potential for significant toxicological impacts from nanoparticle impurities and, perhaps more importantly, to adequately characterize the material prior to use in agriculture. On the whole, engineered nanoparticles that have received most of the attention in other sectors—carbon nanotubes, nanosilver, etc.—have very low potential for large-scale agricultural applications. Interest has also shifted from inorganic toward organic-based nanomaterials such as nanoencapsulates and nanocomposites (Aschberger et al., 2015). Nanoagrochemicals that use organic-based delivery systems developed for food or pharmaceutical applications are, however, often not economically competitive with other agrochemicals/biopesticides. There is a specific need to go for critical investigations assessing whether the products identified in the literature are able to compete with existing formulations in terms of both costs and performance (Kah, 2015). According to Kah et al. (2018a), differences in toxicological effectiveness or efficacies observed in the laboratory conditions were not always repeatable under field conditions. Investigations need to be realistic vis-à-vis the field situations at larger scales. Advantages in comparison to conventional products could only be beneficial if the efficacy, potential cost/benefit to the crop producers and consumers, and environmental impact compete to a large extent with the existing products. This is an observation that cannot be summarily ignored.

Fig. 1.3 Categorisation of engineered nanomaterials.

1.5.1 Impact on Environment

Nano substances do not necessarily constitute a hazard or risk to the environment. However, the specific properties of such materials cannot be summarily ignored. Knowledge of the characteristics, behavior, and effects of nanomaterials has come to the fore over the past decade. It is imperative to assess their environmental risks and these in turn have to be reflected in regulatory requirements. Obviously, the impact on the food chain cannot be ignored (Fig. 1.4). To be precise, relevant toxicity endpoints for ENMs need to be identified and safety evaluations need be done vis-à-vis their application strategies (Nel et al., 2006; Oberdorster, 2010). Safety assessments are not easy because ENM application will be relative to different organisms that will depict the sensitivity to the potential toxic effects. Differences in particle uptake and removal will obviously play a role, but specific cell functions will likely also be involved. Cocultures may better reflect the in vivo exposure situation, although none of the currently described models can be used as a standalone model, replacing the need for in vivo testing. With regard to exposure duration, in vitro studies are only suitable to study ENM effects after relatively short exposure periods. Normally, ENMs are prepared to be virtually nondegradable (though not a generalized phenomenon); therefore, the chances of accumulation increase, which could lead to serious risks. Therefore, to study the behavior of ENMs is also important. What is important is to screen a wide variety of ENMs for toxicity endpoints, and that will determine the comparative hazardous nature of the products. Shaw et al. (2008) have studied 50 different ENMs and demonstrated that the biological activity of these arise from combined effects based on their composition, making it difficult to predict their impact. It is becoming increasingly clear that more than one single physicochemical characteristic determines the toxicity of ENMs. Another perhaps more feasible approach would be to group ENMs according to their biological activity in a test battery, and compare this biological activity to that of an ENM that has been proven safe (Shaw et al., 2008).

Fig. 1.4 Nanomaterial implications on the food chain and possible targets of impact.

1.6 Conclusions

Nanotechnology could contribute to the development of less toxic biopesticides with favorable safety profiles, increased stability of the active agents, enhanced activity on target pests, and increased adoption by the end users. Research has shown that the use of nanoparticles is effective in protecting plant products and plant oils from rapid degradation, allowing a prolonged effect on target pests. Though studies on risk assessment of nanomaterials vis-à-vis the biopesticides toward agroecosystem components after their release into the environment are lacking, it is imperative to add risk assessment protocols into strategies based on nanotechnology. It has been envisaged that nanoformulations may have a greater impact on the fate of active ingredients than commercially available formulations. However, the differences in the fate of products could be moderate, as suggested by Kah et al. (2018b), but the release of products from nanocarrier systems may be quite rapid and thereby the durability of the active ingredient would be short, both in water and in soil environments.

While there is certainly industrial activity aimed in the development of nanoproducts, the technology is still far from proven, with major questions persisting around release rates, storage stability, and cost effectiveness. There is much action going on in the area of biopesticide nanotechnology. Some products of this type may hit the market in the next couple of years. Eden Research in the United Kingdom (edenresearch.com) claims a patented micro encapsulation technology and a collaborative agreement with Sipcam (Italy) for the development and marketing of fungicides and insecticides.

Use of ENMs is a widely known phenomenon in nanotechnology. However, relevant toxicity endpoints for ENMs need to be identified and safety evaluation conducted before their application strategies are employed. Safety assessments are not easy because the application of ENMs will be relative to different selected organisms that will depict the sensitivity to the potential toxic effects.

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