Nano Particles
Nano Particles
Nano Particles
Biotechnology Reports
journal homepage: www.elsevier.com/locate/btre
Review
A R T I C L E I N F O A B S T R A C T
Keywords: Nanotechnology is an interdisciplinary research field. In recent past efforts have been made to improve
Sustained release agricultural yield through exhaustive research in nanotechnology. The green revolution resulted in blind usage
Fertilizers of pesticides and chemical fertilizers which caused loss of soil biodiversity and developed resistance against
Nanoparticles pathogens and pests as well. Nanoparticle-mediated material delivery to plants and advanced biosensors for
Nutrients
precision farming are possible only by nanoparticles or nanochips. Nanoencapsulated conventional fertilizers,
Biosensors
pesticides and herbicides helps in slow and sustained release of nutrients and agrochemicals resulting in precise
dosage to the plants. Nanotechnology based plant viral disease detection kits are also becoming popular and are
useful in speedy and early detection of viral diseases. In this article, the potential uses and benefits of
nanotechnology in precision agriculture are discussed. The modern nanotechnology based tools and techniques
have the potential to address the various problems of conventional agriculture and can revolutionize this sector.
⁎
Corresponding author.
E-mail addresses: [email protected], duhanjs@rediffmail.com (J.S. Duhan).
http://dx.doi.org/10.1016/j.btre.2017.03.002
Received 22 December 2016; Received in revised form 15 March 2017; Accepted 16 March 2017
Available online 24 May 2017
2215-017X/ © 2017 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/).
J.S. Duhan et al. Biotechnology Reports 15 (2017) 11–23
routine monitoring of pathogens and beneficial organisms in a wide carbonate soils are the alkaline pH, which reduces zinc solubility and
range of microorganisms and substrates due to gene profiling of wide the high calcium carbonate (CaCO3) content, which can absorb and
microorganisms [9]. Advances in micro fabrication and nanotechnology precipitate zinc [22,23]. Zinc oxides (ZnO) and zinc sulphates
now play an important role in viral detection and improving the (ZnSO4·H2O) or (ZnSO4·7H2O) are commonly used as zinc fertilizers
detection limit, operational simplicity and cost-effectiveness of viral to correct deficiency of zinc in soils [24]. However, their applications as
diagnostics [10]. fertilizer are limited due to non-availability of zinc to plants. Zinc oxide
nanoparticles can overcome this problem by providing more soluble
2. Biosynthesis of nanoparticles and their use in agriculture and available form of zinc to plants due to their higher reactivity in
comparison to micron- or millimeter-sized zinc particles present in
Many chemical methods are available for synthesis of nanoparticles, bulk. The use of zinc oxide nanoparticles as zinc fertilizers may increase
which use toxic chemicals so the need of the hour is to use envir- zinc dissolution and its bioavailability in soils with calcium carbonate.
onmentally benign, greener and ecofriendly routes. Researchers are Diffusion of dissolved zinc is the main mechanism for the movement of
looking forward for various biological entities like bacteria, fungi, zinc from fertilizer to the plant roots following the dissolution process
higher plants, actinomycetes and viruses for nanoparticles synthesis as [25]. Zinc oxide nanoparticles have shown much better antimicrobial
they can also reduce the salts to corresponding nanoparticles. Different activity than large zinc particles, since the small size less than 100 nm
biological sources have been used for the synthesis of nanoparticles and and high surface-to-volume ratio of nanoparticles allows better inter-
are being used in agriculture for precision farming [11]. Some of them action with bacteria [26]. Zinc oxide nanoparticles have the ability to
are as follows: silver nanoparticles, zinc oxide nanoparticles, titanium induce reactive oxygen species (ROS) generation, which can lead to cell
dioxide nanoparticles. death when the antioxidative capacity of the cell is exceeded [27–31].
Generation of reactive nitrogen species (RNS) and hydrogen peroxide
2.1. Silver nanoparticles (H2O2) upon exposure to silver and zinc oxide engineered nanoparticles
on the duckweed (Spirodela punctuta) suggested that the toxicity of
Silver nanoparticles have a high surface area and fraction of surface silver and zinc oxide nanoparticles predominantly caused by both the
atoms; as a result have high antimicrobial effect as compared to the particulates and ionic forms [32]. Zinc nanoparticles have shown to
bulk silver [12]. Antimicrobial property of silver nanoparticles has been induce free radical formation in wheat, resulting in increased mal-
used against a broad range of human pathogens [13–16]. However, the ondialdehyde and lower levels of reduced glutathione [33] and reduced
full potential is still to be explored for crop protection. Therefore, there chlorophyll contents [34].
