Journal of Agriculture and Food Research 14 (2023) 100687

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Journal of Agriculture and Food Research

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Prospects of plant-derived metallic nanopesticides against storage pests -

A review
Bighneswar Baliyarsingh *, Chandan Kumar Pradhan
Department of Biotechnology, Odisha University of Technology and Research, Ghatikia, Bhubaneswar, 751029, Odisha, India

A R T I C L E I N F O A B S T R A C T

Keywords: The desire to increase agricultural productivity and to alleviate food losses caused by insects during post-harvest
Phyto-nanopesticides storage periods has augmented the rampant use of unsafe chemo-synthetic pesticides. The elevated health risks
Phytochemicals on human or domestic animals and environmental pollution by chemo-pesticides have shifted the focus of getting
Silver nanoparticles
eco-friendly pesticides from biological entities. Research on the nanotechnological application in agriculture has
Green-synthesis
Insect/pest control
become popular and promising. The diversity among plant species as well as the possession of different insect-
specific bioactive compounds makes them the favoured choice for exploring active ingredients, and the appli­
cation of nanoscience has facilitated the development of effective nano-biopesticides. Varieties of phytochemical
groups act as reducing- and stabilizing agents during the biosynthesis of metallic nanoparticles that would be
operated as nanobiopesticides. Moreover, green synthesis of metallic nanoparticles or nano-conjugates, espe­
cially silver nanoparticles have been experimentally proven successful in controlling insects of stored food
products. This review compiles phyto-derived metallic nanoparticles’ potential and effectiveness against storage
insects, and the analysis will augment research in designing and promoting the development of eco-friendly
agrochemicals.

1. Introduction accumulation of fluoride residues has raised concern about its use,
which is now discouraged in developed countries. Apart from this, the
Agriculture is the sole sector that provides the majority of the food insect’s resistance to chemical fumigants is noticed in the stored grain
required to feed the world’s population. Apart from the food demand of insects such as red flour beetle (Tribolium castaneum Herbst.), rice weevil
the growing population which is estimated to reach approximately 9.3 (Sitophilus oryzae L.), and lesser grain borer (Rhyzopertha dominica F.)
billion by 2050 [1], agricultural production confronts several challenges which are posing serious threats to the harvested crops around the globe
such as improvement of nutritional content, enhancement of the crop [6–8]. The negative impacts of inorganic chemical pesticides such as the
yield, and prevention of food loss. Most often the postharvest crop losses bio-magnification of pesticides leading to pollution of soil and water,
can surpass the losses that crops suffer in the field [2]. Not only climatic interference of pesticides in the food-chain ecosystems, pesticides’
factors but biotic factors like pests have a major play in food loss during harmful effects on human health, and development of pesticide resis­
post-harvest periods. Because of the direct availability of nutrients for tance are now being widely acknowledged. The growing demand for
the insects in the stored grains, it becomes an easier target for the storage food coupled with renewed agricultural challenges as well as the need to
pests. Collectively the insects are to be blamed for the decline in food control stored-grain pests has warranted the shifting of the scientific
production, amounting to 14% per year [3]. Because of these pest in­ focus toward developing eco-friendly pesticides.
festations of grains, human consumption as well as the economic value Nanotechnology has the potential to improve pesticide effectiveness,
of these grains are significantly reduced [4,5]. increase the longevity of active components, and reduce the usage of
Among the several insect control strategies that are available, agricultural inputs while overcoming the drawbacks of conventional
fumigation is one of the most common methods of controlling pests in pesticides [9]. Nano-biopesticides are pesticides that have size at the
storage places. Because of routine fumigation at storage places, the nano-scale, and are derived from biological organisms (i.e. natural

* Corresponding author. Department of Biotechnology (Laboratory Building), Odisha University of Technology and Research (OUTR), Ghatikia, Bhubaneswar,
Odisha, 751029, India.
E-mail address: [email protected] (B. Baliyarsingh).

