Silver nanoparticles: Potential as insecticidal and microbial biopesticides

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12

Silver nanoparticles: Potential as insecticidal and microbial biopesticides

Badal Kumar Mandal School of Advanced Sciences, Vellore Institute of Technology (VIT), Vellore, India

12.1 ­Introduction Biopesticides consists of plant secondary metabolites and their mediated metal and metal oxide nanomaterials, but they also include nematodes, entomopathogenic viruses, fungi, and bacteria. Due to their less hazardous and ecofriendly nature, they are considered alternatives to chemical pesticides. Many researchers are doing research on biopesticides for many pest control programs as the key entity. In addition, pests have adopted insecticide resistance while the registration of some insecticides has expired or stopped due to human health and environmental concerns. This demands more novel and stronger pesticides for pest management. In this regard, novel active ingredients on the nanoscale with their formulation and delivery are called nanopesticides. Hence, the application of biopesticides has thus become the target for nutrient management systems in the agrosector. In India, the registered biopesticides are Bacillus thuringiensis var. israelensis, Bacillus thuringiensis var. kurstaki, Bacillus sphaericus, and B. firmus for controlling diamondback moths; Bacillus thuringiensis var. galleriae for controlling Helicoverpa armigera; Trichoderma viride and Trichoderma harzianum for root rots and wilts; neem-based biopesticides for controlling the white fly; NPV of Helicoverpa armigera for controlling Helicoverpa on chickpeas; Cymbopogon for controlling insects; Beauveria bassiana for mango hoppers, mealy bugs, and the coffee pod borer; H. bacteriophora for controlling borers; Pseudomonas fluorescens for controlling bacterial and fungal pathogens; NPV of Spodoptera litura for controlling Spodoptera litura; and the Trichogramma parasitoid for sugarcane borers (Anonymous, 2014; Mishra et al., 2018). Nowadays, mosquito-borne diseases such as the Zika and West Nile viruses, dengue, malaria, and yellow fever are spreading recklessly as well as causing calamity to society due to the multidrug resistance behavior of these vectors (Amerasan et al., 2012; Ankamwar et al., 2005; Appadurai et al., 2015; Benelli, 2016a,b; Kovendan et  al., 2018; Ayya et  al., 2015). Dengue-related fever, chikungunya, and yellow ­fever have become a threat to humans and are spread by Aedes aegypti (Benelli and Govindarajan, 2017), whereas Culex quinquefasciatus is a vector of lymphatic ­filariasis (Benelli and Mehlhorn, 2016). More than 130 crore people from 81 Nano-Biopesticides Today and Future Perspectives. https://doi.org/10.1016/B978-0-12-815829-6.00012-7 © 2019 Elsevier Inc. All rights reserved.

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c­ ountries are severely suffering from lymphatic filariasis globally (Chowdappa and Gowda, 2013; WHO, 2010). Similarly, pests including insects, mites, nematodes, and pathogens are causing issues by limiting profitable crop production.

12.2 ­Role of Nanobiotechnology Nanotechnology has provided tools and materials for the targeted delivery of agrochemicals in a sustainable manner as well as by providing diagnostic tools for early detection. The encapsulation and entrapment of agrochemicals are gaining popularity in controlling pests and microbes. Nanocapsules are used for the delivery of pesticides, fertilizers, and other agrochemicals because they reduce the frequent application of chemicals through a slow release. Also, NPs having a higher surfaceto-volume ratio and stability are more soluble and increased activity many times compared to their bulk form (WHO, 2010). Nanomaterials also play a main role in promoting sustainable agriculture for better food globally (Gruère, 2012). Because nano-based materials show more efficacy as well as the least ecological impact and human toxicity, nanocomposites are considered for overall disease management. Nanosensors are a wonderful nanotechnology product that can detect insects, pathogens, and weeds to promote precision farming as well as provide timely information on the application of required fertilizers, herbicides, and pesticides (Scot and Chen, 2003). Pathogens have become resistant to systemic bactericides and fungicides such as Staphylococcus aureus is resistant to methicillin, Candida albicans is resistant to fluconazole, and Phytophthora infestans developed resistance against metalaxyl (Chowdappa and Gowda, 2013; Schaller et  al., 2003). Biopolymers of natural origin are considered for the preparation of biopolymer nanocomposites for insecticidal and antimicrobial agents to minimize the uses of petrochemicals and toxic chemicals toward pest management, plant diseases, and crop protection in the agricultural sector as well as other fields, including beneficiation of mankind. Pesticide residue in the end products, especially consumable and edible products, has caused serious concern to environmentalists and health workers due to its hazardous and toxic nature. This has spurred the scientific community to urgently search for a replacement or suitable alternate in pest management as well as pathogen control. Ag NPs do not cause the alteration of gene expression in insect trachea and hence are qualified for approval as a nanobiopesticide. Also, they are effective, biodegradable, and do not leave any harmful effects on the environment; they are also less of a threat to human health. Today, nanoparticles are used in the formulation of nano-based pesticides and insecticides, encapsulated nanoparticles, nanoparticle-mediated genes or DNA transfer in plants, and biosensors for remote sensing for precision farming. Treating castor seeds and Ricinus communis L. with Ag NPs did not affect the seed germination rate nor the growth of lepidopteran insects on the seeds (Yasur and Usha Rani, 2013, 2015). However, such particles could penetrate the plant or animal cells and act as potential nanocarriers of agrochemicals such as pesticides, herbicides, rodenticides, fertilizers and therapeutics.