is a growing interest to utilize antimicrobial property of silver Zinc oxide nanoparticles can be synthesized by chemical and
nanoparticles for plant disease management [17]. Silver nanoparticles biological methods. Since chemical methods require toxic chemicals,
have been experimenting as pesticides to reduce burden of pests from biological methods are becoming popular. Synthesis of zinc oxide
crops. Silver nanoparticles can be synthesized from physical, chemical nanoparticles from plants is cost effective and eco-friendly. Plant leaf
and biological methods. Owing to requirement of extreme conditions extract has been used commonly for synthesis of zinc oxide nanopar-
and toxic chemicals in physical and chemical methods, biological ticles. For synthesis of zinc oxide nanoparticles, appropriate concentra-
methods are widely used. Being single step synthesis and ecofriendly, tion of either zinc sulfate heptahydrate (ZnSO4·7H2O) or zinc acetate
different researchers have synthesized silver nanoparticles from differ- dehydrate (Zn(CH3COO)2·2H2O) is dissolved in water. Plant leaf extract
ent sources (plants, bacteria, fungi etc.). These silver nanoparticles have can be prepared in solvents such as water, ethanol or methanol. By
been used to get rid of harmful microorganisms in plants. mixing plant extract and zinc sulfate heptahydrate or zinc acetate
Biological synthesis of silver nanoparticles in sizes ranging from 6 to dehydrate solution at desired pH, zinc oxide nanoparticles are synthe-
38 nm from white radish (Raphanus sativus var. aegyptiacus) has been sized.
documented. The exposure of the snails and soil matrix to silver Zinc oxide nanoparticles have been tested in the laboratory as
nanoparticles in a laboratory experiment reduced the activity and the bactericide and fungicide. Zinc oxide nanoparticles using leaf extract of
viability of the land snail (20% of silver nanoparticles treated snails Moringa oleifera in size range from 16 to 20 nm has been synthesized
died) as well as the frequency of fungal population in the surrounding and antimicrobial activity against bacterial strains such as
soil [18]. Spherical shaped silver nanoparticles in size range of ∼10 to Staphylococcus aureus, Bacillus subtilis, Pseudomonas aeruginosa, Proteus
20 nm using culture supernatant of Serratia sp. BHU-S4 and their mirabilis, Escherichia coli and fungal strains such as Candida albicans and
effective application for the management of spot blotch disease in Candida tropicalis using the agar disc diffusion method has been tested.
wheat have been experimented. Silver nanoparticles exhibited strong The maximum zone of inhibition was observed in Staphylococcus aureus
antifungal activity against Bipolaris sorokiniana, the spot blotch patho- (23.8 ± 0.76) as compared to others [35]. Spherical and hexagonal
gen of wheat [17]. Effect of silver nanoparticles with diameters of zinc oxide nanoparticles from Parthenium hysterophorus L. have been
20 nm on seeds of Fenugreek (Trigonella foenum-graecum) has been synthesized by inexpensive, ecofriendly and simple method using
carried out. [19]. Different concentrations of silver nanoparticles (0, 10, different concentrations of 50% and 25% of Parthenium leaf extracts
20, 30 and 40 μg mL−1) were used and results showed that maximum with size 27 ± 5 and 84 ± 2 nm, respectively. These zinc oxide
seed germination (76.11%), speed of germination (4.102), root length nanoparticles were explored for the size-dependent antifungal activity
(76.94 mm), root fresh weight (2.783) and root dry weight (1.204) at a against plant fungal pathogens i.e. Aspergillus flavus and Aspergillus
concentration of 10 μg mL−1. These results revealed that application of niger. A maximum zone of inhibition was observed for 27 ± 5 nm size
silver nanoparticles could be used to significantly enhance seed zinc oxide nanoparticles against Aspergillus flavus and Aspergillus niger.
germination potential, mean germination time, seed germination index, Parthenium mediated zinc oxide nanoparticles proved to be good
seed vigor index, seedling fresh weight and dry weight. antifungal agents and environment friendly [36]. Spherical shaped zinc
oxide nanoparticles with an average size of 23 to 57 nm were prepared
2.2. Zinc oxide nanoparticles by zinc acetate and sodium hydroxide using leaves of Catharanthus
roseus (L.) G. Don leaf extracts. The synthesized zinc oxide nanoparti-
Zinc deficiency is a most common micronutrient problem that cles were evaluated for antibacterial activity against gram negative
adversely affects agricultural production in alkaline soils with calcium bacteria Escherichia coli (ATCC 25922), Pseudomonas aeruginosa (ATCC
carbonate [20]. The soils with calcium carbonate are a major source of 15442), gram positive Staphylococcus aureus (ATCC 6538) and Bacillus
agriculture in arid or Mediterranean environments of the world [21]. thuringiensis (ATCC 10792). Bacillus thuringiensis indicated the resis-
The parameters that limit zinc availability to plants in calcium tance to zinc oxide nanoparticles followed by Escherichia coli whereas
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Pseudomonas aeruginosa was more susceptible. This study concluded 3. Applications of nanotechnology in precision agriculture
that zinc oxide nanoparticles might be used as antibacterial formula-
tions against Pseudomonas aeruginosa [37]. 3.1. Delivery of fertilizers
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J.S. Duhan et al. Biotechnology Reports 15 (2017) 11–23
[47,48]. Nanocoated urea and phosphate and their sustained release of chitosan nanoparticles has been reported with polymethacrylic acid
will be beneficial to meet the soil and crop demands as majority of soil (PMAA) for loading NPK fertilizers. The stability of the chitosan-
in India is deficient in these macronutrients especially nitrogen. Many polymethacrylic acid (CS-PMAA) colloidal suspension was found to be
natural and synthetic polymers have been used for this sustained higher with the addition of nitrogen and potassium and phosphorus,
release of fertilizers. Biodegradable polymeric chitosan nanoparticles due to the higher anion charge from the calcium phosphate than the
(∼78 nm) showed good results for the slow release behavior of NPK anion charges from the potassium chloride and urea. [60]. The
fertilizer [53]. Kaolin and polymeric biocompatible nanoparticles also dispersions of CS-PMAA combined with 500 ppm of nitrogen were
have potential application in the slow release behavior of fertilizers higher in stability compared with that of phosphorus. Above 500 ppm
[46]. of nitrogen, a reduction of positive charges occurred in the colloidal
Nanofertilizers balances the release of fertilizer nitrogen and dispersion of CS-PMAA due to the presence of negative groups from the
phosphorus with the absorption by the plant, thereby preventing the urea molecules [54]. For dispersion with potassium, the stability of the
nutrient losses and avoiding unwanted nutrients interaction with solution has been confirmed with the addition of 400 ppm. This showed
microorganisms, water and air [54]. Absorption of nutrients by the the presence of Cl− ions (from KCl) which did not affect the stability of
plants from soil can be maximized using nanofertilizer. Nanofertilizer colloidal dispersion with the addition of up to 400 ppm [61,62,63,54].