https://doi.org/10.1016/j.jafr.2023.100687
Received 18 February 2023; Received in revised form 29 May 2023; Accepted 13 June 2023
Available online 15 June 2023
2666-1543/© 2023 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
B. Baliyarsingh and C.K. Pradhan Journal of Agriculture and Food Research 14 (2023) 100687

substances), mostly plants [10] and microbes. In the current agricultural seeing how chemo-synthetic pesticides harm either an ecosystem or
context where challenges of environmental contamination, pest resis­ non-target species has rekindled interest in the use of biopesticides as a
tance, bioaccumulation, and human health hazards are widespread, pest management tool. Bio-pesticides seem to be one of the possible
nanotechnology is emerging as an appealing tool for pest control with solutions to alleviate the adverse effect of chemical pesticides. "Bio­
the use of a minimal amount of chemo-pesticide by offering new pesticides" or "biological pesticides" are pesticides derived from bio­
methods for the formulation and delivery of existing active ingredients, logical organisms such as plants, animals, bacteria, and certain minerals.
as well as novel active ingredients (AI) [11,12]. Nanopesticides are Biopesticides now account for about 5% of the global pesticide business,
broadly divided into two major categories depending on the delivery of which is anticipated to grow dramatically in the future. Some of the
active ingredients. Type-I nanopesticides are metal-based nano­ well-known products of commercialized bio-pesticides are often de­
pesticides that act themselves as active ingredients whereas in type-II rivatives of Bacillus thuringiensis var. Tenebrionis strain Xd3 (Btt-Xd3),
nanopesticides active ingredients are captured inside the nanocarriers Lactobacillus casei strain LPT-111, fungal strain of Talaromyces flavus &
(such as polymers, lipid droplets, and clays) [13]. The green synthesis Trichoderma harzianum [22], Clitoria ternatea plant extract and olive mill
approach to nanoparticle synthesis, in which phytochemicals promote wastes. However, there are some concerns regarding the efficacy of
the manufacturing of various types of metal-based nanoparticles, is biopesticides at different geographical or climatic conditions as well as
growing in popularity because of its eco-friendly nature, slow pest control activities. These limitations can be addressed by
cost-effectiveness, and non-toxic manner. As the science of pest control exploring and applying the concepts of nano-science.
through nanotechnology is evolving, the scientific documents on Nano-technology facilitates the development newer natural pesti­
nanopesticides are sparse. Moreover, the concept of applying cides as well as newer ways to deliver active compounds that are
nano-biopesticides for the management of storage pests is fairly new and effective against specific agricultural pests. The benefits of nano-
information related to their synthesis, variety, effectiveness and mode of biopesticides go beyond target-specificity and include the organic
action, etc. is lacking, which hinders their usage in storage environment occurrence of several types, low environmental contamination, non-
[14,15]. This review presents the results of laboratory experiments and disruption of the ecological food chains, an increase in soil nutrients,
documents about the nanoformulations, particularly phyto-derived reduction in pesticide usage volumes and increase of soil fertility. In
metallic nanopesticides that have been assessed for the control of stor­ addition, pests that are encountered by nano-biopesticides will be less
age insect pests. The article also describes the potential of phytochem­ likely to develop resistance towards them. Nano-formulations of old bio-
icals in the green synthesis of nanoformulations. This compiled review pesticides or innovative nano-composites are now developed not only to
article on eco-friendly nanopesticides, especially plant-derived nano­ control pests during farming but also to protect grains/foods from
pesticides, will augment scientific research on biopesticides of postharvest storage pests. Thus, nano-formulations of pesticides promise
nano-formulations and their applicability. to have diverse functional benefits, viz: increasing longevity and effec­
tiveness of biopesticides, wider dispersion of biopesticides in applied
2. Impact of storage pests on crops areas, and photogeneration potential etc. The kind of nano-carriers
utilized, the mode of delivery, the origin of bioactive compounds or
Irrespective of being a developed or developing nation, post-harvest the conjugates used in nano-form are the basis of grouping and cate­
storage is an important part of crop productivity and economy. To gorizing nano-pesticides.
achieve food demand food and grains must be stored for longer periods.
Even though the applications of newer technologies have facilitated the 4. Major groups of nanopesticides
increase in crop production, postharvest losses during storage have
resulted in a dramatic reduction in grain availability. Many insect pests 4.1. Based on the target organism
have been reported to be associated with stored grains and these bio­
logical agents inflict huge damage on stored grains. World estimation As the conventional pesticides are categorized according to their
suggests pests reduce more than 40% of total food production [16]. targets pests so as the nano-formulations of biopesticides are named
More than 10% of the post-harvest damage in warehouse and granaries according to target organisms viz. herbicides (against parasitic weeds),
occur due to pests and mites infestation [17]. The grain loss condition in insecticides (against insects), acaricides (against mites), molluscicides
developing countries is comparatively worse than in developed coun­ (against snails/slugs), rodenticides (against rodents), bactericides and
tries. About 7.7% of the annual loss was incurred due to insect pests in fungicides [23]. However, significant portions of pesticides are in­
total production in Brazil which is estimated to be an economic loss of secticides. Because of the diversity among plants as well as possession of
USD 17.7 billion [18] while in India, the losses by insects alone different bioactive compounds make them preferred source of devel­
amounted to nearly Rs. 1,300 crores [19]. oping insecticidal compounds. The insecticidal properties of phyto­
The losses can be attributed as quantitative or qualitative losses. The chemicals are of particular interest to study their effect against different
quantitative losses are due to breakage, damage, and eat-away of grains agricultural and stored grain insect-orders which mostly include pests of
while the qualitative loss is caused by the reduction in nutritive value. order Coleoptera (beetles), Diptera (mosquitoes and flies), Hymenoptera
The stored grain pests are grouped into primary and secondary pests (ant, bees, and wasps), Lepidoptera (butterflies and moths).
with the belief of difference that secondary pests cannot infest whole
grain but feed on broken grains or in conjugation with the primary 4.2. Based on delivery system
infestation. Some of the notable primary pests are rice weevil, (Sitophilus
oryzae L.), lesser grain borer, (Rhyzopertha dominica F.), Khapra beetle, Various smart delivery systems of nano-size have been designed and
(Trogoderma granarium Everts.), and secondary pests include red flour introduced to agricultural systems with an objective of controlled
beetle (Tribolium castaneum Herbst.), rusty grain beetle (Cryptolestes release of active compounds against the target pests. Nano-delivery
ferrugineus L.), and booklouse (Liposcelis corrodens Heymons), etc. [20]. methods are either applied individually or collectively according to
There are vivid groups of insect-pests that affect diverse grains and the pest control requirement. Most often they facilitate either as (i) time-
particular species’ presence depends upon the type of grain. controlled release, (ii) target specific release, or (iii) self or remotely-
regulated systems. Many designed and developed methods of nano­
3. Biopesticides vs nanobiopesticides in crop protection formulated pesticides are classified broadly as nanosuspensions [24],
nanoemulsions [25], and nanocapsules [26].
In the 1960s, insects caused damages of 7.2% of total production; by
the 2000s, those damages had increased to 23.3% [21]. Additionally,

