Abstract
In the present situation, it is critical to meet the nutritional needs of the world’s rising population. Nearly one-third of crops are affected in conventional farming due to pathogens infestation. Nanotechnology can change agricultural production and improve plant growth by facilitating the cost-effective management of natural resources and other necessary inputs. Nanomaterials (NMs) in agriculture offer a once-in-a-lifetime opportunity to improve crop yield and preserve soil health. Potential NMs uptake in soil-plant systems and positive and negative effects in various crops have been observed in several studies. Because of their unique properties, NMs have received much attention in agriculture. NMs and nanotechnology improve the stability and dispersion of active ingredients, reduce residual pollution and labor costs, and maintain agricultural systems’ sustainability. Many nanomaterials-based formulations have been extensively used for plant growth and development, including nano-based associated pesticides and fertilizers in the modern agricultural system. Understanding the interactions between plants and NMs opens up new paths for improving agricultural crop yield and quality. This chapter helps readers better understand the role of NMs in plant growth and development.
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1 Introduction
Agriculture serves as the principal pillar of the growing economy, supplying food for a better quality of life. The scenario described above will be crucial for countries, particularly the developing world, where agricultural production is the primary source of economy and face numerous challenges in the sectors of economy, commodity reliance, poverty, and malnourishment. A considerable agricultural output is being achieved by utilizing present nanomaterials (NMs), which are aimed at effective components systems, healthy plant defense strategies, organic farming, and several other applications [1]. Recently researchers noticed that practically introducing based products lines to revolutionize advanced farming techniques. NMs are highly reactive due to high surface area-to-volume ratio and physical and chemical characteristics, delivering a concise benefit in terms of requisite alteration in response to rising supply. With the assistance of these cutting-edge materials, modern agriculture is converting into precision farming, allowing for the most outcome from the resources available. Agriculture has always been the most essential and reliable segment since it generates and supplies crude ingredients to the feed and food industry sectors. Fertilizers are required to boost crop yields, but they also reduce soil quality by disrupting soil nutrient balance [2, 3]. Pesticides, fertilizers, and antibiotics are commonly applied and adequately disintegrate. Also, pesticides cost and fertilizers are extremely huge, and this must be monitored. The use of NMs in agriculture seeks to decrease nutrient shortages to boost yields, decrease product amount lines used for crop safety [4], and mitigate production costs to maximize outcomes. It has not only fundamentally changed agriculture by implementing creative nutrients of nano-fertilizers, but it has also aided in crop protection by developing nano-pesticides, efficient irrigation systems, and rising plant efficiency in using the energy of the sun [5, 6]. The only way to meet demand is to increase productivity and income per unit of limited natural resources through efficient technological improvements.
Nanotechnology can increase agricultural production by the following ways: (1) agrochemical nano-preparations applied as pesticides and fertilizers for crop enhancement, (2) use of nano-sensors for identification of various diseases in crop protection, (3) nano-devices for genetic engineering of plants, (4) diagnosis of plant diseases, and (5) post-harvest management. NMs are materials with particle dimensions of not as much as 100 nm and have exclusive properties like size-dependent abilities, high surface-to-volume ratio, and promise optical characteristics [7]. NMs created using environmentally friendly and green techniques can improve agriculture by enhancing fertilization, plant growth regulators, and pesticides. The use of NMs in agriculture works as an alternative to agrochemicals. Noticeably, NMs increase crop yields by improving agricultural products’ productivity to allow for site-targeted controlled delivery of nutrient content, confirming lesser agrochemical use.
2 Nanomaterials for Sustainable Intensification in Agriculture
In agriculture, nanotechnology offered numerous agri-techniques like nano-fertilizers, nano-pesticides, and nano-sensors, which have all demonstrated meaningful results for sustainable farming exercises. Such nano-inputs decreased the use of fertilizers or pesticides amount and delivered targeted delivery of active compounds. As a result, nontargeted organisms are unaffected by such nano-tools and the environment is protected. The use of nanotechnology in agriculture and the food industry can fundamentally change various sectors by providing modern tools for disease detection and treatment and increasing plant nutrient uptake capacity. Nano-agriculture employs nanotechnology to increase plant yield, fuel, and other drives. Nano-formulations are suggested to enhance agricultural chemical efficacy, delivery systems, plant nutrient uptake and outcome, and food quality. The nano-fertilizers, nano-pesticides, and nano-sensors, among other things, have changed traditional agricultural practices into sustainable farming. It has been reported that using NMs as an agro-based product does not affect nontargeted organisms [8]. It also improved solubilization, increased active ingredient shelf life, and governed discharging capacity. NMs are environmentally friendly for the experiment and are being utilized in field conditions. Due to agri-friendly characteristics, nano-tools are ideal for preserving ecological quality by lowering the damaging impact of synthetic chemicals.
Furthermore, research is necessary to confirm the limit for individual metal NPs in the crop system and maintain the supply of an excellent variety of concentrations. Another biocompatible NMs synthesis route for agricultural applications is green NPs synthesis. These nano-tools would also be much able to reduce the excessive use of chemical fertilizers and pesticides.