encapsulated nanosilica can form a binary films on the cell wall of fungi
or bacteria after absorption of nutrients and prevent infections, hence
improve plant growth under high temperature and humidity and to 3.1.2. Biofertilizers
improve plant resistance to disease [55]. Silicon-based fertilizers used Biofertilizers are living, beneficial microorganisms. These include
to increase plant resistance as silicon dioxide nanoparticles can improve fungal mycorrhizae, Rhizobium, Azotobacter, Azospirillum and blue green
seedling growth and root development [56]. To increase food produc- algae, phosphate solubilizing bacteria like Pseudomonas and Bacillus
tion, TiO2 or titanium that is non-toxic can be used as additives in [64]. Microorganisms convert organic matter into simple compounds
fertilizers. The additives in fertilizers can increase water retention [54]. that provide essential nutrients to plants, improve soil fertility, main-
Due to the high solubility of many nitrogen fertilizers and their tain the natural habitat of the soil and increase crop yield. The
potential vulnerability to leaching and denitrification (especially in preparation, storage and method of application are crucial to the
the nitrate form); a wide range of slow-release fertilizers (SRFs) and success of biofertilizers application [65]. Drawbacks in usage are short
controlled-release fertilizers (CRFs) have been developed using syn- shelf life, temperature sensitivity and storage desiccation problems.
thetic or biopolymers [57,58]. The adsorbents zeolite, halloysite, Potential applications of polymeric nanoparticles for coating of biofer-
montmorillonite and bentonite nanoclays were used to develop nitro- tilizer preparations to yield formulations that are resistant to desicca-
gen fertilizers with controlled release characteristics where nanoclay tion have been utilized. Water-in-oil emulsion is one of the techniques
purification comes to be a costly affair except zeolite [59]. Preparation for storage and distributes microorganisms through liquid formulations
[66]. The oil traps the water around the microorganism hence down
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water evaporation. This is particularly favorable for microorganisms these traits was found as compared to control one [81]. Increase in
that are susceptive to desiccation. Water-in-oil emulsions also improve chlorophyll contents in sub-apical leaves of soybeans in a greenhouse
both cell viability and release kinetics by addition of substances to the test under hydroponic conditions have been reported using low
oil and/or aqueous phases. However, sedimentation during storage is concentrations of superparamagnetic iron oxide nanoparticles. This
one of the major issues of concern. Hydrophobic silica nanoparticles study concluded that iron oxide nanoparticles could be used as a source
reduced cell sedimentation and improved cell viability by thickening of iron for soybean for reducing chlorotic symptoms of iron deficiency
the oil phase during storage [67]. [82]. Foliar application of 500 mg L−1 iron nanoparticles to black-eyed
Due to limited availability of land and water resources and peas significantly increased the number of pods per plant (by 47%),
development of horticultural crops of Fabaceae, use of silver and gold weight of 1000-seeds (by 7%), the iron content in leaves (by 34%), and
nanoparticles as a growth promoting materials could be effective [68]. chlorophyll content (by 10%) over those of the controls. Application of
These nanoparticles with natural biofertilizers such as Pseudomonas iron nanoparticles also improved crop performance more than that by
fluorescens, Bacillus subtilis and Paenibacillus elgii have shown very good application of a regular iron salt. These parameters were increased by
growth promotion under in vitro conditions. Hence, needs in very 28%, 4%, 45%, and 12%, respectively, under the iron nanoparticles
minute amount in comparison to other fertilizers and their costs are treatment compared with these under treatment with iron salt. [83]. In
manageable as one liter of nano-biofertilizers can be used in several addition, iron nanoparticles significantly improved the beneficial effect
hectares of crops. Several soil microorganisms are present in the of magnesium nanoparticles used as nanofertilizer on black-eyed peas.