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B. Baliyarsingh and C.K. Pradhan Journal of Agriculture and Food Research 14 (2023) 100687

4.2.1. Polymer-based encapsulation materials that offered excellent loading capacity for the pesticides. A
The encapsulated polymeric nanostructures of natural polymers such typical example is a urease-responsive herbicide formulated with pen­
as poly-ϵ-caprolactone, cellulose, chitosan, and alginate-gelatin are dimethalin cross-linked to isocyanate-silica against weeds of Amaranthus
more common due to their environment-friendly and biodegradable retroflexus L. and Echinochloa crussgalli L [34].
nature [27,28]. Similarly, nanogels are polymeric nanocarriers with
promising features of high stability such as citric acid-carboxymethyl 4.2.4. Metal-based nano-formulations
cellulose-bentonite hydrogel composites carrying thiamethoxam insec­ In general, these metal formulations are synthesized from metal
ticide [29]. Polymeric carriers facilitate controlled release of bioactive clusters or ions that work as nucleation centers which are interconnected
compounds like botanical repellents encapsulated in zein nanoparticles by organic ligands (Fig. 1). The metal-based encapsulation or metal-
mostly used in crop protection [30]. On the other hand, the efficacy of organic framework (MOFs) possess many advantageous properties
different types nano-carriers of polymeric nano-formulations such as which include high surface/volume ratio, voluminous pores, adjustable
aqueous-based, particulate-based, microcapsule, and microemulsion pore size, efficient surface chemistry, high thermo-stability, and multi­
nanoparticles depends on temperature, solar radiation, enzymes, or pH ple topologies [35–37]. Because of the nano-technology, prominent
which sometimes becomes its limiting factor. However, benefits of features like presence of numerous active sites for the release of bioac­
controlled release have edge over their limitations; for example, the tive molecules, ion exchanging properties, high adsorption ability [38],
release of acetamiprid pesticide contained in alginate-chitosan polymer and exceptional electronic characteristics [39] motivates the develop­
nanocapsules can be controlled by pH [31]. ment of metal based nano-biopesticides.

