Introduction
Nanoparticles ranging from 1 to 100 nm are very minute particles and follows the principles of quantum physics. For example, a nanoparticle will exhibit various electrical and optical properties at different scales i.e. at nanoscale and macroscale levels. The study of such minute particles behaviour in the nanoscale (typically between 1 to 100 nanometre) and their application is nanoscience. The technology that develops from the study of nanoscience leads to nanotechnology which are commercially employed in the welfare of humans.[1].
Nanotechnology offers advanced research in the field of agriculture, energy, and life sciences, biotechnology, electronics, medicine and various branches of natural sciences and applied in the production of chemical sensors, cleaning water, prevention of diseases, reproductive science and treatment of plants using nanocides [2].
Fertilisers are a basic requirement for the growth of plants, but most of them are not available to the plants due to factors like draining off of the fertilisers, hydrolysis, photolysis and decomposition. Thus, nanomaterials and nanotechnology in this matter can minimize the losses in agriculture like nutritional loss and enhance yield production as well by using nanofertilisers and nanocapsulated nutrients. These nanofertilisers can release nutrients when required and regulate growth and enhance target activity [3].
Nanoparticles (Properties)
Nanoparticles despite of their small size has a larger surface area with respect to their volume but with significantly small size (in nanometres) allowing them to absorb more solar radiation [4]. Nanoparticles are also used in the food packaging industry for the control of spoilage of food and prevent the occurrence of disease causing organisms. They lessen the entry of moistures and inhibit the transport of gas [5]. Nanoparticles possess physical properties that shows great potential in medical science like diagnosis of diseases (cancer, Alzheimer’s, etc), transport of drugs, and targeted imaging. They can easily penetrate and enter cells, enhancing organ and tumour images. Their anti-inflammatory properties also aid in cell apoptosis [6,7]. Nanoparticles, with their strong, tough, and ductile properties, are used as spark plugs in automobiles coated with nanocrystalline ceramics like zirconia and alumina for efficient fuel combustion [8]. Nanoparticles because of their small size shows interesting optical properties and produces unexpected quantum effects [9]. This was observed in gold nanoparticles which appeared deep reddish but turns black in solution. Conductivity is the electron’s property in solids, while resistivity is its inverse. Metals have low resistivity, while nanosized grains generally have high resistivity due to electron scattering [10].
Classification
Nanoparticles are classified into two parts: Organic nanoparticles and inorganic nanoparticles.
Organic nanoparticles
Organic nanoparticles are known to have small size and show unique properties, that attracts a lot of researchers in the area of material and life sciences. They are utilized in bioanalysis, basic science, sensor applications, drug delivery and more. In nanotechnology, nanomaterials are used in electronic circuits, molecular switches, biosensors and nanosized microchips and in medical sector, nanoparticles are used on disease treatment, diagnosis and targeted delivery of pharmaceuticals. Biopolymer nanoparticles are one such particles which are developed for drug delivery and much more advantageous as they are easy to prepare from polymers that are biodegradable and highly stable in biological fluids. Biopolymer nanoparticles are further used in immunoassays and devices of drug delivery as they are nondegradable polymer overloading and pose very less risk of chronic toxicity [11].
Inorganic nanoparticles
Inorganic nanoparticles are non-toxic, biocompatible with living systems and are hydrophilic in nature. Magnetic nanoparticles (mNPs) with a magnetic core like maghemite or magnetite are significant inorganic nanomaterials. Along with it, other metals like nickel and cobalt are also used, but they are less utilized due to toxicity and oxidation vulnerability. Iron oxide nanoparticles help in the digestion of irons and restore the iron supply in the human body. These cationic mNPs are continuously present in endosomes for a long time, and during post cellular absorption, the elements like iron and oxygen are brought into the storage of body. In human body, haemostasis maintains the iron levels through adsorption, excretion and storage which helps in the digestion of excess irons which are essential for tissues but has very less bioavailability [12]. Inorganic nanoparticles consist of metal nanoparticles such as Au, Pd, Ag and Pt, magnetic nanoparticles and semi-conductor nanoparticles (TiO2, SiO2, ZnO2).
Synthesis of nanoparticles
The synthesis of nanoparticles involves two processes: top-down and bottom-up approach. The Conventional methods are expensive and environmentally unfriendly, using toxic chemicals. Green chemistry and bioprocesses, often uses naturally occurring elements like sugars, vitamins, extracts of plants, polymers which are biodegradable and microorganisms for greener synthesis. Plant parts, with polyphenols as key active agents, are used for metal nanoparticle synthesis. Nowadays mycosynthesis of nanoparticles are also widely used for green synthesis of nanoparticles [13].