rhizosphere zone, especially plant growth promoting rhizobacteria For an optimal growth, most of the plants generally required
(PGPR) have the best plant growth-promoting activities. The impact 1–5 mg L−1 iron in soil solution [84]. Manganese nanoparticles have
of gold nanoparticles on PGPR was investigated viz., Pseudomonas been reported to enhance growth of mung bean (Vigna radiata) and
fluorescens, Bacillus subtilis, Paenibacillus elgii, and Pseudomonas putida. photosynthesis [85]. Enhanced growth of mung bean and chickpea
No positive or negative impact was observed in Pseudomonas putida to (Cicer arietinum) seedlings at low concentrations using zinc-oxide
gold nanoparticles. Significant increase was observed in case of P. nanoparticles with plant agar method were observed, however a decline
fluorescens, P. elgii and B. subtilis and hence gold nanoparticles can be in growth rates of roots and shoots were observed beyond optimal
exploited as nano-biofertilizers [69]. A list of nanofertilizers tested and concentrations [86].
their action against plant pathogens is given in Table 1.
3.3. Insect pest management
3.2. Micronutrient supply Synthetic agrochemicals have changed the face of agriculture, but it
has also developed new challenge in form of insect pest resistance.
It’s a well-established fact that micronutrients like manganese, Nanoparticles have a great promise for the management and control of
copper, boron, iron, molybdenum, zinc etc. are important for the insect pest of modern agriculture. Insecticidal activity of garlic essential
growth and development. A substantial increase of crop yields with oil against Tribolium castaneum (red flour beetle) has been increased by
the green revolution and new farming practices has progressively polyethylene glycol-coated nanoparticles [87]. Using this formulation
decreased the micronutrients of soil like zinc, iron and molybdenum the control efficacy against adult T. castaneum was calculated about
[77]. Foliar application of micronutrients can enhance uptake by the 80% which was presumably due to the slow and sustained release of the
leaves [78]. Nanotechnology can be used to make the availability of active components from the nanoparticles. Applications of different
micronutrients to plants. Nano formulations of micronutrients can be kinds of nanoparticles such as silver nanoparticles, aluminium oxide,
sprayed on plants or can be supplied to soil for uptake by roots to zinc oxide and titanium dioxide in the control of rice weevil (caused by
enhance soil health and vigor [79]. The release of behavior of 1- Sitophilus oryzae) and grasserie disease in silkworm (caused by Bombyx
naphthylacetic acid (an important plant growth hormone) from chit- mori and baculovirus BmNPV(B. mori nuclear polyhedrosis virus) were
osan nanoparticles has been tested at different pH’s and temperature. studied [88]. Das et al. [89] studied the transformation of Bombyx mori
The formulation was found to have potential for the slow release of nucleopolyhedrovirus by lipophilically coated silica nanoparticle, alu-
agrochemicals such as hormones [80]. Different nanoparticles have mina nanoparticles in the hexagonal close-packed α structure and
been tested to provide appropriate level of micronutrients in plants. aspartate capped gold nanoparticle in B. mori cell line using cytopathic
Iron deficiency is a widespread problem in plants growing mainly in effect and plaque reduction assay. A moderate polyhedra roughening
high pH and calcareous soils. Foliar application of iron compounds with was observed for alumina nanoparticles, and no roughening was
the technology of nanoparticles may be a solution to the problem. Effect noticed for gold nanoparticles. When leaves of mulberry (B. mori) were
of spraying of iron oxide nanoparticles on the response of wheat treated with ethanolic suspension of hydrophobic alumino-silicate
growth, yield and quality has been assessed. The concentrations of nanoparticle, a significant decrease in viral load was reported [7].
iron nano-oxide solution has been used in five levels (0, 0.01%, 0.02%, Insecticidal activity of nanostructured alumina against Sitophilus oryzae
0.03% and 0.04%) to check the effect on spike weight, 1000 grain L. and Rhyzopertha dominica reported significant mortality after 3 days
weight, biologic yield, grain yield and grain protein content. Increase in of continuous exposure to nanostructured alumina-treated wheat. So,
commercially available insecticides, inorganic nanostructured alumina
Table 1 may provide a cheap and reliable alternative for control of insect pests
Nanofertilizers and their action against plant pathogens. [90]. Debnath et al. [91] tested the entomotoxicity of silica nanopar-
Type Nanofertilizers Antimicrobial action References
ticles against rice weevil Sitophilus oryzae and compared the efficacy
against plant pathogens with bulk-sized silica (individual particles larger than 1.0 μm). Amor-
phous silica nanoparticles was found to be highly effective against this
Plant growth Ag Bacillus cereus [70] insect pest causing more than 90% mortality, indicated the effective-
promoting Ag Escherichia coli, Bacillus [71]
microorganisms subtilis and Streptococcus
ness of silica nanoparticles to control insect pests. Nano-encapsulation
thermophilus of pesticide allows proper absorption of the chemical into the plants
Ag and TiO2 Lactobacillus strains [72] due to slow and sustained release and has a long lasting and persistent
Ag Corynebacterium sp. [73] effect unlike the normal agrochemicals [92]. Synthetic pesticides have
Au Klebsiella pneumoniae [74]
detrimental environmental impacts, but their specificity towards the
Ag Fusarium oxysporium [75]
Ag Aspergillus fumigatus [76] targeted pests is high. So there is a need to come towards botanical
insecticides with the use of nanotechnology to expand the frontiers for
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Fungal diseases among crops cause major loss to the production. Ag Bipolaris sorokiniana [100]
Although there are a number of fungicides available commercially, Bipolaris sorokiniana and Magnaporthe grisea [101]
Fusarium sp., Alternaria solani, Pythium spinosum, [102]
their application causes detrimental effects to plants also.