12.3 ­ Ag NPs as biopesticides

12.3 ­Ag NPs as Biopesticides Among metal nanoparticles, silver nanoparticles (Ag NPs) have been used as antimicrobial agents since ancient time due to their broad spectrum and multiple modes of antimicrobial activity (Figs.  12.1 and 12.2) (Kiran Kumar et  al., 2014; Sireesh Babu et al., 2017a; Jo et al., 2009; Kim et al., 2012; Wei et al., 2009). Ag NPs exhibit antimicrobial activity by different modes. It is seen that Ag NPs are more toxic to microorganisms compared to mammalian cells. They have shown antifungal activity to rose powdery mildew (Kim et al., 2008). Also, they act as plant-growth stimulators, insecticides, germicides, bactericides, antimicrobial agents, and sterilizers (Baier, 2009). Silver is used in many applications in its pure metallic form or as a compound because it possesses antimicrobial activity against pathogens but remains nontoxic to humans (Elchiguerra et al., 2005; Yeo et al., 2003). In addition, Ag NPs are more active and sensitive to antibiotic-resistant microbial cells due to their greater penetrating power compared to many organisms (Samuel and Guggenbichler, 2004). Ag NPs (@100 ppm) showed very good inhibitory activity to different fungi, that is, Colletotrichum gloesporioides, Bipolaris sorokiniana, and Magnaporthe grisea as well as the plant pathogenic fungi Rhizoctonia solani, Sclerotinia sclerotiorum, and S. minor, compared to commercial fungicides (Lamsal et al., 2011a,b; Aguilar-Méndez et al., 2011; Jo et al., 2009; Kim et al., 2012; Min et al., 2009). Among nanomaterials, mostly inorganic nanomaterials, that is, metal and metal oxides, silica- and carbon-based materials, semiconductors, and quantum dots are functionalized for delivery or tracking purposes (Kunzmann et al., 2011). Polymer NP-based formulations are coming up nowadays in different fields, especially the pharmaceutical and cosmetic sectors. These sectors are using different polymeric materials such as polysaccharides (chitosan, alginates, and starch), polyesters, and polyethylene glycol (PEG), and biogenic biodegradable materials such as beeswax, corn oil, lecithin, or cashew gum (Abreu et al., 2012; Nguyen et al., 2012).

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FIG.12.1 Antibacterial activity of synthesized Ag NPs on S. aureus (A), E. coli (B) and histogram showing zone of inhibition (C). Reprinted from [Kiran Kumar et al., 2014] with permission from Elsevier.

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FIG. 12.2 Cell viability of mouse fibroblast 3T3 cells after 24 hours treatment with increasing amounts of diastase stabilized Ag NPs. Reprinted from [Sireesh Babu et al., 2017a] with permission from Elsevier.

Among them, polyethylene glycol-based amphiphilic copolymers are so far the most attractive due to their biodegradability, easy processing, and well-explored properties (Torchilin, 2006; Shakil et al., 2010). Some literature has documented different opinions on polymer-based nanoformulations, which include very slow release, less environmental stability, higher synthesis cost, and high-energy requirement (Torchilin, 2006). Interestingly, solid inorganic NPs have eliminated and overcome the drawbacks due to their combined properties of nanoemulsions, liposomes, and polymer NPs (Dimetry and Hussein, 2016; Benelli, 2016a).