4.2.2. Lipid nanomaterial/nano-droplet encapsulation 4.2.5. Mixed nanostructures-based delivery

Lipid nanomaterials as colloidal nanocarriers, mostly of size 20-200 In order to combine advantages associated with different types of
nm, are also considered as a preferred delivery system which is due to delivery systems, mixed nanostructures are used. For example, to in­
their non-toxic property, good carrying capacity, and target specificity crease the efficiency of targeting the desired nanoparticles and also to
[32]. Nano-droplet based delivery comprises lipophilic compounds that increase the thermal-stability of the nanoparticles, liposomal formula­
are most productive for a liquid-based colloidal system in pesticide tion containing silver nanoparticles are introduced. This increases the
formulations. These can be conveniently applied as a nano-emulsion bioavailability of the nanoparticles for target delivery and increase the
where their size helps in enhancing bioavailability, firmness, and secu­ concentration of nanostructure at the site of action [40]. Particularly
rity to active compounds of biopesticides. However, the size of nano­ this method of delivery is more impactfully used now in clinical studies
droplet is inversely related to the bioavailability of entrapped for targeted drug delivery, using liposome or silica coated gold nano­
biopesticides [33]. particles [41].

4.2.3. Clay based nanoformulations 5. Green synthesis of metal nanoparticles for pesticides usage
Clay-based nanoformulations have the advantage of promoting
adsorption neutral and hydrophobic active compounds as well as a slow The chemo-synthetic method of making nanoparticles calls for the
release of them. Nanoclays are cost-effective and biocompatible apt utilization of highly reactive chemicals, the release of noxious

Fig. 1. Schematic representation of the synthesis of different types of bio-nanopaticles that can be used as nanopesticides.

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B. Baliyarsingh and C.K. Pradhan Journal of Agriculture and Food Research 14 (2023) 100687