Pythium aphanidermatum, Cylindrocarpon
Nanotechnology can play a very important role in solving this problem. destructans, Cladosporium cucumerinum, Glomerella
Nanoparticles have been experimenting as antifungal agents against cingulata, Didymella bryoniae, Stemphylium lycopersici
pathogenic fungi. Antifungal activity of nanoparticles of zinc oxide and Monosporascus cannonballus
(35–45 nm), silver (20–80 nm) and titanium dioxide (85–100 nm) has Alternaria alternata, Penicillium digitatum [103]
and Alternaria citri
been tested against Macrophomina phaseolina, a major soil borne
Bipolaris sorokiniana [104]
pathogen of pulse and oilseed crops. The higher antifungal effect was Candida spp., Aspergillus spp., Fusarium spp [105]
observed in silver nanoparticles at lower concentrations than zinc oxide Cu Aspergillus flavus, Aspergillus niger, Candida albicans, [106]
and titanium dioxide nanoparticles [93]. Maize treated with nanosilica Staphylococcus aureus, Escherichia coli, Micrococcus
luteus, Klebsiella pneumoniae, Pseudomonas
(20–40 nm) has been screened for resistance against phytopathogens,
aeruginosa
Fusarium oxysporum and Aspergillus niger as compared with that of bulk Phoma destructiva, Curvularia lunata, Alternaria [107]
silica. Nanosilica-treated plant showed a higher expression of phenolic alternata and Fusarium oxysporum
compounds (2056 and 743 mg/mL respectively) in collected leaf Fusarium equiseti, F. oxysporum, F. oxysporum [108]
extracts and a low expression of stress-responsive enzymes against Fusarium sp. [109]
Cu-chitosan Alternaria alternata, Macrophomina phaseolina and [110]
these fungi. These results showed significantly higher resistance in
Rhizoctonia solani
maize in treated with nanosilica than with bulk in terms of disease Zn Aspergillus niger and Fusarium oxysporum [111]
index and expression of total phenols, phenylalanine ammonia lyase, S Aspergillus niger and Fusarium oxysporum [112]
peroxidase and polyphenol oxidase, at 10 and 15 kg/ha. So silica ZnO Botrytis cinerea and Penicillium expansum [113]
Aspergillus fumigatus and Candida albicans [114]
nanoparticles can be used as an alternative potent antifungal agent
Fusarium oxysporum and Penicilium expansum [115]
against phytopathogens [94].
The silver has much higher antifungal activity than that of other
metals. This is because silver ions cause the inactivation of cell wall and atrazine against alga Pseudokirchneriella subcapitata and the micro-
thiol groups of fungal cell wall resulting in disruption of transmem- crustacean Daphnia similis has been tested. Herbicides encapsulated in
brane, energy metabolism and electron transport chain. Mutations in the poly(ε-caprolactone) nanocapsules resulted in lower toxicity to the
fungal DNA, dissociation of the enzyme complexes that are essential for alga (Pseudokirchneriella subcapitata) and higher toxicity to the micro-
the respiratory chain, reduced membrane permeability and cell lysis are crustacean (Daphnia similis) as compared to the herbicides alone [122].
also other mechanisms [95]. The efficacy of silver nanoparticles is A list of nanoparticles used as herbicides against weeds in different
dependent on particle size and shape and decreases with increasing vegetable crops is given in Table 3.
particle size. It has been found that truncated triangular particle shape
showed greater “cidal” effect than spherical and rod shaped particles
[96,97]. Antifungal properties of silver nanoparticles for plant disease 3.6. Biosensors in precision agriculture
management have been utilized [98]. Well diffused and sustained silver
nanoparticles solution can act as an excellent fungicide due to good Precision farming has been a long-desired goal to maximize output
adhesion on bacterial and fungal cell surface [99]. Table 2 shows from crops while minimizing the input of fertilizers, pesticides,
nanoparticles with their fungicidal action against pathogenic fungi. herbicides, etc. through monitoring environmental variables and apply-
ing targeted action. Precision farming makes use of computers, sensors,
3.5. Nanoherbicides global satellite positioning systems and remote sensing devices to
measure highly localized environmental conditions and helps in
Weeds are the biggest threat in agriculture and decline the yield of determining whether crops are growing at maximum efficiency or
crop to a greater quantity by using the nutrients which otherwise were precisely identifying the nature and location of problems. Ultimately,
available to the crop plants. Eradicating weeds by conventional means precision farming with the help of smart sensors will allow enhanced
are time consuming. There are a number of herbicides available productivity in agriculture by providing accurate information thus
commercially. They kill the weeds in the fields, but also damages crops helping farmers to make better decisions [131].