12.4 ­Pest Management by Ag NPs Several chemical insecticides are used to control different houseflies, resulting in insecticide resistance in the insect, which causes a negative impact on nontarget organisms including humans (Acevedo et  al., 2009; Hemingway and Ranson, 2000; Naqqash et  al., 2016). So, there is an increasing demand to search for alternative ­control materials that are highly effective and safe for humans. Among different alternate control materials spherical Ag NPs has been considered as one of the best and promising antimicrobials (Figs.  12.1 and 12.2) (Kiran Kumar et  al., 2014; Sireesh Babu et al., 2017a). Moringa oleifera leaf extract (Mo-LE)-mediated synthesized Ag NPs and ZnO NPs showed larvicidal and pupicidal toxicity against Musca domestica at a low dose. The authors did a larvicidal bioassay against the pupae (pupicidal activity) and larvae and the LC50 values were 16.50, 2.03, and 6.41 mg/mL for the leaf extract, Ag NPs, and ZnO NPs while the LC50 values were 129.77, 9.604, and 17.10 mg/ mL for the leaf extract, Ag NPs, and ZnO NPs, respectively, against the pupae. Also, fecundity of the female and a reduction in egg hatchability were noticed. In addition,

12.4 ­ Pest management by Ag NPs

the total protein content and some important enzymatic activities of esterases, acetylcholine esterase, and glutathione S-transferase enzymes were significantly decreased in larvae after exposure to the NPs (Abdel-Gawad, 2018). The M. oleifera synthesized Ag NPs (Mo-Ag NPs) had insecticidal activity against Aedes aegypti (Sujitha et al., 2015) and Culex quinquefasciatus (Murugan et al., 2016). Kamaraj et al. (2012) evaluated the toxicity of the Manilkara zapota leaf extract and its synthesized silver nanoparticles against the adults of M. domestica (LD50=3.64 mg/mL) (Kamaraj et al., 2012). Furthermore, Gul et al. (2016) found that melon aqueous extract synthesized Ag NPs showed significantly high mortality against housefly adults (Gul et al., 2016). Roni et al. (2015) reported that Hypnea musciformis extract and Ag NP strongly reduced the longevity and fecundity of A. aegypti and Plutella xylostella adults (Roni et al., 2015). Also, the pungam oil-based gold nanoparticles significantly reduced the fecundity of Pericalia ricini (Sahayaraj et al., 2016). Plant, bacteria, fungi, and algae extracts are capable of synthesizing silver nanoparticles (Ag NPs) (Borase et  al., 2014). Secondary metabolites of plants are capable to reduce metal ions and tune size and shape of the synthesized metal nanoparticles by controlling nucleation/coalescence/aggregation after stabilizing nanoparticle surface via surface coating of oxidized phytochemicals especially polyphenols (Figs. 12.3–12.5) (Kiran Kumar and Mandal, 2015; Sireesh Babu et al., Reduction Silverions gets reduced to there nano form (Ag+ to Ag0)

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FIG. 12.3 Plausible mechanism of reduction and stabilization involved in the formation of stable SNPs. Reprinted from [Kiran Kumar and Mandal, 2015] with permission from Elsevier.

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High availability

Oxidized

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FIG. 12.4 Mechanism showing how oxidized polyphenols involved in tuning size and shape of AgNPs. Reprinted from [Sireesh Babu et al., 2017b] with permission from Elsevier.

FIG. 12.5 Study of morphology of Ag NPs: (a) and (b) TEM, (c) HRTEM, and (d) SAED pattern of Ag NPs. Reprinted from [Mohan Kumar et al., 2012] with permission from Elsevier.

12.6 ­ Ag NPs-composites for pest management

2017b; Mohan Kumar et al., 2012). Ag NPs were synthesized by using Syzygium cumini seed extract and they showed mosquito ovicidal, larvicidal, and adulticidal activity against three important adult female mosquitoes—Anopheles stephensi, Aedes aegypti, and Culex quinquefasciatus—with doses of An. Stephensi (LC50 = 14.58 μg/mL), Ae. aegypti (LC50 = 16.45 μg/mL), and Cx. quinquefasciatus (LC50 = 18.83 μg/mL) larvae. Ag NPs with S. cumini showed higher effective doses to An. stephensi (LC50 = 35.51 μg/mL), Ae. aegypti (LC50 = 47.94 μg/mL), and Cx. quinquefasciatus (LC50 = 61.79 μg/mL). Hence, these could be environmentally safer biopesticides to control mosquito vectors (Kanthammal et al., 2018).