byproducts, a significant amount of energy, and the requirement for 6. Phytochemicals potential as nanopesticides
skilled labour, all of which have prevented their wider use. There has
been a desire to find reliable, inexpensive, and eco-friendly approaches Although little is documented on nanopesticides of phyto-origin,
for the synthesis of stable metal nanoparticles with defined size and many plant species show natural resistance against many pests, and
shape. Moreover, nature already has mastered in devising and synthe­ identifying such active compounds will improve the scope of controlling
sizing nano and microscale inorganic materials which led the research pests. Many of the plant species with insecticidal property belong to
on the biosynthesis of the nanomaterials. Almost a century ago, Molisch families of Lamiaceae, Cupressaceae, Rutaceae, Apiaceae, and Myrtaceae
[42] and Iwase [43] studied respectively the reduction of silver and gold such as Blumea densiflora (DC), Auxemma glazioviana (Taub.), Callitris
metal ions by chlorophyll molecules and fresh leaf extract of plant. glaucophylla (J. Thompson & L. Johnson), Cinnamomum mollissimum
However, the prominent work on plant-mediated biosynthesis of (Hook. fil.), Cinnamomum microphyllum (Thunb. Nees.) and Zanthoxylum
nano-particles was reported in the early 21st century on Alfalfa (Medi­ oxyphyllum (Edgew.) [63]. It is the byproducts of the plant metabolism i.
cago sativa) plant [44]. e phytochemicals and essential oils that exhibit antagonistic activity
Green synthesis methods involving plants for preparation of nano­ towards insects by behaving as a fumigant, repellent, and chemo ster­
particles bearing active agents with insecticidal properties are now ilant or antifeedant substance [64]. Alkaloids, among the largest classes
gaining importance for the production of nano-agrochemicals. Plants of phytochemical compounds with one or more nitrogen atoms in their
facilitate an efficient platform for nanoparticles synthesis as they do not structure, affects generally acetylcholine receptors or sodium pump in
generate toxic chemicals. The phytochemical groups facilitate reduction the nervous systems [65] (Fig. 2). Moreover, these alkaloid compounds
and caping of metallic ions by hyper-accumulation of the metal mole­ also act as good repellents. The Phenolic molecules cause dissipation of
cules [45]. The mechanism behind nanoparticle biosynthesis is very the proton motive force and disruption of membrane structure. Simi­
simple that is mixing of desired plant material with appropriate metallic larly, terpenes and terpenoids after entering to insect cells increase the
ions solution (ranges 0.01 M to 1 M) at a optimized concentration ratio, fluidity of the membrane which leads to loss of membrane structure and
temperature and pH (mostly accomplished at room temperature and eventually disruption of the cell [66]. Notable common examples of
between neutral to pH-8). Reduction of ions takes place immediately identified compounds used widely as natural pesticides are Azadirachtin
after mixing and the genesis of nanoparticles is denoted by change in from Neem plant (seed or leaves) which down-regulates the larval
colour of the running solution where the metallic ions get converted to growth and body development, Sabadilla from seeds of Sabadilla lily
zero-valent state (Fig. 1). Various phytochemical compounds present in (Schoenocaulon officinale) have antagonistic effect on caterpillars,
plants such as phenolics, alkaloids, terpenoids, sugars, and proteins first squash bugs thrips, Curcumin derived from Curcuma longa are effective
reduce the metallic ions and then stabilize them [46] The disparity in against stored grain pests like ticks and mites [67]. Besides, some other
presence of active compounds in the plant sample and their type of notable examples of plant derivatives which are being used for a
interaction with the extracting solvent defines the shape and size of the consistent period include Pyrethrum from Tanacetum cinerariaefolium
extracted nanoparticle (Fig. 1). It can be inferred from a typical example (flowers) known for anoxic poison affecting the impulse transmission
that the aqueous extract of Alfalfa generates nanoparticles of triangular through axons, Rotenone from rhizomes of legume are cytotoxins that
shape while isopropyl alcohol extract generates decahedron and icosa­ block electron transport chain in mitochondria, and Nicotine isolated
hedron nanoparticles [47]. from tobacco plant act as synaptic toxins (mimics acetylcholine).
Diverse phytochemical-groups such as ketones, terpenoids, amides, Transportation of these phytochemicals through nano-carriers or
flavonoids, carboxylic acids, aldehydes [48] ascorbic acid, quinines, reducing their size to nano-scale has improved their efficacy signifi­
flavones, saponins, tannins, phenols, glucose, and starch [49,50] are cantly. The essential oils from Cinnamomum zeylanicum encapsulated
involved in the plant-mediated synthesis of metal nanoparticles through with nano-chitosan has not only increased the storage period of Cucumis
reduction of metal ions. Some of the notable phytochemicals viz. sativus (cucumbers) from Phytophthora drechsleri attack but also main­
Berberine, Scopolamine (alkaloids) [51], Limonene, Geraniol (Terpe­ tained the colour & water content in cucumbers [68]. Although different
noids) [52], Quercetin, Rutin (Flavonoids) [53], Catechins (poly­ forms of nano-carriers are designed such as core-shell NPs, polymer
phenols), Ginsenosides (Saponins) [54] facilitate the synthesis of metal conjugated NPs, polymer-coated NPs, organics, and inorganics magne­
nanoparticles. Plant derived bioactive groups such as catechnis and tite NPs, the metal-based nano-pesticides are widely studied and
hydroxyflavones of Carica papaya, Trianthema decandra [55], and Mor­ developed because of their easy biogenic synthesis process and higher
inda tinctoria [56], polyols of Achyranthus aspera and Anacardium acci­ efficacy against different stages of insects (Fig. 2).
dentale, vitamin C and volatile oils of Citrus sinensis [57,58] facilitate
synthesis of nanoparticles that can be used as pesticides. The anthra­ 6.1. Phyto-derived silver nanoparticles against storage insects
quinone and emodin from xerophytes help in the formation of AgNPs by
self-tautomerization [57]. The glycosidic component verbascoside in the Plants are becoming a more plausible source or component for the
Lippia citrodora extract acts as a reducing and capping agent in the creation of AgNPs due to their rapid, environment friendly, non-
synthesis of AgNPs, resulting in improved AgNP stability [59]. Similar to pathogenic, low-cost technique, and ease of scaling-up for large-scale
this, Coseri’s group [60] investigated the role of pullulan and oxidised synthesis [69]. Some notable plants whose phytochemicals serve as a
pullulan polysaccharides in the biosynthesis of AgNPs and showed that chelating agent during green synthesis of AgNPs, are Ocimum basilicum
the size variation of the nanoparticles depends on the chemistry of (basil) [70]; Ananas comosus (pineapple) [71]; Andrographis paniculate
polysaccharides structure, with natural pullulan producing 30-50 nm [72,73]; Vitex negundo; Cinnamomum camphora [74]. Swallow grass leaf
and oxidised pullulan producing 8-25 nm-sized nanoparticles. In gen­ extract of Euphorbia prostrate mediated biosynthesis of silver nano­
eral, bioactive compounds in plant extract reduce the Ag+ ions by particles showed significant mortality against S. oryzae on a 7-day
trapping on its surface through electrostatic interactions. However, treatment period, even reaching 100% mortality [75]. Similarly,
metallic nanoparticles synthesized through green methods may exhibit AgNPs prepared from pomegranate extract showed significant mortality
limited stability and shorter shelf-life due to their susceptibility to effect against Spodoptera litura, a polyphagous pest [76]. Significant
agglomeration, oxidation or degradation over time [61]. Apart from the mortality effect of Cissus quadrangularis extract mediated AgNPs against
limitation of stability the scalability and optimized protocol usually pose adult flies, Hippobosca maculate, when applied in 25 mg/L concentration
a challenge as the composition and properties of these natural sources [77]. Additionally, biosynthesis of AgNPs utilising Saponaria officinalis
that are often used can vary leading to inconsistency in the size, shape, root extract has acaricidal and anti-ovipositional efficacy against Tet­
and stability of the resulting nanoparticles. Standardization of synthesis ranychus urticae, a polyphagous pest [78,79]. Research studies also
protocols is necessary to ensure consistent and reliable production [62]. indicated the insecticidal potential of nanostructured alumina over two