plants. They are also responsible in decreasing soil fertility and creating
soil pollution. Nanoherbicides can play a very important role in
removing weeds from crops in an eco-friendly way, without leaving Table 3
any harmful residues in soil and environment [116]. Encapsulation of Nanoparticles used as herbicides in commercial vegetable crops.
herbicide in polymeric nanoparticles also results in environmental
safety [117]. Disproportionate use of herbicides for longer period of Sr. No. Nanoparticles Nanoherbicides used against References
herbs/weeds
times leaves residues in soil, which cause damage to succeeding crops
[118]. Continuous use of same herbicide for constant period of time 1. Silver nanoparticles- Eichhornia crassipes [123]
cause weeds resistance against same herbicide. Effectiveness of nano chitosan encapsulated
zerovalent iron (nano ZVI) has been assessed to dechlorinate herbicide paraquate
atrazine (2-chloro-4ethylamino-6-isopropylamino-1, 3, 5-triazine) from 2. Ag, Cu, Fe, Zn, Mn Allium cepa (L.) [124]
atrazine-contaminated water and soil [119]. Target specific nanoparti- 3. Cu Cucurbita pepo [125,126]
cles loaded with herbicide has been developed for delivery in roots of 4. CuO Raphanus sativus, Lolium [127]
weeds. These molecules enter into the roots system of the weeds, perenne and Lolium rigidum
5. CuO and ZnO Fagopyrum esculentum [128]
translocate to cells and inhibit metabolic pathways such as glycolysis.
6. Cu Elodea densa [129]
This ultimately leads to death of plants [120,121]. 7. CuO and ZnO Cucumis sativus [130]
Toxicity of poly(ε-caprolactone) nanocapsules containing ametryn
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3.6.1. Normalized difference in vegetative index (NDVI) sensor or green spectroscopy has been reported with high sensitivity (1.0 μmol/dm3)
seeker [144].
NDVI is a device which uses light emitting diodes (nano-based) to
generate red and near infrared light which are used to calculate NDVI 3.6.3. Quantum dots (QDs)
values. Green seeker calculates the normalized difference in vegetative Quantum dots are far better and rapid than organic fluorescent dyes
index using red and near infra-red light. It is based on the simple due to more efficient luminescence, small emission spectra, excellent
principle that plant chlorophyll absorb red light as an energy source photostability and tenability according to the particle sizes and material
during photosynthesis. Therefore, healthy plants absorb more red lights composition. By a single excitation light source, QDs can be excited to
and reflect larger amounts of near infra-red light than those that are all colors due to their broad absorption spectra [145]. Quantum dots
unhealthy and thus give higher NDVI value. have been used to detect pathogens associated with different plant
NDVI is calculated using the equation: diseases.
NDVI = NIRreflected − Redreflected/NIRreflected + Redreflected Quantum dots-fluorescence resonance energy transfer based sensors
have been developed to detect witches’ broom disease of lime caused by
Green seeker is an excellent indicator of biomass. This tiny device Phytoplasma aurantifolia. The immunosensor developed showed a high
makes plants speaks up for their nitrogen needs [132]. sensitivity, specificity of 100%, and a detection limit of 5 ca. P.
aurantifolia per μL [146]. Rhizomania is the most destructive disease
in sugar beet caused by beet necrotic yellow vein virus. Polymyxa betae
3.6.2. Nanobiosensors (Keskin), the only known vector of beet necrotic yellow vein virus, for
Nanobiosensors can be productively used in sensing a broad array of transmission of the virus to the plants was successfully detected by
agriculture like in fertilizers, herbicide, pesticide, insecticide, moisture quantum dots-fluorescence resonance energy transfer-based sensor
and soil pH. Controlled use of biosensors can assist in sustainable [147]. To detect organophosphorus pesticides (OPs) in vegetables and
agriculture for increasing crop productivity. Precision farming, with the fruits; the optical transducer of cadmium telluride semiconductor
aid of smart sensors, could enhance productivity as this technology quantum dots integrated with acetylcholinesterase enzyme by the
ensures better fertilization management, reduced input cost and layer-by-layer assembly technique. This resulted in a highly sensitive
environment safety. Nanosensors based smart delivery systems could biosensor based on enzyme inhibition mechanism with detection limits
help in the efficient use of natural resources like water, nutrients and of 1.05 × 10−11 M for paraoxon and 4.47 × 10−12 M for parathion
agrochemicals by precision farming [133]. which was far better than the conventional gas chromatography
The presence of plant viruses, the level of soil nutrients and crop methods or amperometric biosensors (0.5 nM) [148]. Unique optical
pathogens can be detected by nanosensors [134,135]. A nanobiosensor property of thiol-stabilized luminescent cadmium telluride (CdTe)
based on atomic force microscopy tip functionalized with the acet- quantum dots has been used to detect smethyl parathion at picogram
olactate synthase enzyme was detected for herbicide metsulfuron- levels [149]. Water-soluble CdTe quantum dots and highly fluorescent
methyl (an acetolactate synthase inhibitor) through the acquisition of silica molecularly imprinted nanospheres embedded cadmium telluride
force curves [136]. Bionanosensors also makes it possible for rapid quantum dots have been used as a biosensor for determination of
detection of bacteria and viruses with precise quantification and deltmethrin in fruit and vegetable samples [150].