12.5 ­Synthesis of Ag NPs by Marine Organisms Several researchers have attempted to synthesize Ag NPs using different marine plants for pest management in the public health sector or agriculture. Sargassum muticum (Yendo) Fensholt (Fucales: Sargassaceae) aqueous extract-mediated synthesized Ag NPs were able to suppress the growth of Ariadne merione (Cramer) (Lepidoptera: Nymphalidae) fourth instar larvae (Vinayaga Moorthi et al., 2015). In another study, Ag NPs were synthesized by the aqueous extract of Caulerpa scalpelliformis (R. Brown ex Turner) C. Agardh (Bryopsidales: Caulerpaceae) and showed mortality to all larvae of C. quinquefasciatus at a dose of 10 mg/L (Murugan et al., 2015), whereas Mesocyclops longisetus showed higher toxicity to C. quinquefasciatus larvae at the same dose (Amerasan et al., 2016). Rouhani et al. (2012) synthesized Ag NPs and Ag-Zn NPs using the solvothermal method (Rouhani et al., 2012); these acted as insecticides against the oleander aphid A. nerii Boyer de Fonscolombe (Hem.: Aphididae). The LC50 values of Ag NPs and Ag-Zn NPs were 424.67 and 539.46 mg mL−1 against imidacloprid ([E]-1-[6-chloro3-pyridylmethyl]-N-nitroimidazolidin-2-ylideneamine)] drug as 0.13 μL mL−1, respectively, after dipping first instar nymphs infested leaves in nanoparticles and drug solutions (Rouhani et al., 2012). Enzymes are also used to synthesize metal nanoparticles. Some bacteria can secrete enzymes containing cofactor NADH and NADH, especially nitrate reductase, and can reduce Ag ions to Ag Ag NPs in a greener way (Kalimuthu et al., 2008).

12.6 ­ Ag NPs-Composites for Pest Management Many polymeric materials have been used to prepare Ag NP-doped polymeric composites/films for antimicrobial and antifungal applications in different fields. Normally, chitosan, pullulan, and nonionic surfactant tween-80 (0.1%) can increase the wettability and sticking property of the coating solution, which results in a significant reduction of disease growth compared to control (Chowdappa and Gowda, 2013). Pullulan-based Ag NP-doped polymeric films showed high inhibitory activity to fungal sporulation of Aspergillus niger (Pinto et al., 2013; Rabea et al., 2003). A chitosan-based Ag NP-doped composite was used as a fruit coating material to prevent the growth of C. gloeosporioides

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with mango anthracnose (Chowdappa and Gowda, 2013). Normally, fungicides such as mancozeb and carbendazim are used to inhibit the growth of anthracnose after submerging the fruit for 5 min in hot water (52°C) containing a fungicide within 24 h of postharvest. Rouhani et al. (2011) checked the insecticidal activity of ZnO-TiO2-Ag NPs against Frankliniella occidentalis pergande and found that 28%ZnO-70%TiO22%Ag showed the maximum mortality effect (LD50 = 195.27 mg L−1), whereas the Guan et  al. (2008) NP-coated imidacloprid (IMI) enhanced the mortality effect of 50% nano-SDS/Ag/TiO2-IMI to the adult stage of Martianus dermestoides Chevrolat (Coleoptera: Tenebrionidae) with reference to 95% IMI. Also, pure Ag NPs showed a higher mortality effect than Ag-Zn NPs (Guan et al., 2008).

12.7 ­Modern Mode of Biopesticides Delivery Many pesticides and insecticides are encapsulated for targeted and slow release. Biopolymer chitosan alginate (635 nm in size) beads were used to entrap herbicide paraquat for slow release so that plants can absorb completely without wasting the chemical from treatment to absorption (Silva et al., 2011; Scrinis and Lyons, 2007). Other modes of delivery, that is, microemulsion, nanoemulsion, nanodispersion, a polymer-based nanoparticle, a solid lipid nanoparticle, clay, porous hollow silica nanoparticles, layered double hydroxides, and metal-based nanoparticles were used for plant protection. Nowadays, liposomesbased encapsulation of biocides is coming in the field to sustain and prolong the action of different agrochemicals to plants (Kah et al., 2012). Nano-formulations and dispersions may bring advancements in properties such as stability in the applied field, prevention of pest defense, and penetration of the cell walls, benign to both plants and animals and killing the pests with new modes of action. Finally, these formulations might be formulated easily at the lowest possible cost within a short course of time (Athanassiou et al., 2018; Smith et al., 2008; Benelli, 2016a). In addition, nano-based formulations improve the water solubility of water-insoluble active ingredients, remove the uses of toxic organic solvents, introduce the sustained or controlled release of active ingredients, improve the mobility of active ingredients as well as insecticidal activity with extended longevity due to smaller particles having a higher surface-to-volume ratio (Sasson et al., 2007).