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B. Baliyarsingh and C.K. Pradhan Journal of Agriculture and Food Research 14 (2023) 100687

Fig. 2. Schematic representation of different mode of action of bio-nanopaticles against crop/grain damaging insects.

stored food pests, S. oryzae and R. dominica [78,79]. Silver NPs have nanoparticles (AuNPs) have significant biocidal properties as well as
became most common and excellent nanopesticides against storage in­ lower toxicity towards mammalian cells [91]. The significant antimi­
sects (see Table 1). crobial effect over S. aureus than E. coli was observed by spherical AuNPs
of size 5 to 25 nm that was prepared using leaf extract of the Parkia
6.2. Phyto-derived metalic nanoparticles other than silver metal as roxburghii [92]. Similarly, biosynthesized AuNPs using the extract of
nanopesticides flower from Couroupita guianensis with the averaged size of 29.2 - 43.8
and cubic geometry showed larvicidal activity against larvae, pupae,
The main criteria for choosing different metallic compounds for the and adults of Anopheles stephensi [93]. Monodisperse CuNPs (Copper
synthesis of nanoparticles (NPs) utilising plants are stability, rate of nanoparticles) with an average diameter of 50 nm and spherical shape
synthesis, variety of forms and sizes generated (see Table 2). Gold exhibited antifungal and antibacterial (gram-positive) activity. A rice

Table 1
Plants/ plant parts that are useful in the green synthesis of silver nanoparticles and effective against stored grain pests.
NPs Metal Salt Plant Phytochemical Agent Extracting NPs Structure Target Pest Reference
Solution Condition