Biobased nanoparticles
Biobased nanoparticles obtained from natural sources like plants, animals and microbes are now widely used due to their exclusive properties and advantages over chemically based nanoparticles. The biobased nanoparticles are a sustainable alternative which reduces the dependence on fossil fuels, and are biocompatible, due to which they are used for applications in the medicinal industry like drug delivery systems and imaging agents. They can be modified through surface functionalization or encapsulation techniques, and their production is cost-effective due to readily available raw materials [14].
Hazardous chemicals and energy-intensive procedures that increase pollution and carbon emissions are often used in the synthesis of nanoparticles based on chemicals. On the other hand, because they employ natural resources and need less energy, biobased nanoparticle production techniques often have smaller environmental impacts. Because biobased nanoparticles are similar to traditional materials used in sectors like electronics, textiles, and cosmetics, they can be incorporated into current manufacturing processes without causing major changes or interruptions [15]. All things considered, the sustainability, biocompatibility, low toxicity profile, adaptability, affordability, improved functioning, less environmental impact, and compatibility with current technology are what make biobased nanoparticles significant. These benefits are essential for the sustainability of the environment and issues related to the health associated with chemical-based alternatives, making them attractive options for a broad range of applications across different industries [16].
Use of Nanoparticles in the growth and development of plants
Nanoparticles significantly impact a plant’s metabolic pathway which has different beneficial results such as disease resistance, high yield and better growth [17, 18] (Figure 1). Silicon among different nanoparticles improves resistance ability of plants. This can help in severe situation like droughts [19], nutrient imbalances, metal toxicity, radiation and high amounts of salinity [20,21]. Silicon dioxide also known as silica (SiO2) with a low concentration (about 10 and 20 ppm) significantly increase the success of germination. This was seen in Sorghum bicolor [22]. Seedlings of Vigna radiata exposed to SiO2 NPs of various concentrations [23, 24]. The inoculated seedlings showed increased root weight, shoot weight, biomass of plants and height of plants.
Zinc oxide is another significant NPs that induces growth of plants and overall development. The deficiency in this NP can significantly impact the growth. ZnO is a semiconductor which is n type metal oxide that have pyroelectric and piezoelectric properties. It was reported that spraying ZnO NPs in plants in which Rhizobium is absent improved the growth, number of pods, photosynthetic pigment content and nitrogen reductase activity [25]. Similar results were observed in eggplants under greenhouse conditions. NPs at a specific concentration promoted plant growth, the weight of fruits and the development of crop. It also increased the yield of fruits and accumulation of biomass as compared to ZnSO4 treatments on habanero pepper. It was observed that the yield was improved, with better quality and nutraceutical properties of fruits [24].
The effect of Gold NP was studied on Brassica juncea which resulted in increased stem height and diameter, with that there were increase numbers of leaves and shoots, and improved productivity which signified increased yield [26]. A similar study was conducted in a rhizome extract of Alpinia galanga (L.) Willd. plant at room temperature [27]. The initiative promotes green nanotechnology in agriculture, showing that gold nanoparticles can activate maize germination and early growth, and enhance seedlings’ physiological and biochemical properties. This non-priming agent has potential for naturally aged crop seeds [28].
Silver nanoparticles have also been reported to accelerate the growth and development in treated seedlings. It was reported that the treated seedlings of Boswellia ovalifoliolata with silver nanoparticles accelerated the germination of seeds and growth of the seedlings [29]. Similar observations were made on seeds of Asparagus officinalis L. when exposed to silver nanoparticles [30]. The results showed that the seedlings treated with silver NPs had more ascorbic acid and chlorophyll.The addition of silver NPs to the nutrient medium significantly decreased seed germination, decreased the formation of nodules and the growth of shoots, and reduced root length which was observed in Vicia faba L. [31]. In hydroponic culture, the seed germination in Solanum lycopersicum L. [32] and in Raphanus sativus L. [33] was not affected by silver NPs, but it affected root and shoot length and photosynthetic activity which was slightly reduced. Additionally, the exposure of the microalga Skeletonema costatum Grev. to silver NPs decreased cell viability and chlorophyll content because of reactive oxygen species present [34].
Titanium dioxide nanoparticles, due to their unique physicochemical properties are used in the growth experiments of plants. Titanium dioxide nanopartciles are known to increase salt tolerance in barley [35]. Similar studies on Thymus vulgaris were conducted in which the effect of TiO2 NPs under stress of water-deficient stress was studied [36].