12.8 ­ Control of Pest and Related Information Although the majority of plant-mediated nanomaterials have been used as insecticides to control mosquitoes (Benelli 2016a,b; Sujitha et al., 2015), a few other researchers used biogenic metal nanoparticles for controlling louse flies (Hippobosca maculata) (Jayaseelan et al., 2012), moths (Roni et al., 2015), hard ticks (Haemaphysalis bispinosa) (Abduz Zahir and Abdul Rahuman, 2012), and lice (Pediculus humanus capitis) (Jayaseelan et al., 2011). Ag NPs (~20 nm) coated on wool fibers prevented completely the growth of the clothes moth, Tinea pellionella (L.) larvae (Lepidoptera: Tineidae) after four days of exposure to nanosilver (Ki et  al., 2007). Tinospora

12.9 ­ Antifungal activity of Ag NPs

­cordifolia leaf extract-mediated synthesized Ag NPs showed complete mortality to the adult head louse P. humanus capitis De Geer (Phthiraptera: Pediculidae) within 1 h after exposure of a 25 mg/L Ag NP dispersion (Jayaseelan et al., 2011). In another study, 30 ppm of Sargassum muticum-synthesized Ag NPs completely prevented the egg hatchability of A. stephensi, A. aegypti, and C. quinquefasciatus (Madhiyazhagan et al., 2015). Also, the Mimosa pudica L. (Fabales: Fabaceae) leaf extract-mediated synthesized Ag NPs killed completely the mosquito larvae of A. subpictus and C. quinquefasciatus after 24 h exposure of a 20 mg/L Ag NP dispersion (Marimuthu et  al., 2011). Also, 89% of the exposed tick Rhipicephalus microplus Canestrini (Acari: Ixodidae) larvae was dead within 24 h at a dose of 20 mg/L (Yasur and Usha Rani, 2013). Similar observations are documented elsewhere (Veerakumar and Govindarajan, 2014; Veerakumar et al., 2014). Arjunan et al. (2012) synthesised Ag NPs using Annona squamosa L. (Magnoliales: Annonaceae) leaf extract and applied to C. quinquefasciatus and Anopheles stephensi Liston (Diptera: Culicidae) pupae at a dose pf 10 mg/L, which killed more than 90% of the larvae (Arjunan et al., 2012). Similarly, Delphinium denudatum Wall (Ranunculales: Ranunculaceae) root aqueous extract-mediated synthesised Ag NPs killed completely the larvae of A. aegypti L. (Diptera: Culicidae) after 48 h of exposure at a dose of 1000 mg/L (Suresh et al., 2014). The Phyllanthus niruri L. (Malpighiales: Phyllanthaceae) leaf aqueous extract-mediated synthesized Ag NPs showed a time-dependent mortality to A. aegypti larvae and killed all larvae after 72 h of exposure (Athanassiou et al., 2018). Many other plant-based Ag NPs are used for controlling mosquitoes, including Feronia elephantum Correa (Sapindales: Rutaceae) leaf extract-mediated Ag NPs (Veerakumar and Govindarajan, 2014), Heliotropium indicum L. (Eudicotidae: Boraginaceae) leaf extractmediated synthesised Ag NPs (Veerakumar et al., 2014), neem leaf extract-mediated Ag NPs (Soni and Prakash, 2012, 2014), Phyllanthus niruri-synthesized Ag NPs (Suresh et al., 2015), Mimusops elengi L. (Ericales: Sapotaceae)-synthesized Ag NPs (Subramaniam et al., 2015), and Hypnea musciformis (Wolfen) (Ericales: Cystocloniaceae)-fabricated Ag NPs (Roni et al., 2015). Manilkara zapota (L.) P. Royen (Ericales: Sapotaceae) leaf extract-mediated synthesized Ag NPs suppressed completely the adult stage of Musca domestica L. (Diptera: Muscidae) after 4 h of exposure at a specified dose (10 mL Ag NP dispersion in one liter) (Kamaraj et  al., 2012). Euphorbia hirta L. (Malpighiales: Euphorbiaceae) leaf extract was used to synthesize Ag NPs and then the synthesized Ag NPs was also used to kill the cotton bollworm, Helicoverpa armigera (Hubner) (Lepidoptera: Noctuidae). It killed all stages of larvae and pupae after four days of 10 ppm Ag NP exposure (Durgadevi et al., 2014).

12.9 ­Antifungal Activity of Ag NPs Different fungus species also are used to synthesize Ag NPs. Filamentous fungus such as Cochliobolus lunatus and Anopheles stephensi Liston (Diptera: Culicidae) (Salunkhe et  al., 2011), Chrysosporium keratinophilum conidia (Onygenales: Onygenaceae) (Soni and Prakash, 2012), and Trichoderma harzianum Rifai