Nano-fertilizers are a relatively new agricultural advancement. Silver, iron, zinc, titanium, carbon nanotubes, molybdenum, and silica are some nano-fertilizers that are established and used in different crop frameworks. NMs are added to soil as per nano-structured fertilizers (similar to Fe, Mn, Zn, Cu, Mo NPs) or improved transport schemes to progress absorption and efficiency of fertilizer application [6]. Metallic NPs based on Fe2O3, ZnO, TiO2, and Cu are used as nano-fertilizers in the soil through irrigation or foliar applications [9,10,11]. More prospects for using nanotechnology in agriculture exist in the sectors of plant genetic improvement [12], transfer of genes and drug particles to exact sites at cell level in plants, and nano-array-based technologies for expression of genes in plants to resolve stress, as well as the advancement of sensors and procedures for their use in smart agriculture [13]. The majority of early research for NM-based plants genetically engineered has been done in plant cell cultures. Magnetic NPs were used to ensure an effective, stable genetic transformation in cotton. Mesoporous silica NPs with lox P site integrated into chromosomal DNA was used like transporters to carry Cre recombinase in undeveloped embryos of maize. The lox P correctly recombined after introducing engineered mesoporous silica NPs in plant materials, attempting to establish an effective genetic modification [14].
Weeds are the most dangerous threat to crops because they consume nutrients that would otherwise be available to plants. Traditional methods of weed eradication, such as hand weeding, are time-consuming and labor-intensive. Several herbicides exist in the market that can destroy weed growth while causing crop damage and decreasing soil fertility. Nano-herbicides are created by utilizing nano-technological possible for active distribution of biological or chemical herbicides through nano-size or NMs established herbicide compositions. Compared to conventional herbicides, NMs-based designs might improve herbicide efficacy, solubility, and lower toxicity. Early weed management using NP-based herbicide release systems has the potential to reduce herbicide resistance, preserve active substance activity, and extend herbicide discharge over a more extended period [15]. The innovation of a particular herbicide compound encapsulated in an NP targets specific receptors found at the root of the aimed weed. The advanced NP inserts the weed's root system and is translocated to undertake its action, preventing plant root glycolysis. The focused action causes the plant to starve and thus kills it. Nano-herbicides may be a more excellent, more environmentally favorable option for weed controllers that do not leave toxic remains in the soil.
Nanotechnology applications in plant protection have impacted agriculture and enhanced yields. Metal NPs of various types like nano-formulations, nano-encapsulated active constituents, and nano-composites are reported for crop protection. Several NMs were shown to have a more significant inhibition effect against crop pathogens in the lab and the greenhouse. Nano-sensors also supplied fast and precise evidence about soil environments or pathogen recognition, allowing for a timely controller and crop safety, which aids farmers in reducing losses and improving their economic condition. Because of their recognition efficacy in small quantities, nano-sensors lessen significant crop harm by monitoring field conditions and pest attacks.
NMs are used to develop biosensors or used as “sensing materials” in crop biotechnology, agriculture, and the food industry [16]. Various nanosensors viz., plasmonic nanosensors, fluorescence resonance energy transfer-based nanosensors, carbon-based electrochemical nanosensors, and nanowire and antibody nanosensors have been used in agricultural practices. Even though the usage of nano-sensors is still in its early stages [17], some remarkable findings suggest the usage of NMs, such as apparatuses for detecting and quantifying plant metabolic flux, pesticide residues in food, bacterial and bacterial, and viral, fungal pathogens. NMs-based biosensors seem to be very encouraging because they allow for the early screening and precise quantification of virus, bacteria, and fungi in plants [18, 19]. We have summarized the agricultural applications of some metal NPs in tabular form (Table 1).
3 Nanomaterials: A New Carrier in Agricultural Development
3.1 Sources and Synthesis
Based on their origin, NMs sources can be divided into three major categories: (a) incidental NMs, which are generated as a by-product of industrial processes; (b) engineered NMs, which are produced by living beings that have specific properties required for different applications; and (c) naturally produced NMs.
3.1.1 Incidental NMs
Usual procedures that lead to the manufacture of NMs include forest fires, volcanic eruptions, and photochemical reactions. Furthermore, detaching of skin and hair by plants and animals, which frequently occurs in nature, contributes to the composition of NMs. Natural measures like forest fires, volcanic eruptions, and dust storms have produced a large amount of nano-particulate material, significantly impacting global air quality. Similarly, human activities such as transportation, industrial operations, and charcoal burning contribute to the emergence of synthesized NMs. Throughout the universe, various types of NMs are sorted, mixed, and amended in multiple systems. In the desert and terrestrial regions, dust storms are the primary source of NMs. According to satellite images, dust storms in one province transport nano- and micro-sized crystals and pollutants thousands of kilometers away from the start. Dust storms seem to be the most significant single contributor to environmental NMs. Volcanic eruptions release a vast volume of aerosols and small elements into the atmosphere, ranging in size from micrometers to numerous nanometres. A solitary volcanic eruption can spew up to 30×106 tons of NPs into the atmosphere in ash form [34]. Grass/forest fires have been a portion of the earth's natural history for a long time and are caused mainly by lightning strikes or anthropogenic. Significant fires can have distributed ash and smoke over hundreds of square miles, increasing the amount of particulate matter, including NMs.
3.1.2 Engineered NMs
Anthropogenic actions that contribute to the development of NMs include simple combustion in vehicles, coal for power generation and fuel oil [35], chemical engineering, welding, and airplane engines [36]. Carbon and TiO2 NPs and hydroxyapatites are examples of NMs [37] found in various marketable cosmetics, sunscreen, toothpaste, etc. In the city, diesel and automobile exhaust are the leading causes of atmospheric nano- and micro-particles. Anthropogenic activities such as cigarette smoking and building demolition lead to the dissemination of NPs into the environment. Cigarette smoke contains a composite mix of approximately 1 lakh chemical components in NPs varying in size from 10 to 700 nm [38]. Likewise, nano- and micro-particulates smaller than 10 m are released into the atmosphere [39]. Aside from construction remains, glass, repairable fibers, and other poisonous elements from domestic resources are released as nano-sized compounds around the demolition location [39].