Ag AgNO3 Cissus quadrangularis Stem extract/Polysaccharides with Aqueous, 60 0C Spherical, Hippobosca maculata (Leach.), [77]
(L.) hydroxyl or hemiacetal ends for 5 min 05–35 nm Rhipicephalus (Boophilus)
microplus (Canestrini.)
Ag AgNO3 Euphorbia hirta (L.) Leaf extract Aqueous, Boiling Spherical or Helicoverpa armigera (Hübner.) [80]
condition cubic-shaped, 30-
60 nm
Ag AgNO3 Euphorbia prostrate Leaf extract/(2,3-dihydrobenzofuran) Aqueous, Boiling Rod Shape, Sitophilus oryzae (L.) [75]
(Aiton.) cond. 25–80 nm
Ag AgNO3 Ficus religiosa (L.), Leaf extract Aqueous Extract, Spherical, Helicoverpa armigera (Hübner.) [81]
Ficus benghalensis (L.)
0
Ag AgNO3 Hibiscus tiliaceus (L.) Leaf extract/(Tannins) 100 C for 5 min irregular shape, Tribolium castaneum (Herbst.), [82]
20-65 nm Rhyzopertha dominica (F.),
Sitophilus oryzae (L.)
Ag AgNO3 Manilkara zapota (L.) Leaf extract 60 0C for 5 min Spherical and Musca domestica (L.) [83]
P. Royen oval, 70-140 nm
0
Ag AgNO3 Moringa oleifera (F.) Leaf extract/Glucosinolates (4-O-(a-L- Aqueous, 100 C Spherical, 9 - 11 Sitophilus oryzae (L.), Musca [84]
rhamno pyranosyloxy) for 30 min nm domestica (L.)
-benzylglucosinolate)
Ag AgNO3 Musa paradisiaca (L.) Peel extract/(phenolics, flavonoids, Aqueous, Boiling Rod shape, Haemaphysalis bispinosa [85]
alkaloids, tannins, terpenoids and cond. 50–150 nm (Neumann), Hippobosca
sterols) maculate (Leach.)
Ag AgNO3 Myriostachya Whole Plant Aqueous, Boiling irregular shape, Tribolium castaneum (Herbst), [86]
wightiana (Nees ex cond. for 5 min 15-65 nm Rhyzopertha dominica (F.)
Steud.)
Ag AgNO3 Ocimum sanctum (L.) Leaf extract/(flavonoids and tannins) Aqueous, Boiling Spherical, 16- Corcyra cephalonica (Stainton), [87]
cond. for 5-10 127 nm Helicoverpa armigera (Hübner)
min
Ag AgNO3 Peganum harmala (L.) Seed extract/(Alkaloids) 80 0C for 30-45 Spherical, 22.5 Trogoderma granarium (Everts) [88]
min and 66.2 nm
Ag AgNO3 Pongammia Punnata Seeds, Pungam oil Aqueous, Spherical, Pericalia ricini (F.) [89]
(L.)
Ag AgNO3 Saponaria officinalis Root extract/(steroids, terpenoids, 24 h in room Spherical and Tetranychus urticae (Koch) [79]
(L.) flavonoids, alkaloids, glycosides) temp cubical, 10-20
nm
Ag AgNO3 Suaeda maritime (L.) Leaf extract/(alkaloids, steroids, Aqueous boiling Cubical, 20-60 Spodoptera litura (F.) [90]
Dumort. tannins, saponins, ascorbic acid) for 72 h nm

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B. Baliyarsingh and C.K. Pradhan Journal of Agriculture and Food Research 14 (2023) 100687

Table 2
Plants/ Plants/ plant parts that are useful in the green synthesis of non-silver metal NPs and effective against stored grain pests.
NPs Metal Salt Solution Plant Phytochemical Agent Extracting NPs Structure Target Pest Reference
Condition

Au Chloro auric acid Jatropha Latex from stem and leaves Room temp Irregular shape Callosobruchus maculates (F.), [96]
(HAuCl4) gossypifolia incubation, (grain shape, Callosobruchus chinensis (L.),
(L.) triangular, Maconellicoccus hirsutus (Green),
hexagonal), 70-100 Helicoverpa armigera (Hübner)
nm
Au HAuCl4 Pongamia Oil Aqueous, 30 C Spherical, Pericallia ricini (F.) [89]
glabra (Vent.) for 10-15 min
Ni Ni(NO3)2.6H2O Rauvolfia Leaf extract/(Alkaloids, 400 0C for 5 min Cubic, 9-10 nm Callosobruchus maculates (F.) [97]
serpentine (L.) tannins and phenolic
Benth. compounds)
Pb Pb(CH3COO)2 Avicennia Leaf extract/(polyphenols, 60 0C for 30 min Spherical, 71 and Sitophilus oryzae (L.) [98]
marina flavonoids and tannins) in water bath 110 nm
(Forssk.)
Pd Lipoic acid Solanum Triterpenoid Room temp Hexagonal, 60–100 Henosepilachna vigintioctopunctata [99,100]
trilobatum (L.) nm (F.)
Pd Palladium chloride Terminalia Leaf extract/Polyphenols as Aqueous, Cubic, 80-100 nm Culex gelidus (Theobald) [101]
chebula stabilizer Stirred for 2hr
(Retz.)
Ti TiO(OH)2 Calotropis Flower extract/(Di-(2- 60 0C for 20 min Spherical, 160-220 Rhipicephalus microplus [102]
gigantean (L.) ethylhexyl) Phthalate and nm (Canestrini), Haemaphysalis
anhydrosophoradiol-3- bispinosa (Neumann)
acetate)
In Indium acetyl Aloe vera (L.) Ethyl acetate 400–600 ◦ C Cubic nanoparticle Tetranychus cinnabarinus [103,
acetonate Burm. of 5–50 nm (Boisduval) 104]
Au–Ag HAuCl4 + AgNO3 Camellia Dextrose & Ethanol, Macerating & Triangular, 92 nm Blattella germanica (L.) [105,
alloy sinensis (L.) Epicatechin Microwaving 106]
Kuntze.
Fe2O3 FeCl2•4H2O Ailanthus Leaf extract/(tannin like Aqueous Spherical, 5–200 nm Aphidoidea [107]
excels (Roxb.) ascorbic acids and solution boiled
polysaccharides) for 10 min
ZnO Zinc nitrate Moringa Leaf extract/ Aqueous, Spherical, Musca domestica (L.) [108]
hexahydrate oleifera (Lam.) Boiling cond
(80 ◦ C)
ZnO Zinc acetate Pongamia Leaf extract Aqueous, Spherical, 30-60 nm Callosobruchus maculates (F.) [109,
dehydrate and pinnata (L.) Boiling cond. 110]
gelatin as stabilizer Pierre for 60 min
ZnO ZnC4H6O2.2H2O Punica Peel extract/(phenolic group, Aqueous Nano-platelets, 40 Aphidoidea [111]
granatum (L.) carboxylic group and solution boiled nm
alkenes) for 10 min
ZnO Zn(NO₃)₂ Sargassum Leaf extract/(alkaloids, Aqueous Irregular shape, 20- Helicoverpa armigera (Hübner) [112]
wightii carbohydrates, flavonoids, solution boiled 62 nm
(Greville.) saponins) for 5 min
CuO Cu(CH3COO)2⋅H2O Punica Peel extract/(flavonoid and Aqueous Spherical, 10–100 Aphidoidea [113]
granatum (L.) phenolic group) solution boiled nm
for 10 min
TiO2 TiO(OH)2 Jatropha Latex/Curcain Room temp Spherical, 25-50 nm Bombyx mori (L.) [114]
curcas (L.)