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(Hypocreales: Hypocreaceae) (Sundaravadivelan and Padmanabhan, 2014) were used to synthesize Ag NPs. The synthesized Ag NPs showed complete mortality to the first, second, third, and fourth instar larvae or pupae of A. aegypti and A. stephensi with less than 1% nanoparticle dispersion after 24 h exposure. Fluconazole has good antifungal activity to different fungi such as Phoma glomerata, P. herbarum, Trichoderma sp., F. semitectum, and Candida albicans. When this drug was applied with Ag NPs, its activity was increased, but not uniformly (Gajbhiye et al., 2009). This study showed enhanced activity to C. albicans, Trichoderma sp., and P. glomerata, but almost no increment was observed for F. semitectum and P. herbarum. Similar synergistic results of Ag NPs with fluconazole were noticed against fungi A. alternate, F. oxysporum, and Cladosporium herbarum (Bholay et al., 2013). There are different plant pathogenic fungi such as Alternaria alternata, S. sclerotiorum, Macrophomina phaseolina, Rhizoctonia solani, Botrytis cinerea, Curvularia lunata, Bipolaris sorokiniana, Magnaporthe grisea, Fusarium oxysporum f.sp. vasinfectum, Aspergillus niger, A. flavus, S. rolfsii, A. alternate, F. oxysporum, Cladosporium herbarum. Gloeophyllum abietinum, G. trabeum, Chaetomium globosum, Phanerochaete sordida, S. rolfsii, R. bataticola, and A. niger. Kim et al. (2012) applied an Ag NP colloidal dispersion to 18 different plant pathogenic fungi on potatoes, malls, and corn dextrose agar in the range of 10–100 mg/L and found that 100 mg/L dispersion showed high antifungal activity. Also, Acalypha indica leaf extract-mediated synthesized Ag NPs showed antifungal activity to Macrophomina phaseolina, Botrytis cinerea, Curvularia lunata, Rhizoctonia solani, Alternaria alternate, and S. sclerotiorum at a dose of 15 mg/L (Krishnaraj et al., 2012). Jo et al. (2009) tested the antifungal activity of different forms of silver, that is, silver ions (Ag+) and Ag NPs to plant pathogenic fungi Magnaporthe grisea and Bipolaris sorokiniana and found that both forms of silver showed antifungal activity with an effective concentration (EC50) of 1–8.8 mg/L for an exposure time of 1-6 hr. Actually silver nitrate showed higher antifungal activity (EC50 as 1.2–2.2 mg/L) compared to Ag NPs (EC50 as 4.8–8.8 mg/L). Another study informed the antifungal activity of plant-mediated synthesized Ag NPs on cotton plants against the growth of Fusarium oxysporum f.sp. vasinfectum (Sahayaraja et  al., 2012). Similarly, Ag NPs showed antifungal activity on shade-dried leaves of Conyza ambigua due to an attack of the fungi Aspergillus niger, A. flavus and S. rolfsii (Elumalai and Vinothkumar, 2013). Wood-degrading fungal pathogens, that is, G. trabeum, Gloeophyllum abietinum, Phanerochaete sordida, and Chaetomium globosum are causing huge problems for farmers and carpenters. Narayanan and Park (2014) studied the efficacy of Ag NPs against these pathogens and Ag NPs effectively inhibited these pathogens in degrading woods. Ag NPs are also effective in controlling the growth of stems, roots, and collar rot causing fungi S. rolfsii, R. bataticola, and A. niger (Papaiah et al., 2014). The fungal hyphal growth is a problematic issue in day-to-day life. The sclerotial germination of S. sclerotiorum, R. solani, and S. minor requires extreme attention in protecting against damage in the agrosector. Ag NPs as biopesticides inhibited the growth of hyphae, suggesting their usefulness in the management of scleotiumforming phytopathogenic fungi (Min et al., 2009).

12.11 ­ Mechanism of antimicrobial activity by Ag NPs

Several reports have demonstrated the usefulness of Ag NPs as biopesticides in controlling fungal attacks on onions by S. cepivorum (Jung et al., 2010), rice seedlings by M. grisea (Elamawi et  al., 2013), wheat germination by B. sorokiniana (Sandhya et al., 2014), and powdery mildews of pumpkins by Pythium ultimum (Park et al., 2006), whereas bacterial spots in tomatoes by X. perforans were inhibited by DNA-directed synthesized Ag NPs (Ismail et al., 2013). Also, Ag NPs showed higher antifungal activity to A. alternata and B. cinerea compared to the combined application with Cu NPs (Ouda, 2014).