3.1.3 Naturally Produced NMs
NMs are found in living organisms like fungi, bacteria, algae, and viruses to plants. The understanding of nanostructures found in microorganisms is critical for future usage of these organisms in agricultural applications. A wide range of NMs derived from natural products have incredible power, light weight, transparency, and biocompatibility, making them the best products for coatings, packaging, medicine, construction, electronics, filtration, transportation, and other applications. Given the growing concerns about environmental and sustainability, NMs derived from natural sources are gaining traction in scientific and agricultural communities. We summarized some NPs synthesized in tabular form from plants, bacteria, fungi, algae, and viruses (Table 2).
3.1.3.1 By Bacteria
Bacterial strains are broadly used as nano-factories for the production of numerous metallic NPs. It has been demonstrated that both extracellular and intracellular approaches can be used. Extracellular biosynthetic pathway happens outside of the bacterial cell using a variety of techniques, including (a) use of bacterial biomass, (b) use of bacterial culture supernatant, and (c) use of cell-free extracts. Because it does not require complex downstream processing, extracellular synthesis is favored over intracellular synthesis [56]. These NPs have found use in a variety of fields, including agriculture. Bacteria established the most significant consideration in the area of metallic NPs biosynthesis between many microorganisms. Bacteria have the unusual ability to mobilize and immobilize components, and in some cases, they can precipitate metals as small as nanometres. As a result, bacteria are referred to as bio-factories for manufacturing NMs such as silver, gold, palladium, titanium, magnetite, cadmium, and platinum. Bacterial enzymes are used in this procedure to catalyze a particular breakdown response and start producing NPs [57]. Polysaccharides, vitamins, enzymes, biodegradable polymers, and biological systems can all be used to create NPs. Extracellular secretion enzymes benefit by manufacturing many NMs ranging in size from 100 to 200 nm in pure form, free from other materials. Numerous metal NPs, including gold [58], nonmagnetic oxide [59], and ZnS [60], have been produced by various bacteria strains. The use of bacterial cells in the synthesis of NPs allows for a suitable controller of size [61]. These organisms tolerate heavy metals through various adaptations and decontamination methods and ion efflux by vigorous membrane channels. So many factors, like, alkalinity, temperature, incubation period, and substrate concentration, can influence the rate at which bacterial species synthesize NPs [61].
3.1.3.2 By Fungi
Myco-nanotechnology is a new term that refers to the production of NPs by fungi and their subsequent use. Fungi have several benefits over other microorganisms for NP synthesis, including being comparatively easy to separate, having much simpler downstream processing than bacterial fermentations, secreting huge volumes of extracellular enzymes, having an extensive range and diversity. Fungi produce more extracellular enzymes than bacteria, which has a more significant impact on NM synthesis. As opposed to bacteria, fungi can be used to make more NMs because they secrete more proteins, which subsequently increase the formation of NMs. The catalytic effect of enzymes produced by fungi during metal NP synthesis reduces salts to solid metallic NMs [62]. Fungi are generally regarded as the best source for NMs synthesis compared to other biological systems due to their ease of handling, low cost, and vast diversity.
3.1.3.3 By Plants
Plant-mediated biosynthetic pathway is a simple and low-cost method for producing NPs. Contamination makes it challenging to maintain and preserve a microbial culture. Plants could be used for this purpose to avoid the time-consuming steps of maintaining cell cultures. Plant-mediated biosynthesis is a simplified and appropriate process for making NPs on a large scale without contamination. Green NP synthesis refers to the creation of NPs from plant extract. It is currently gaining popularity due to the single-step involved in biosynthesis. As a result, it is a time-saving process with no toxicants and the availability of natural capping agents [63]. Plant material is widely existing, safe, and contains a wide range of chemical compounds. All these factors make plants preferable to other materials for NP synthesis. When compared to fungi and bacteria, phytochemicals require less time to reduce metal ions. It demonstrates that plant materials are a superior choice for the biosynthesis of NMs than bacteria and fungi. Plants are widely used in the medicinal sector for the synthesis of NPs. The choice of phytoconstituents extracts to synthesize NPs is also influenced by the source or origin of the biological matter. Plant extracts of leaves, stems, latex, roots used in green synthesis of NPs. Parts of the plant like root, stem, fruit, leaf, etc., are broadly used for green synthesis of NPs due to the high levels of phytoconstituents they yield [64]. The nature of leaf extracts and their concentration, temperature, pH, and interaction period have also influenced the rate of production and quantity of the NPs [65].
3.1.3.4 By Algae
Algae are also another significant class of living organisms that can be used in the efficient and environmentally friendly production of NMs. Heavy metals are thought to accumulate in algae, which could be used in the biologically active synthesis of metal NPs. Algae are autotrophic organisms that can thrive with only a few medium supplements. Algae cells contain various secondary metabolites and biologically dynamic composites that act as capping mediators throughout NP synthesis, transforming algal cells into a one-of-a-kind “nano-factory” for synthesizing several NPs [66]. The Chlorella vulgaris alga synthesizes NPs of various forms, including decahedral, icosahedral, and tetrahedral [67]. Numerous algae, including Kappaphycu salvarezii [68], Fucus vesiculosus [69], Tetraselmisko chinensis [70], Chondrus crispus, and Spirogyra insignis [71], were found to synthesize Ag and Au NPs. Algae is widely used for the green synthesis of several metallic and metal oxide NPs since they grow fast, are easy to handle, and their biomass growth rate is ten times faster than higher plants. To date, various algal species are studied for the green synthesis of different NPs.