The result of research showed that the spraying TiO2 NPs on thyme increased growth characteristics. A study on Coriander (Coriandrum sativum L.) [37] of the effect of TiO2 NPs concluded that the nanoparticles led to significant increase in height of plants, yield of fruits and number of branches. It also led to an increase in biochemical content, total indoles and pigments.
Recently research on the toxicity of TiO2 NPs have gained significant importance. The effects of different concentrations of TiO2 NPs on the growth of mulberry seedlings (Morus Alba L.) using transcriptomics and metabolomics approaches were reported [38]. The research showed that exposure to TiO2 nanoparticles resulted in the damage of the plant. Moreover, it also reduced the number of chloroplast and pigment concentrations. The authors concluded that the TiO2 NPs should be monitored comprehensively to avoid the potential risk of NPs on plants because of its toxicity. Similar findings were concluded on Halophila stipulacea were also reported [39].
Carbon nanotubes (CNTs) are graphene sheets rolled up into cylinders with diameters as small as one nanometre [40]. CNTs play a vital role in the early stage of plant growth. This was observed in Brassica juncae and Phaseolus mungo [41]. Both the sample showed 100 percent germination and growth of seedlings. Especially Brassica juncea seedlings which showed increased vegetative biomass at different CNT concentrations [42, 43]. Multi-walled carbon nanotubes (MWCNTs) have also shown to increase water uptake by activating gene expression of encoding gene water channel protein (LeAqp1) [43,44]. Moreover, CNTs have gained significance as a plant growth regulator on two times yield of tomato with regular soil than control. It has been also reported that CNTs influence the cell walls of tomato seed coats and hence stimulate growth of the seedling [45,46].
Nanoparticles in Agriculture
Before in the agriculture system, farmers used to used chemicals such as pesticides, fungicides and herbicides to control pests and diseases. This in turn causes water pollution, soil pollution, air pollution [47]. The chemicals used are very harmful to both human health and disrupts the ecological balance [48]. It affects sustainability. The main objective of the above-mentioned chemicals is to increase the yield but often negates the said effects by ultimately harming the benefactors in return by causing soil contamination and nutritional stress [49]. While some greener approaches have been taken to ensure better disease prevention and pest control, the market today is still heavily dependent on harmful agents. Nano scale chemicals with green synthesis maybe a solution to this problem. The production of pesticides and chemical fertilisers using nanoparticles and nano capsules can decrease the environmental pollution through a greener approach. Although the modern chemical agents are effective, but it can reach its target site only 10% from its given concentration. So, to increase the efficiency of agent’s multiple doses are given increasing the use of chemicals on the soil leading to soil degradation [50]. There are various ways in which nanoformulations can be used in agriculture (Figure 2).
Nanofertilisers is another aspect of application of nanoparticles, which offers lower dosage and high returns as it enhances crop growth and quality. This was seen extensively in the reports from Merghany et al (2019) [51] and Babu et al. (2022) [52]. In the former case study, the effects of nanoparticles as fertilisers in the yield of cucumber was studied [51]. The treatment of NPK fertilisers increase the yield by 4.84% and 53.42%, respectively in first and second seasons. Similar conclusions were observed when the use of nano fertilisers against traditional chemical fertilisers were studied [52]. Nanofertilisers are nutrients encapsulated or coated within nanomaterials which slowly diffuse into the soil. They minimize the loss of nutrients, reduce degradation of soil, and enhances the fertility of soil, promoting productivity of crops. They also reduce environmental hazards and increase crop yield by helping in germination of seeds, nitrogen metabolism, photosynthesis, protein and carbohydrate synthesis, and stress tolerance. Nanofertilisers are easier to apply and transport, as they are provided in smaller quantities, enhancing ease of application and transportation costs [53].
Traditional fertilisers have low uptake efficiencies and rapid chemical changes, negatively impacting soil and the environment. They maintain fertility of soil and improve crop yield and can be applied directly or through foliar methods. Nanomaterials like silver, gold, aluminium, and magnetised iron NPs have high receptivity, allowing plants to effectively absorb nutrients. The efficiency of nanofertilisers depends on intrinsic and extrinsic factors in crops, and their absorption through roots and leaves influences their behaviour and bioavailability. Nanofertilisers should be synthesized according to crop needs, and biosensors added to control nutrient supply [53].
