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Bio-Science Research Bulletin http://www.bpasjournals.com Print version ISSN 0970 0889 Online version ISSN 2320 3161 DOI: 10.5958/2320-3161.2021.00006.7 Original Research Article Vol. 37 No. 1, January-June 2021: P.23-34 Nanoparticles and Nanotechnology: From Source, Properties, Types, Synthesis to Multifaceted Functional Potential in Agriculture 1 Anjali 2 Raj Singh 3 Indu Sharma 4 Pooja Sharma 5 Mahiti Gupta 6 Paavan Singhal 7 Soniya Goyal 8 Mukesh Yadav 9 Sushil Kumar Upadhyay*# Author’s Affiliation: 1,2,3,4,5,6,7,8,9 Department of Biotechnology, Maharishi Markandeshwar (Deemed to be University), Mullana-Ambala, Haryana- 133207, India *Corresponding author: Dr. Sushil Kumar Upadhyay, Department of Biotechnology, Maharishi Markandeshwar (Deemed to be University), Mullana-Ambala, Haryana- 133207, India E-mail: [email protected] # ORCID: https://orcid.org/0000- 0002-1229-4275 Received on 14.02.2021 Accepted on 27.05.2021 ABSTRACT Nanoparticles are a solid colloidal particle which ranges in size from 10 to 1000nm. The nanoparticles differs from its own bulk form in its physical properties and more over toxic than its bulk form. Due to these properties, nanoparticles can be used for a wide range of applications in various fields of science. Nanoparticles may be produced naturally, incidentally or can be engineered. These have profound multifaceted agricultural applications such as bioimaging, biosensors, nano-heribicides, nano-pesticides, nano- fertilizers, etc. This study is focused on to review the properties, types, synthesis and multifaceted potential of different nanoparticles in agriculture fields for effective management, improved productivity and sustainable development. KEYWORDS: Nanoparticles, Agriculture, Nanosensors, Nano-fertilizers, Nano-heribicides, Nano-pesticides Disease management, Sustainable development. INTRODUCTION Nanotechnology refers to an emerging field of science that includes synthesis and development of various nano materials (Yadav et al., 2016). Nanoparticles are solid colloidal particles that exist on a Nanometer scale with at least one dimension less than 100nm at atomic, molecular and macromolecular scales (Dan et al., 2021). The nanoparticles are differs in physical and chemical properties from its own bulk form (Pramanik et al., 2020; Singh et al., 2021a). The very high surface area to volume ratio is an essential characteristic of nanoparticles (Rudner, 2006). The characteristic features of nanoparticles cause plausible novel quantum mechanical effects (Klostranec et al., 2006). This effect is not dominant at micro level and it comes into account at nano scale only (Thaxton et al., 2009). Due to these properties nanomaterial can be used for ample applications in various fields of science including biomedical to agriculture (Rani et al., 2015; 2018a; Upadhyay et al., 2021). In fact, the country is in need of a second green revolution and it might be possible due to recent advances in nanobiotechnology and its multifaceted

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Bio-Science Research Bulletin http://www.bpasjournals.com

Print version ISSN 0970 0889 Online version ISSN 2320 3161

DOI: 10.5958/2320-3161.2021.00006.7 Original Research Article Vol. 37 No. 1, January-June 2021: P.23-34

Nanoparticles and Nanotechnology: From Source, Properties, Types, Synthesis to Multifaceted Functional Potential in Agriculture

1Anjali 2Raj Singh 3Indu Sharma 4Pooja Sharma 5Mahiti Gupta 6Paavan Singhal 7Soniya Goyal 8Mukesh Yadav 9Sushil Kumar Upadhyay*#

Author’s Affiliation: 1,2,3,4,5,6,7,8,9Department of Biotechnology, Maharishi Markandeshwar (Deemed to be University), Mullana-Ambala, Haryana- 133207, India *Corresponding author: Dr. Sushil Kumar Upadhyay, Department of Biotechnology, Maharishi Markandeshwar (Deemed to be University), Mullana-Ambala, Haryana- 133207, India E-mail: [email protected] #ORCID: https://orcid.org/0000-0002-1229-4275 Received on 14.02.2021 Accepted on 27.05.2021