12.10 ­ Nanoformulations and Nanoencapsulation-Based Pest Control Methods The modern nanopesticide formulations such as nanoencapsulates, nanoemulsions, nanocages, and nanocontainers have opened the smart nanopesticide delivery techniques, which are highly effective to plant protection programs (Lyons and Scrinis, 2009). These techniques are immensely important for poorly soluble drugs under a sustainable pattern of release. In the agrosector, farmers are facing challenges from poorly soluble drugs/pesticides/agrochemicals due to their quick release/poor solubility/higher exposure causing toxicity to crops or washing away quickly. Ultimately the farmers are facing monetary or crop losses or more pest attacks. The concept of nanoemulsions, nanoencapsulation, or nanoformulations has improved the mode of delivery, which has improved pest management in a targeted manner and consequently the production of crops as well as earnings/profits (Chowdappa et al., 2014; Chowdappa and Gowda, 2013). Chowdappa et  al. (2014) synthesized AgNPs using chitosan as the reducing and stabilizing agent and evaluated against the seed-damaging pest Colletotrichum gloeosporioides in mango (cv. Alphonso). It was observed that application of Ag NPs improved postharvest decay in the mango, which highlighted its commercial value in harvesting different types of mangos throughout India and promoted to earn lot of foreign currency after export of high quality mangoes. Nanotechnology in conjunction with biotechnology, that is, nanobiotechnology, has done wonders in different fields, especially in the agrochemical sector. It has brought many novel ways of delivery that have extended the applicability of nanomaterials in crop protection and production. Nanoencapsulation shows the benefits of more efficient and targeted use of pesticides, herbicides, and insecticides in an environmentally friendly way.

12.11 ­ Mechanism of Antimicrobial Activity by Ag NPs Smaller nanoparticles, having more surface-to-volume ratio, can interact more with microbes, leading to a broad range of probable antimicrobial activities (Martinez et al., 2010).

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Ag nanoparticles

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NO2 DPPH (stable Yellow color)

FIG. 12.6 Plausible mechanism involved in the antimicrobial activity (1) and antioxidant activity (2) of SNP. Reprinted from [Kiran Kumar and Mandal, 2015] with permission from Elsevier.

Examples of such mechanisms include the generation of reactive oxygen species, oxidative stress, membrane disruption, protein unfolding, and/or inflammation (Fig. 12.6) (Kiran Kumar and Mandal, 2015; Bragg and Rannie, 1974; Feng et al., 2000; Samuel and Guggenbichler, 2004; Elchiguerra et al., 2005; Reddy et al., 2007; Meng et  al., 2009; Donaldson et  al., 2009). Ag NPs can penetrate cell walls and inhibit protein expression used in ATP production (Yamanaka et al., 2005) as well as damage cells after binding to phosphorus and sulfur containing DNA and proteins (Amarendra and Krishna, 2010). Subsequently, Ag NPs interfere in the oxygen metabolism inside cell matrixes, which critically disturbs the oxygen supply chain, which results in suffocation followed by killing the particular microorganism. Sideby-side Ag NPs alter the basal metabolism of electron transfer systems and transport of substrates via the microbial cell membrane (Lamsal et al., 2011). Nematicidal activity is to kill plant-parasitic nematodes. Xerophytes, mesophytes, and hydrophytes are used to synthesize nanoparticles within a size range of 2–50 nm, which are highly active as nematicidal agents (Jha et al., 2009). Ulva fasciata-mediated synthesized Ag NPs inhibited the growth of X. campestris pv. Malvacearum with ZOI of 14.00±0.58 mm at MIC of 40.00±5.77 mg/L (Rajesh et al., 2012) whereas marine alga Padina pavonica (Linn.)-mediated synthesised Ag NPs showed higher microbicidal activity against X. campestris pv. Malvacearum (Sahayaraja et  al., 2012). Mahmood Chahardooli et  al. (2014) ­ performed the