3.1.3.5 By Viruses
Viruses hold excessive potential for accumulating and connecting nano-sized elements, permitting the development of organized NPs assemblies. Because of their small size, monodispersed nature, and wide range of chemical groups available for alteration, they serve as excellent support for molecular assemblage in nanoscale strategies. Because of their capacity to correlate into preferred structures with various morphologies, virus-based nanomaterials can be used as an engineering component to building smart nano-objects. Viruses are an ideal framework for the formation of nano-conjugates with noble metal NPs. Plant viruses and bacteriophages have recently gained popularity in nano-biotechnology due to their structural and chemical stabilization. The ease of manufacture, absence of toxicity, and pathogenicity in animals or humans [72] also play a key role. Viruses hold potential for gathering and linking nano-sized elements; as nanotechnology advances, such organized assemblies will interact with well-developed technologies such as lithography [73]. Viral NPs can be created by takeout viruses' genetic material and transforming them into “nano-cargoes.” The virus’s outer capsid protein serves a valuable purpose in synthesizing NPs by providing a susceptible surface that interrelates with metallic ions [74].
3.2 Synthesis
In recent times, there was a surge of attention in the synthesis of ecologically friendly NPs which do not generate hazardous sludge during manufacturing. It could be accomplished via biological synthesis methods with biotechnological practices deemed harmless and environmentally for NM production as a substitute for chemical and physical approaches. In the synthesis of NPs via the natural scheme, three main steps are followed: selecting a solvent medium, an eco-friendly reducing agent, and safety matter as a capping mediator to stabilize synthesized NPs [75]. Nanotechnology benefits over conventional tactics because of the accessibility of additional compounds by the biological organization for the development of NPs. The biodiversity of biological machinery has been investigated to synthesize eco-friendly NMs that can be used in various agricultural applications. Any NMs synthesis method aims to produce a material with properties that result from their characteristic length scale being in the nanometre range 1–100 nm. There are many synthesis methods reported in the literature, which are divided into two main groups, namely “Top Down” and “Bottom-Up” (Fig. 1).
Metal nanoparticles synthesis via the top-down and bottom-up method
3.2.1 Synthesis of NMs by Top-Down Method
The top-down synthesis produces NPs by reducing the size of a suitable starting content. Various physical and chemical treatments are used to reduce size. Top-down production approaches present flaws in the product's surface structure, which is a significant restriction since surface chemistry and additional physical characters of NPs are extremely dependent on it [76]. This method primarily employs solid and state handling of resources; it entails breaking down bulk material into minute elements via physical procedures like crushing, milling, and grinding. The main challenge of this procedure is the scarcity of surface structure, which influences the physical characteristics and surface chemistry of NMs. Furthermore, processed shapes suffer from significant crystallographic loss as a result of this method. Laser thinning [77], liquid exfoliation through mechanical strength [78], liquid exfoliation by oxidation [79], liquid exfoliation by ion intercalation [80], mechanical cleavage [81], selective etching [82], and ion exchange [83] are examples of top-down approaches.
3.2.2 Synthesis of NMs by Bottom-Up Method
Bottom-up approaches involve creating NPs from smaller components such as molecules and atoms that grow into nanoscopic particles using various chemical and biological methods. Bottom-up synthesis creates NPs from smaller entities, such as assembly atoms, molecules, and smaller elements. Bottom-up synthesis begins with forming nanostructured building blocks for NPs, which accumulated to yield the final part [76]. Raw materials used in these methods can be in the form of liquids, solids, or gases. NMs can be prepared molecule by molecule or atom by atom in this method to produce a large quantity. This method is more commonly used to create the majority of NMs. This method is capable of producing NMs with uniform size, shape, and distribution. It precisely controls the chemical synthesis process to avoid unwanted particle progress. This system is critical in constructing and processing NMs with improved particle dimension supply and morphology and an environmentally friendly and cost-effective approach for producing NPs. Combustion synthesis [84], gas-phase methods [85], hydrothermal synthesis [86], microwave synthesis, and sol-gel processing are just a few of the methods used to create NMs.
4 Nano-based Essential Metals
Metal NPs can be designed and synthesized through diverse functional groups, like DNA, antibodies, peptides, RNA, and prospective biocompatible polymers, such as polyethylene glycol [87]. This metal group includes NPs made of Zn, Cu, Fe, Mn, and their oxides. Zn and ZnO NPs are derived and used in many agricultural practices.
4.1 Zinc Based
Zinc is a core element of many enzymes, including alcohol dehydrogenase RNA polymerase, superoxide dismutase, and carbonic anhydrase. It also helps in chlorophyll synthesis. Zn NPs have been used as a nano-fertilizer on various crops, with positive results in optimal concentrations. Zinc NPs are metal particles that are spherical and have a large surface area. ZnO NP is also visible in agricultural sprayers as an ultraviolet ray’s safeguard material [88]. ZnO contributes to protecting photosensitive pesticides in conjunction with an organic filter and is used straight for crop protection against crop protection UV radiation [89]. ZnO NPs revealed positive impacts on germination, phosphorus uptake and mobilizing enzymes, stem and root growth, and showed antifungal activities. Several studies reported that nano-Zn prevents bacterial infection [90], fungal infections [91, 92], and nematode infection [93]. Several laboratories have investigated the antagonistic activity of Zn NP against plant pathogens in the same way that Ag and Cu have [90, 92, 94].