thereby increasing the food safety for the customer [137]. A highly
sensitive organophosphorus pesticide biosensor constructed with the
help of surface functionalized carbon nanotubes tailored with amino 3.6.4. Nanobarcodes
groups to control the efficient immobilization of acetylcholinesterase Nanobarcode particles are manufactured via a semi-automated and
onto the surface of glassy carbon electrode and these have been highly scalable process of electroplating of inert metals such as gold,
successfully used for the direct analysis of vegetable samples [138]. silver, etc. into templates defining particle diameter and thus resulting
An acetyl cholinesterase biosensor based on assembly of multiwall nanorods from the templates are released. These nanobarcodes are used
carbon nanotubes onto liposome bioreactors was developed for detec- as identification tags for multiplexed analysis of gene expression.
tion of organophosphates pesticides [139]. A highly sensitive acetyl- Nanotechnology assisted advancement in the field of biotechnology
cholinesterase biosensor modified with hollow gold nanospheres with has seen improvement in the plant resistance to environmental stresses
the detection limits 0.06 μg/dm3 for chlorpyrifos and 0.08 μg/dm3 for such as drought, salinity and diseases. Nanotechnology-based gene
carbofuran was developed [140]. Zn-Se quantum dot immobilized sequencing is capable of rapid and cost effective identification and
acetylcholinesterase has been used for detection of organophosphate utilization of plant gene trait resources [151]. So there are a number of
pesticides using graphene-chitosan nanocomposite modified electrode. applications of nanotechnology in agriculture which have been shown
Organophosphate pesticides have been detected with this biosensor by schematic representation in Fig. 3. A schematic representation of
using methyl parathion as a model enzyme inhibitor, with a detection different aspects of nanotechnology in agriculture is shown in Fig. 4.
limit of 0.2 nmol/dm3 [141]. For determination of pesticides methyl-
parathion and chlorpyrifos; an electrochemical biosensor based on 4. Nanotechnology and agribusiness
acetylcholinesterase immobilized on polyaniline precipitated on verti-
cally assembled carbon nanotubes and wrapped with ssDNA was According to global economic reports, an estimated global agribusi-
prepared. The pesticides were determined via inhibition of enzyme ness market in 2010 ranged from about US$ 20.7 billion to US$ 0.98
reaction acetylcholinesterase-acetylcholine that caused small changes trillion. By 2020, the market will be estimated to be more than US$ 3.4
of local pH in the surrounding of an electrode surface and the detection trillion [152,153]. At present the United States of America leads with a
limit of the biosensor for both the pesticides was found to be 4 year, 3.7 billion USD investments through the National Nanotechnol-
1 & 903;10–12 mol/dm3 [142]. ogy Initiative (NNI) [154,155]. The USA is followed by Japan and the
Electrochemically functionalized single walled carbon nanotubes European Union and these countries have abundant funds (US$ 750
(SWCNTs) based nanosensors with metal/metal oxide nanoparticles or million and US$ 1.2 billion, including individual country contributions,
nanotubes for gases viz. ammonia, nitrogen oxides, hydrogen sulfide, respectively per year [156]. Today, more than 400 companies in the
sulfur dioxide and volatile organics have potential application in world are active in nanotechnology research and development and this
monitoring agricultural pollutants and assessment of impacts on living number is expected to increase to more than 1000 in next 10 years
matter or health and in increase of crop productivity [143]. Screening [157]. Different nanoproducts in agriculture have been produced by
of organophosphorus agents with gold nanoparticles and fluorescence different organizations and a list of these is given in Table. 4.
17
J.S. Duhan et al. Biotechnology Reports 15 (2017) 11–23
18
J.S. Duhan et al. Biotechnology Reports 15 (2017) 11–23
Table 4
Nanotechnology based products and their applications in agriculture.
Nano-sized nutrients (ZnO and TiO2 2015 Washington University in St. Louis Boost in growth and antioxidants in tomatoes [158]
nanoparticles)
Biodegradable thermoplastic starch (TPS) 2002 Pusan National University, Korea Good tensile strength and lowered water permeability [159]
Hydrolyzed collagen/sodium alginate 2008 Sichuan University, Chengdu, Preservation of loquat and cherry [160]
nanocomposite Sichuan, China
Macronutrient fertilizers coated with zinc oxide 2012 University of Adelaide, AU, Enhancement of nutrients absorption by plants and the delivery of [161]
nanoparticles CSIRO Land and Water, AU, nutrients to specific sites
Kansas State University, US
Primo MAXX 2011 Syngenta, Greensboro, NC, USA Grass growth regulatory [162]
Nanoemulsion 2012 VIT University, INDIA Neem oil (Azadirachta indica) nanoemulsion as larvicidal agent [163]
Zeolites and Nano-clays – Geohumus-Frankfurt, Water retention and slow release of agrochemicals for proper [164]
DE absorption by the plants
Nanosensors 2007 (University of Crete, GR) Pesticide detection with a liposome-based nano-biosensor [165]
Acetamprid loaded alginate-chitosan 2015 GJUS & T Improved delivery of agrochemicals in the field, better efficacy, [166]
nanocapsules Hisar, better control of application/dose.