12.11 ­ Mechanism of antimicrobial activity by ag nps

a­ ntimicrobial activity of leaf and fruit extracts of oak and Quercus infectoria against plant pathogenic bacteria, that is, Erwinia amylovora, Pectobacterium carotovorum, X. citri, and Ralstonia solanacearum. Entomopathogenic fungus Beauveria bassiana extract-mediated synthesized Ag NPs showed bioefficacy against the mustard aphid (Lipaphis enysimi Kalt.) (Kamil et al., 2017). The green synthesis of Ag NPs by the entomopathogenic fungus Beauveria bassiana showed their bioefficacy against mustard aphid (Lipaphis enysimi Kalt.) and Euphorbia armigera-mediated synthesized Ag NPs showed significant effects on the cotton bollworm Helicoverpa armigera (Durgadevi et al., 2014).   The deadly pest Helicoverpa armigera causes damage in the fields and to horticulture crops around the globe. More than 180 cultivated hosts and 45 families of wild plant species are affected by this pest (Sullivan and Molet, 2007). Interestingly, more than 150 different pests attack cotton plants at different stages of their life (Gandhi and Nimboodiri, 2009). The secondary metabolites of plants possess biopesticidal activity and as a natural source, these metabolites are ecofriendly and could be used to control pests. Such natural plant metabolites are low-risk as compared to the synthetic pesticides and suitable alternate strategy for pest management to save huge agriculture losses. The word “cide” means “to kill.” There are different types of pesticides such as nematicides, molluscicides, insecticides, acaricides, miticides, piscicides, avicides, rodenticides, bactericides, algicides, fungicides, and herbicides (Lade et  al., 2017). Thus, nano-based innovative nanopesticides such as Ag, Cu, SiO2, and ZnO and nanoformulations show better broad-spectrum pest protection efficiency while reducing water, soil, and environmental pollution in comparison with conventional pesticides (Chhipa, 2017). Biopesticides act in different ways to control pests: (i) induced resistance, (ii) competition, (iii) antibiosis, and (iv) parasitism/hyperparasitism (Adams, 1990; Lo et al., 1998). Defense mechanisms within plants or or animals can be enhanced by incorporating, one’s proteins or related biomolecules for acquiring induced resistance for protecting the attack of pests and microbes (Deshmukh et  al., 2006). If biochemicals produced by a microorganism cause inhibition of another organism’s growth, this is considered “antibiosis.” This suggests a continued competition among animals, pathogens and pests which reminds us the Darwin’s survival theory that is, survival of the fittest in the ecosystem. Similarly, there is a tight competition/ war between microbes and pests for the available micronutrients in the environment, especially soils and plants (Pal and McSpaddon Gardener, 2006). This leads to pathogen exclusion, which is essentially important for a healthy ecosystem. This signifies the importance of biologically important chemicals that control the spread of pests and microbes by controlling the excess micronutrients in the environment. In addition, parasitism is common in the fungal kingdom. Campoletis chlorideae larvae exhibits simple parasitism on H. armigera (Pillai et al., 2016). The reduction of the nematode (Rotylenchus reniform) population was seen in soybean cultivation when Paecilomyces lilacinus, Pochonia chlamydosporia, Aspergillus nidulans var. dentatus, and T. harzianum were applied at a dose of 2 g/kg soil. Also, this action improved the plant growth (Gurjar et al., 2012; Singh and Prasad, 2014).

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Normally, the oil seed crop Castor Ricinus communis (Linn) (Euphorbiaceae) is infected by Pericallia ricini in many countries. Pungam oil-based Ag NPs were effective against Pericallia ricini inducing larval mortality, and also had impact on development, and fecundity (Sahayaraj et  al., 2016). Ag NPs can conjugate with protein-lipids by a green method using Sterculia foetida L. (Malvales: Sterculiaceae) seed extract and its biomedical applications, that is, an antiproliferative activity against the HeLa cancer cell has proofed its biocompatibility as well as its translocation into the HeLa cells (Rajasekharreddy and Usha Rani, 2014a) which warrants its promising scope in cancerous cell controlling/arresting/killing (Rajasekharreddy and Usha Rani, 2014a). Hopefully, in the near future, a more rational approach will be gradually adopted toward biopesticides and the fate of biopesticides will not be determined by short-term profits from chemical pesticides (Usta, 2013).

12.12 ­Conclusion Nanotechnology is everywhere in our daily life. Our society is extracting its beneficial effects. The agricultural sector needs to use nanobiotechnology smartly for drug delivery and disease identification by using smart nanodevices at the early stage to control pest attacks. By this way, farmers can increase their production manyfold. In addition, we need nanomaterial-based biopesticides to overcome multidrug-resistant microbes before they spread and create a challenge for farmers. In this context, Ag NPs could be an alternate choice for pest management in the near future. Although many methods are available for the synthesis of Ag NPs, we need compound methods where smaller particles will be synthesized with nanoencapsulation, nanoemulsions, or nanoformulations so that agrochemicals could be delivered effectively in a low dose without running away. In addition, all essential micronutrients could be applied at the nanolevel to get the advantages of nanotechnology. Finally, we must judge and scrutinize sincerely any adverse effect of nano-based biopesticides so that the benefit of nanobiotechnology would not disturb its ecofriendly tag with reckless utilization of nanotechnology and related products.

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­Further Reading Rajasekharreddy, P., Usha Rani, P., 2014. Biosynthesis and characterization of Pd and Pt nanoparticles using Piper betle L. plant in a photoreduction method. J. Clust. Sci. 25, 1377–1388. Deshmukh, S.G., Sureja, B.V., Jethva, D.M., Chatar, V.P., 2010. Field efficacy of different insecticides against H. armigera (Hubner) infesting chickpea. Legum. Res. 33, 269–273. Kumar, S., Nehra, M., Dilbaghi, N., Marrazza, G., Hassan, A.A., Kim, K.-Y., 2018. Nanobased smart pesticide formulations: emerging opportunities for agriculture. Corel. https:// doi.org/10.1016/j.jconrel.2018.12.012. Lade, B.D., Gogle, D.P., Nandeshwar, S.B., 2017. Nano biopesticide to constraint plant destructive pests. J. Nanomed. Res. 6, 00158. https://doi.org/10.15406/jnmr.2017.06.00158.