4.2 Copper Based
Cu has long been known to inhibit fungi spore germination, but a large amount of copper is required to achieve this effect. Cu is a constituent of several plant enzymes and is also needed for plant development. According to [95] Cu NPs have antibacterial action against gram-positive and gram harmful bacteria, and are also used as a fungicide. Some researchers [96] investigated the antifungal efficacy of a Cu polymer nanocomposite against phytopathogens. Because of Cu's well-known antimicrobial properties and long record of controlling diseases in plants, nano-Cu is a rational option for plant protection. Compared to the product with cupric hydroxide, Cu NPs increase efficacy against pathogenic fungus [88]. CuO NPs were found to increase ROS (Reaction Oxygen Species) production in plants [97]. Instead, various antioxidant substances have improved in plants when treated with NP, representing that plants' protective mechanisms have been activated [97]. CuO NPs were found to reduce photosynthetic action by neutralizing PS II reaction centers [98].
4.3 Carbon Based
According to some studies, carbon-based NMs are excellent components for enhanced plant yield quality as fertilizers and products for plant protection such as pesticides and herbicides. Their connection and impacts, however, will be determined by the characteristics of the plant and NM. Carbon-based NM can boost ROS generation [99], and they can pass through different types of cells depending on their size. Carbon is an essential component of lipids, proteins, and carbohydrates. Plants use CO2 to make food and O2 by transforming sunlight through photosynthetic activity. A variety of carbon-based NPs, namely, single-walled carbon nanotubes (SWCNT), double-walled carbon nanotubes (DWCNT), and multi-walled carbon nanotubes (MWCNT), and fullerenes) have been tested in precision agriculture and were found to be effective in seed germination and plant growth. Carbon-based NPs have both advantages and disadvantages in terms of seed and seedling germination [100]. According to [101], the use of SWCNT can improve the germination of barley, rice, tomato, soybean, maize, and tobacco.
Furthermore, the usage of MWCNTs aided in the uptake of water by tomato seeds after rapid germination [102]. Again, some researchers [103] found that MWCNT can trigger a stress-related gene in tomatoes, causing improved seed germination. Carbon NMs have recently been shown to have antibacterial and antifungal activities and positive effects on plant growth [104].
4.4 Manganese Based
Mn is considered as a micronutrient required for plant growth. It is essential for both direct and indirect oxygenic photosynthesis. Plant nutritional disorders are the most severe consequences of manganese deficiency. [105] also demonstrated that MgO NPs efficiently inhibited R. solanacearum, which caused bacterial wilt in tobacco. Physical damage to cell membranes and ROS accumulation were proposed as mechanisms. [106] synthesized magnesium hydroxide NPs and compared their antimicrobial effects to marketable pesticides such as Kocide 3000, which contains copper hydroxide. Pseudomonas syringae, Xanthomonas alfalfae, and E. coli are all inhibited by magnesium hydroxide NPs. [107] created MgO NPs and investigated their antibacterial properties. On tomatoes, researchers confirmed that MgO NPs increased systemic resistance against Ralstonia solanacearum. They also discovered that MgO-treated roots generate ROS rapidly, upregulation of PR1, ethylene, jasmonic acid, and systemic resistance-associated genes [50].
4.5 Titanium Based
Photochemically active TiO2 NPs have antimicrobial activities; they have agricultural significance as nano-pesticides. TiO2 NPs also revealed an excellent correlation with plant enzymatic activity, promoting crop growth when exposed to sunlight; they enhance photosynthetic action. [108] discovered that photocatalytic TiO2 NPs have antibacterial activity against Xanthomonas perforans (a pathogen that causes spot disease in tomato). Nano-photocatalytic TiO2 actions may contribute to its antifungal action. [108] synthesized TiO2/Zn NPs to prevent Xanthomonas sp. that cause bacterial leaf spot on rose. Researchers [109] reported that nano-TiO2 showed high antifungal activity. TiO2 NP exposure improved chlorophyll content and biomass by activating antioxidant enzyme, after lower hydrogen peroxide and malondialdehyde levels, increased generation of soluble sugars and proline, thereby sustaining osmotic balance [110]. TiO2 can increase plant hydration by enhancing the action of the nitrate reductase (NR) enzyme, which increases osmolyte gathering. Increased NR enzyme activity results in the production of nitric oxide, which induces the synthesis of glycine betaine and proline [111]. TiO2 NPs had enzymatic as well as nonenzymatic stress defense schemes in plants. Another study on medicinal herbs [112] discovered that providing salicylic acid, methyl jasmonate, and TiO2 NPs alleviated drought stress. The foliar application of TiO2 NP resulted in improved plant growth, increased fruit yield, and chlorophyll content in tomatoes [113].
4.6 Silver Based
Because of their historically known antimicrobial action, Ag NPs were investigated for managing plant diseases. Ag NPs have received much consideration as a potential nano-pesticide in agriculture due to their broad spectral range of antibacterial efficacy. Furthermore, Ag NPs are found to be effective against nematodes, a common soil-borne pathogen. Several metabolites found in plants or bacteria act as reducing and capping mediators during the fabrication of Ag NPs. [114] green-synthesized Ag NPs from turnip leaf extract demonstrated antifungal potential against some wood-degrading fungi, including Chaetomium globosum, Phanerochaete sordida, Gloeophyllum abietinum, and G. trabeum. Plant pathogens like F. culmorum, Phythium ultimum, R. solani, Biploaris sorokiniana, B. cinerea, Colletotrichum gloeosporioides, Magnaporthe grisea, Scalerotinia sclerotiorum, and Magnaporthe grisea are reported to be controlled by Ag NPs [115, 116]. [115] studied the impact of biologically synthesized Ag NPs against Candida albicans, Trichoderma sp., and Phoma glomerata. Plant growth was enhanced using Ag NP of 200–800 nm size [117], whereas Ag NP of 35–40 nm positively influenced several crops’ growth [117]. According to recent research, when Ag NP is combined with different composites, diverse influence on plants is reported [118]. Ag NP has also been evaluated as fungicidal activity, and their significant impact was observed [119]. However, their usage in agriculture is still debatable because Ag NP is known to release silver ions as it ages, and they can also affect biomass accumulation [120].