India
toxicity of zinc oxide and titanium dioxide nanoparticles on rice (Oryza negative and positive effects of nanoparticles on plants is given in
sativa L.) roots. The three parameters examined were: seed germination Tables 5 and 6.
percentage, root length and number of roots. The results showed that
there was no reduction in the percent seed germination from zinc and 6. Conclusion
titanium dioxide nanoparticles. However zinc oxide nanoparticles
showed detrimental effects on rice roots at the early seedling stage. Nanotechnology has shown great potential in precision agriculture.
Zinc oxide nanoparticles were found to stunt roots length and reduce Nanoparticles with unique properties can be easily synthesized from
the number of roots. Whereas titanium dioxide nanoparticles had no different biological sources and can be applied in agriculture. Among
effect on root length. This study showed that direct exposure to specific biological sources, plant extracts (leaves, flower, stem, roots) from
types of nanoparticles could cause significant phytotoxicity and em- diverse range of plant species have been successfully used in synthesiz-
phasized the necessity for ecologically responsible disposal of wastes ing nanoparticles. Biomolecules present in plant extracts reduce metal
containing nanoparticles and further use in agricultural and environ- ions to nanoparticles in a single-step green synthesis process. This
mental systems. Chai et al. [171] studied the effect of metal oxide process of green synthesis is environment friendly, easy to perform, can
nanoparticles (ZnO, SiO2, TiO2 and CeO2) on functional bacteria and be performed at room temperature without the need of sophisticated
metabolic profiles in agricultural soil. They treated agricultural soil instrument and can be easily scaled up or modified according to the
with ZnO, SiO2, TiO2 and CeO2 nanoparticles at 1.0 mg g−1. The needs. In this process the various water soluble plant metabolites (e.g.
toxicity effect was evaluated by thermal metabolism, the abundance alkaloids, phenolic compounds, terpenoids) and co-enzymes are re-
of functional bacteria and enzymatic activity. ZnO and CeO2 nanopar- duced to nanoparticles. The nanotechnology based delivery of nano-
ticles were observed to hinder thermogenic metabolism, reduced particles has given promising results for plant disease resistance,
numbers of soil Azotobacter, P-solubilizing and K-solubilizing bacteria enhanced plant growth and nutrition via site specific delivery of
and inhibited enzymatic activities. Whereas TiO2 nanoparticles reduced fertilizers and other essential nutrients with the help of controlled
the population of functional bacteria and enzymatic activity. SiO2 release formulations of nanoparticles. Nanoencapsulation can also
nanoparticles slightly boosted the soil microbial activity. A list of improve herbicide application by providing better penetration and
Table 5
Adverse effects of nanoparticles on plants.
1. TiO2 Inhibition in cell growth and nitrogen fixation activity Anabaena variabilis [172]
2. TiO2 Reduced germination Triticum aestivum L. var. Pishtaz [173]
2. Al Decreased root length Lolium perenne [174]
3. Al Reduced germination Lolium perenne [174]
4. Al Reduced root length Zea mays, Lactuca sativa [174]
5. Ag Reduced shoot and root length Triticum aestivum L. [175]
6. Ag Reduced germination (Hordeum vulgare L., cv. Annabell [176]
7. Ag Decreased mitosis, disturbed metaphase, sticky chromosome, cell wall Allium cepa [177]
disintegration and breaks
8. Ag Reduced shoot length Linum usitatissimum L., [176]
cv. Electra, Lolium perenne L., cv. Tove
9. Ag Reduced transpiration Cucurbita pepo [178]
10. Zn Reduced root growth and elongation Zea mays, Cucumis [174]
Sativus, Lactuca sativa, Raphanus sativus, Brassica napus,
Lolium perenne
11. Cu Reduced seedling growth Phaseolus radiatus [179]
12. Cu Reduced biomass and root growth Cucurbita pepo [178]
13. Al2O3 Reduced root growth Zea mays, Cucumis sativus, Brassica oleracea, Daucus carota [180]
14. Al2O3 Reduced root length Zea mays [174]
15. CeO2 Reduced shoot growth Lycopersicon esculentum [181]
16. CeO2 Reduced shoot growth Zea mays [181]
17. ZnO Reduced germination Zea mays [174]
19
J.S. Duhan et al. Biotechnology Reports 15 (2017) 11–23
Table 6
Positive effects of nanoparticles on plants.
allowing the slow and sustained release of the active substances. Hence Stenotrophomonas maltophilia, PLoS One 8 (2013) e59140, http://dx.doi.org/10.
1371/journal.pone.0059140.
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