Nanopesticides are pesticides that are made from nanomaterials. Nanopesticides are a great way to explore pesticide activities in noncarrier innovative formulation that are based on several materials like silica, copolymers, polymers, lipids, ceramic, metal carbon and others [54]. Nanopesticides enhance water solubility and bioavailability, but they also pose toxicity in the cells and the genes. The undiscerning use of these pesticides can cause threat to the ecosystems and pose risk to human health, especially children. A thorough assessment of their activity and toxicity is crucial for safe and sustainable agriculture development. Their biomimetic properties and high bioaccumulation ability can cause various diseases [55]. Nano pesticides are classified into two types in which (a) base is metal and other in which (b) materials contain AIs enclosed with nanocarriers, such as clays, polymers and zein nanoparticles. Type 1 considers analytes of Ag-, Ti- and Cu- based nanomaterials.
While there are positive cases of nanopesticides which had reduced the negative effect that is seen in traditional chemical pesticides as seen in Cu(OH)2. The effect of nanopesticide was observed for 365 days on wetland systems and fungal communities that are present there [56]. But cases where overuse of nanopesticides leads to the negative impact on earth has also been reported. This was reported on long term exposure to high dosage of atrazine which contains nano pesticides that harmed the metabolic capacity of bacterial communities [57].
In a broader aspect nanopesticide is still seen a better option due to its high effectiveness and high productivity with lesser application than traditional pesticides. The positive outweighs the negatives that are seen in some nanopesticides. The future looks promising with a greener approach to pesticides and fertilisers with application of nano materials.
Ecotoxicology of nanoparticles
In nanotechnologies the manufactured nanoparticles are released into the environment, raising concerns about human and plant health. Recent studies have highlighted the toxic effects of nanomaterials used in industry. Metal nanoparticles exhibit antibacterial, anticandidal, and antifungal activities, with cytotoxicity depending on the charge at the membrane surface. Some NPs, like TiO2, ZnO, SiO2, and Fullerenes, are photochemically active, generating superoxide radicals when exposed to light. Further research is needed to determine the delayed impacts and adaptive mechanisms [58].
Nanoherbicides
Nano-herbicides are artificially synthesized herbicides in which the nano molecules are coated or loaded with nano size (1-100 nm) carrier materials [59]. Nano herbicides are tiny particles with active ingredients or structures that transport herbicide molecules, improving weed management. They are incorporated into nanomaterials (NMs) to enhance bioavailability and control the release of active ingredients. Delivery techniques include nanoemulsions, capsules, nanocontainers, and nanocages. Encapsulating herbicides follows the apoplastic and symplastic pathways for movement within plants and radial movement for transition between pathways to reach the plants [60]. Nano-enabled herbicides, such as nanoencapsulated atrazine, clodinofop propargyl, and fenoxaprop-p-ethyl, reduce herbicide quantity and require fewer active compounds in their primary field application. These nano herbicides have better weed control efficiency as compared to other herbicides and reduce environmental threats, as they obtain a high surface area and require fewer active compounds [61].
Nanobiosensors
Nanosensors are essential in agricultural applications as they are used to detect plant signals such as electrical, phytohormone, and chemical signals. They can be applied to individual plants in real time using techniques like FRET, SERS, and molecular recognition. These sensors can also help in diagnosis of plant diseases, identifying pathogens like DNA, protein, and VOCs. However, there is a need to check the stability of these nanosensors while employing them in the agricultural systems [62]. Agrochemicals can be made more effective and less polluting by using nanobiosensors, as they can detect the biotic and abiotic stressors in plants before they influence the productivity in plants. Nano fertilisers are emerging as cutting-edge materials with a broad range of formulations based on nanoparticles, including fungicides, insecticides, herbicides, and fertilisers. By making site-targeted controlled distribution of agrochemicals easier, they increase their effectiveness and lower dosages. To support sustainable agriculture, smart farming seeks to track and identify variables pertaining to environmental factors and plant health. By providing real-time analytical information on temperature, moisture of soil, pathogen presence, metabolites, pesticides, and nutrient levels, nanobiosensors can support precision farming methods and maximize resource use [63].
Conclusion
Nanotechnology in agriculture can address the demand for food by extracting nanoparticles from agricultural waste. These nanoparticles can be added to fertilisers and insecticides, increasing yield in crops, through targeted delivery of fertilisers and pesticides, while also enabling precision farming techniques.
Acknowledgements
We acknowledge the help and support received from the authority of Jagannath Barooah College (Autonomous) now upgraded to a university for providing the necessary guidance and support in the preparation of the manuscript.
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