4.7 Silicon Based
Silicon (Si) is the second most common element in the earth after oxygen and is regarded as a nonessential component for plants; if present, plants can benefit adequately. Si NPs interact with plants directly or indirectly, causing morphological and physiological alterations that deliver stress tolerance. They promote the growth of plants, increase biomass, physiology, and anatomy, alter tissue diversity, stimulate defense schemes, and aid in acclimatization to environmental stresses [121]. Si NPs exhibited anti-stress properties against drought stress in Crataegus sp. at several concentrations; the diverse responses in seedlings depend upon concentrations. Among these effects are increased photosynthetic capacity, membrane electrolyte leakage, water content, more levels of proline, carotenoids, and chlorophylls [122]. Furthermore, under salinity stress, SiO2 NPs increased water use efficiency, transpiration proportion, stomatal conductance, and decreased chlorophyll degradation [123]. Silica [124] also helped the expansion of diseased plants’ stress resistance ability.
4.8 Other Metal Based
Iron (Fe) NP represents an emerging generation of ecological remediation machinery that can deliver cost-effective resolutions to some problematic matters. Iron oxide (Fe2O3) NPs could be used in place of Fe fertilizers in agriculture. [125] investigated efficacy of Fe2O3 NPs as fertilizer to replace traditional Fe fertilizers. In another study, Fe2O3 NPs after foliar spray had a significant impact on the yield of Vigna unguiculata, Fe content in leaf, stability of plasma membrane, and chlorophyll content [126]. According to [127], Fe NP for wheat seed treatment can enhance germination frequency and shoot and root length. Lower concentrations of Fe2O3 NP have helped plants and improved germination [128]. Some researchers [129] observed an increase in germination and root length percentage in rice seeds treated with silica and molybdenum (Mo) NP. Researchers [53] recently designed a greenhouse assay to examine cerium oxide (CeO2) NP-mediated Fusarium wilt suppression in tomatoes. Experiments in the field and on the soil with wheat and rice revealed that the use of CeO2 NP reduced grain quality [130]. Molybdenum (Mo) NP is a significant component of the nitrogen fixation scheme in plants. Researchers [131] found that applying Mo NP to chickpea seedlings increased growth by two 2-3 times. According to researchers [132], gold (Au) NP used for seed treatment of maize positively affects germination and increases seed quality parameters. [133] produced nano-Au from the extract of lady’s finger and demonstrated its antifungal activity against Candida albicans, Aspergillus niger, A. flavus, and Puccinia graminis. In vitro data presented by [134] showed that nano-sulfur inhibits Venturia inaequalis and Fusarium solani. Without affecting photosynthetic activity at low concentrations, cadmium oxide (CdO) NPs enhanced amino acid production [135].
5 Mechanism of Nanomaterial Uptake, Translocation, and Action
Plants are exposed to NPs through two routes: foliar and root exposure. The cuticle is thought to be primarily a physical border against NPs entering, since the waxy cuticle protects the leaves of higher plants from water loss and uncontrolled exchange of other solutes [136]. The bioavailability and toxicity of NPs are determined by a series of bio/geo-transformations in soil. Subsequently interacting with plant roots, NPs translocate to the aerial side and collect in cellular or subcellular organelles. The initial step in accumulation is the adsorption of NPs from the soil through roots. The size of NP is directly related to its absorption as it is an important factor that permits it to enter via cell wall pore spaces or stomata. Small NPs have been observed to pierce plant roots via capillary forces, osmotic pressure, or directly by root epidermal cells [137]. Epidermal cells of the root are semipermeable and comprise minor pores, limiting the passage of large NPs. Nano-pores aid foliar entry in leaves, which facilitate NP uptake and transport within leaves. Aquaporins have been proposed as NMs transporters inside the cell [138]; however, their minor pore diameter, varying between 2.8 and 3.4 A° [139], marks them unlikely as NP penetration frequencies [140]. NMs can also enter cells via plasmodesmata, which are particular structures transporting materials between cells [141]. The uptake of NP by plants is influenced by numerous factors related to NP nature, plant physiology, and NM interaction with the environment. The properties of NP will significantly impact their behavior and, as a result, whether or not plants will absorb them. Size appears to be among the most significant barriers to penetration into plant tissues. Some reports have been on maximum dimensions that allow NP to move and accumulate inside cells, with 40–50 nm as a size exclusion limit [142]. Furthermore, the type of NP and its chemical composition impact uptake [138], and morphology is determinant in several conditions [143]. The functionalization and coating of NM surfaces can substantially modify and affect NM absorption and accumulation properties by plants [144]. Furthermore, the occurrence of other organisms like fungi and bacteria affects the uptake of NPs by plants, particularly if those microorganisms form symbiotic relationships with plants, as mycorrhizal fungi do [145]. Prospective strategies must be developed for tracking NMs inside plants; additionally, more critical data is required to measure uptake and translocation of NPs within plants and as discharge in the environment. The uptake and dispersal of TiO2 NPs studied in rice plants and found that NPs transported long distances via the vascular scheme. Photosynthate, sugars, and macromolecules have conventionally been able to transport downward to shoots and roots by phloem system [146]. Overall, long-distance liquid transportation in higher plants happens via the vascular system, consisting of the xylem and phloem. Flow direction in the xylem system is from bottom to top (from root to shoot), whereas flow direction in the phloem system is from top to bottom (from shoot to root). The whole plant's vascular scheme is noncirculatory, representing substances moving downward in phloem that do not return to their original locations via xylem [146]. Once inside the plant, NPs can move through two types of pathways: apoplast and symplast. Apoplastic transportation occurs in the outer plasma membrane via extracellular places, cell walls of neighboring cells, and xylem vessels [147]. In