pathogen named Xanthomonas oryzae pv. oryzae, the causative agent of envisioned as antifeedant, insecticidal, larvicidal, pupicidal, or
bacterial leaf blight of paddy is inhibited by CuNPs synthesized using an anti-developmental agents.
aqueous leaf extract of Datura innoxia [94]. Spherical PdNPs (Palladium
nanoparticles) with average particle sizes of 10–20 nm which was pre­ 7. Challenges and future prospects
pared using Melia azedarach leaf extract showed larvicidal activity
against the larvae of Anopheles aegypti [95]. Considering the negative impacts of conventional chemical pesti­
Among the Nobel metals, silver (Ag) is the metal of high preference cides, the use of biopesticides in crop protection is gaining traction as a
in the domain of biological systems as silver ions are widely known for viable alternative. The introduction of nano-science in agriculture
their high reactivity and destabilizing effects on cell membranes. The Ag promises to transform agricultural practices without hampering the
nanoparticles can perforate through the outer skin layer of insects and environment. Nano-biopesticides being the derivative of the bio­
can travel through the mouth, setae, abdominal prolegs, spiracles, and pesticides, it has added advantages of increased efficacy against the pest,
anal prolegs. Silver nanoparticles or its oxide form inversely influence easy penetrating through biological systems, target specificity, and
antioxidative mechanisms and detoxifying enzymes present inside the controlled release. Researchers have shown that the appliance of
insect body; thereby inducing oxidative stress and cell death. In some nanoparticles is not only effective in protecting crops in the field but also
cases AgNPs are associated with restricting the functioning of acetyl­ during the storage of grains from rapid degradation. Along with the pest
choline esterase and release of gonadotrophin, resulting in develop­ control efficacy of nanomaterials, it was observed that nanomaterials
mental loss and reproductive failure respectively [115]. Research has can serve as carriers for pesticide delivery. The preparation of emulsion-
depicted that concentration of nano-biopesticides (nanoparticles) is an based nano-size droplet-oriented pesticide formulation increases the
important factor as they affect morphology and physiology of insects, solubility and stability of pesticide molecules. However, the green syn­
damaging insect head, abdomen, and thorax region [116]. Overall, sil­ thesis of metallic nanoparticles has limitations of its own which include
ver nanoparticles disrupt important functions in insect body and can be a slower rate of production, the potential of entering into another

6
B. Baliyarsingh and C.K. Pradhan Journal of Agriculture and Food Research 14 (2023) 100687

natural ecosystem of agriculture, the impact of non-homogenous laboratory facilities.

composition on stability and poor understanding of the dynamics asso­
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