contrast, symplastic transport occurs within the cytoplasm of adjacent cells via specific structures known as plasmodesmata [141] and sieve plates. The apoplastic process is essential for radial mobility within plant tissues because it enables NMs to attain the central cylinder of root and vascular tissues. They can move upwards to the aerial part [148]. NPs can move through the xylem to the aerial part of the central cylinder by subsequent transpiration stream [148, 149]. Significant symplastic transport is also possible, utilizing sieve tube components in phloem and permitting dispersion to nonphotosynthetic tissues and organs [143]. In the scenario of foliar spray, NMs must pass through the cuticle barrier, either via lipophilic or hydrophilic way [150, 151]. Since the diameter of cuticular pores is approximated to be about 2 nm [151], the stomatal pathway has seemed to be the best possible path for NPs penetration, with the size limit of 10 nm or greater [152]. The movement of NMs within plants is critical because it can indicate which plant parts they could attain and wherever they may accumulate. For instance, NPs transported primarily via xylem rather than phloem, most possibly move from root to shoot and leaves rather than downwards, so applied to roots to ensure good distribution in the plant. On the opposite, foliar spraying must be used if NPs show significant translocation by phloem. Furthermore, NMs trying to move along phloem are likely to acquire plant organs that act as sinks. Though translocation is not always limited to a single cell type, lateral movement of NMs among xylem and phloem is possible. The features and nature of NMs and plant types had an important effect on translocation and gathering in plant tissues. For instance, variances in translocation and accumulation of the same NP were observed in diverse plant species, so even small alterations in analogous NMs lead to altered outcomes within the same plant [153].
Nanoscience is a new scientific innovation platform that entails the progress of strategies to various low-cost applications and is helpful to improve the growth and development of plants. In this regard, numerous research shows that the use of NMs had a positive effect on germination and plant growth. Still, fundamental mechanisms by which NMs can stimulate germination remain unknown. The application of nano-SiO2 and -TiO2 encourages the germination of seeds [154]. Research has shown that NMs can pierce seed coats and improve water absorption and consumption, regulate enzymatic scheme as a result, and increase germination and seedling growth [155]. NMs like ZnO, TiO2, MWCNTs, FeO, Zn, Fe, CuO, and hydroxy-fullerenes also shown to enhance the growth and development of crops while improving crop quality in a variety of crops such as mustard, peanut, potato, tomato, spinach, onion, wheat, soybean, and mung bean [156, 157]. Although the exact mechanism underlying the improvement of plant growth is unknown, it might be clarified that NMs absorb more nutrients and water, which supports the vigor of root systems through improved enzymatic action [156]. TiO2 NMs promote plant growth by enhancing photosynthesis and nitrogen (N2) metabolism [158]. Plant contact with NMs caused excitation of genes associated with water channel protein and for better cell growth by regulating cell cycle; these impacts of NMs are reflected in the form of enhanced seed germination and plant growth [159]. Treated plants with NMs are more resistant to abiotic stresses, and these treated plants have higher photosynthesis rate, transpiration activity, water use efficiency, chlorophyll (Chl), proline content, stomatal conductance, and high concentrations of carbonic anhydrase action [123, 160]. NPs could mitigate damaging photosynthesis, which is caused by Ultraviolet-B (UV-B) radiations. NPs also improve photosynthesis by preventing oxidative stress, increasing Chl synthesis, Rubisco activity, energy transformation, and light absorbance [161, 162]. Plants are protected against different abiotic stresses by NMs, which stimulate antioxidant enzymes' actions and gather free amino acids, nutrients, and osmolytes. Mesoporous Si NPs enhance photosynthesis by interacting with chloroplasts, resultant in enhanced chlorophyll content, total protein, and seed germination. Interaction, translocation, and mechanism induced by NPs in plants are given in (Fig. 2).
Interaction, translocation, and mechanism induced by nanoparticles in plants
6 Nanomaterials Interaction and Physiochemical Response of Plants
With the development of nanotechnology, more effective and contaminant-free nano-formulations for sustainable farming are being developed regularly. The uptake of NMs within plants is heavily influenced by the chemical properties, size and functional groups, and coating type. Interaction and uptake of NMs cause molecular deviations that affect plant physiology [163]. Adsorption on the root surface, integration into the cell wall, and cell uptake are all potential interactions of NPs with plant roots [164]. Furthermore, knowledge of the interaction of NMs with plants, whether negative or positive, is mandatory for the controlled delivery of bioactive substances. The potential of NMs to pierce tough coating of seeds and permit water import determines increased growth and vigor. The NPs transported to various parts of the plant and interact with cellular mechanisms, stimulating the growth of plants. NMs can essentially be applied to either root or vegetable parts of plants, preferentially leaves. NPs can be passively taken up at shooting surfaces via natural plant openings like stomata and hydathodes. [165]. NPs availability may be influenced by symbiotic relationships between organisms, soil organic matter, and mucilage and exudates. To better understand the dynamics of NPs-plant connections, plant anatomical, and physiological characteristics must be measured. Damages and injuries in plants' aerial and hypogeal parts also serve as feasible for NPs internalization [166]. In the root, rhizodermis lateral root may allow easy entry of NMs, particularly close root tip, whereas the upper portions are impermeable due to the presence of suberin [167]. Root mucilage and exudates, e.g., which are generally excreted in the rhizosphere, play two roles: firstly, they promote NP adhesion to the root's surface and may enhance NP internalization proportion. Secondly, these jelly components also stimulate NP absorption and accumulation [168]. The rate of NPs accumulation by roots of plant is influenced by NPs’ properties and ecological factors.
NPs gain entry plants through a variety of ways, most common of which are roots and leaves. Different NPs have been shown to encourage the germination of seeds, development, and growth [169]. The mechanism by which NPs application increase germination of seeds remains unknown. Treatments with NPs increase seed absorption and moisture holding, which enhance the germination of seeds [170]. NPs have been shown to benefit crop plants in the following ways: improve metabolites compounds [171], enhanced root and shoot measurement [172], increased production of fruits, and significantly increased seedlings and vegetative biomass of several crops. Likewise, the impact of NPs on various biochemical parameters such as improved N2 efficacy and enhanced photosynthetic activity in some chief crops, including soybeans [173], peanuts [174]. NPs are also well-recognized for increasing nutrient consumption and resistance to plants against several diseases and abiotic stresses [175]. NPs can influence plant growth and development by altering a few physiological processes in plants. Numerous studies show that foliar application of metal NPs significantly increases chlorophyll content, allowing them to absorb extra light energy and improve photosynthesis. SiO2 NP treatments significantly increased photosynthesis rate due to higher action of carbonic anhydrase and photosynthetic pigment synthesis [176]. Many research indicates that NPs caused toxicity above specific concentrations, and plant toxicity evaluated their effect on germination percentage and biomass production [177]. Zn has been used as a cofactor in some enzymes, including catalase & superoxide dismutase, and protects plant cells from oxidative damage [143]. We have summarized some physiological responses of various metal nanoparticles on different host crops in tabular form (Table 3).
7 Toxicological Impact and Health Hazards in Agriculture
Diverse research has also found that the use of metals and metal oxides in the synthesis of nano-fertilizers and nano-pesticides had adverse and toxic effects on plants and the environment. Metal, metal oxide, and synthetic polymers have been discovered to be nonbiocompatible, nondegradable, and harmful at various concentrations, raising serious concerns about the utilization of nanotechnology in agriculture. NMs persist in the environment, and their concentration rises as a result of their nano-size, according to researchers. Excess amounts of NMs are toxic to people, nontargeted lifeforms, and affect climate. NPs accumulation in plants can modify physiological activities. In specific scenarios, reductions in photosystem quantum yield and transpiration were also detected [206]. According to a series of studies, NPs can affect crops by minimizing germination of seeds, reducing shoot and root length, varying photosynthesis, inducing oxidative stress, antioxidants, and balancing the nutritional substance of eatable crops and yield [206, 207]. Deposition of NPs in plant tissues may also harm protein, lipid, and nucleic acid content via hydroxyl radicals [208]. NMs promote plant growth and productivity while protecting against biotic and abiotic stresses.
On the other hand, NMs cause cytotoxicity and genotoxicity in plants [209]. It prominently diminished biochemical and physiological activities [210], growth [211], and compact nutritive worth of crops [212]. Toxic effects of NMs on plants are primarily determined by the size, concentration, and chemistry of the NMs and the chemical properties of subcellular where NMs deposited [213]. NPs larger than cell wall pore size stick to epithelial root cells caused mechanical damages of cells [214], blocking pores, and reducing hydraulic conductivity, resulting in decreased water uptake and nutrient acquisition capability [215]. The direct interaction of NPs with the cell surface and cellular membranes induces mechanical interruption and impacts the integrity and role of the cell membrane and walls [216]. NP accumulation leads to the decline of the PSII reaction center, modification of O2 evolving complex, downregulation of electron transport and chlorophyll composition [217], a smaller proportion of thylakoids, lower transpiration, stomatal conductance, CO2 absorption, and photosynthetic pigments [98]. Understanding NM toxicity in crops is still in its early stages but critical for developing innovative nanotools and functions. With the rapid evolution of nanotechnology, there is apprehension about the accumulation of NMs and their potential entrance into the food chain [218]. Conventional foods have various NMs, but the use of many engineered NMs in water, agriculture, and food may pose hazards for human service, usage, the atmosphere, or all of them. Furthermore, a category of NPs are found to be toxic to plants by retarding germination and root elongation. Phytotoxicity of NPs is connected with the discharge of lethal elements from NPs, generating radicals via NPs interaction with plant or environment.
8 Concluding Remarks and Future Directions
Considering the significant challenges we will be facing, mainly due to a growing worldwide population and climate change, the application of NMs in agriculture can potentially contribute as a unique carrier in agricultural practices. According to data gathered, the influence of NPs differs from plant to plant and is dependent on the mechanism of application, size, morphology, and concentrations. Nanotechnology seems to have the ability to change pest management technologies and provide solutions for agricultural applications. A piece of complete knowledge about properties of NMs like morphology, functional groups, and size serves as a beneficial preliminary fact for selecting appropriate NMs. Agricultural nanotechnology is encouraging options for the emerging quality output, which are being discovered. A few specific areas of agricultural nanotechnology research may require additional attention shortly: (1) New eco-friendly and reliable delivery methods for specific food/feed substances, plant nutrients, and so on, (2) Nanotechnology-related (bio)sensors play a vital role in controlling pests and agricultural food products, (3) The characterizations of NMs should be closely reviewed, and (4) Nano-toxicity is critical with fertilizers; ideal dose estimation should also be inspected.
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Khan, A., Ahmad, F. (2022). Nanomaterials as Unique Carriers in Agricultural Practices for Plant Growth and Development: A State of Current Knowledge. In: Chen, JT. (eds) Plant and Nanoparticles. Springer, Singapore. https://doi.org/10.1007/978-981-19-2503-0_11
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