ABSTRACT Nanoparticles are a solid colloidal particle which ranges in size from 10 to 1000nm. The nanoparticles differs from its own bulk form in its physical properties and more over toxic than its bulk form. Due to these properties, nanoparticles can be used for a wide range of applications in various fields of science. Nanoparticles may be produced naturally, incidentally or can be engineered. These have profound multifaceted agricultural applications such as bioimaging, biosensors, nano-heribicides, nano-pesticides, nano-fertilizers, etc. This study is focused on to review the properties, types, synthesis and multifaceted potential of different nanoparticles in agriculture fields for effective management, improved productivity and sustainable development. KEYWORDS: Nanoparticles, Agriculture, Nanosensors, Nano-fertilizers, Nano-heribicides, Nano-pesticides Disease management, Sustainable development.

INTRODUCTION Nanotechnology refers to an emerging field of science that includes synthesis and development of various nano materials (Yadav et al., 2016). Nanoparticles are solid colloidal particles that exist on a Nanometer scale with at least one dimension less than 100nm at atomic, molecular and macromolecular scales (Dan et al., 2021). The nanoparticles are differs in physical and chemical properties from its own bulk form (Pramanik et al., 2020; Singh et al., 2021a). The very high surface area to volume ratio is an essential characteristic of

nanoparticles (Rudner, 2006). The characteristic features of nanoparticles cause plausible novel quantum mechanical effects (Klostranec et al., 2006). This effect is not dominant at micro level and it comes into account at nano scale only (Thaxton et al., 2009). Due to these properties nanomaterial can be used for ample applications in various fields of science including biomedical to agriculture (Rani et al., 2015; 2018a; Upadhyay et al., 2021). In fact, the country is in need of a second green revolution and it might be possible due to recent advances in nanobiotechnology and its multifaceted

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application perspective to agriculture (Tuli et al., 2020; Singh et al., 2021b). Nano fertilizers are imagined to have the potential to develop agriculture and agriculture products (Marchiol, 2018; Iqbal, 2019). Now a day nanotechnology is providing different nano devices and nanomaterial which having a unique role in agriculture (Singh et al., 2020; Aggarwal et al., 2021). The nano biosensor is helpful to detect moisture content and nutrients in the soil (Chinnamuttu and Kokiladevi, 2007). Nano-herbicides are used to control the weed in the crop fields, and nano-pesticides to control pests and associated diseases (Gutierrez, 2011). Hence, nanotechnology have greater role in crop production with environment safety, and ecological stability (El-Raie et al., 2015; Shang et al., 2019). Nano fertilizer are synthesized or modified form of traditional fertilizers, fertilizers bulk material or extracted from different vegetative or reproductive parts of the plant by different chemical, physical, biological methods with the help of nanotechnology to improve soil fertility, productivity and quality of crops (Singh et al., 2017; Biswas and Kumar, 2021; Seleiman et al., 2021). Rock phosphate if used in nano form it may increased availability of phosphorous to the plants (Kannan and Gopalu, 2012). The direct application of rock phosphate nano particles on the crops may prevent fixation in the soil similarly there is no silica acid, iron and calcium for fixation of phosphorous hence it increase phosphorous availability to the crop plants (Kannan and Gopalu, 2012; Bindraban et al., 2020). TYPES OF NANOPARTICLES Nanoparticles are tiny materials and can be classified into different classes based on their properties, shapes or sizes. There are mainly four types of Nanoparticles based on the number of dimensions including zero-dimensional (0-D), one-dimensional (1-D), two-dimensional (2-D), and three-dimensional (3-D) structures (Tiwari et al., 2012). i. 0-D nanoparticles: These include Nano cluster materials and nanospersions, i.e. materials in which nanoparticles are isolated from each other.

ii. 1-D nanoparticles: 1-D nanoparticles have thin films or surface coatings and are used in the circuitry of computer chips and for antireflective properties and hard coatings on eyeglasses. Carbon nanotubes, natural semi 1-D nanoparticles, can be used as a template for synthesis (Horn et al., 2006). iii. 2-D nanoparticles: 2-D nanoparticles are crystalline materials consisting of a 2-D single layer of atoms. These have fixed and long nanostructures with thick membranes. They are used to prepare Nano pore filters used for small particle separation and filtration, e.g., Asbestos fiber (Tiwari et al., 2012). iv. 3-D nanoparticles: 3-D nanoparticles are Nano phase materials consisting of equated Nanometer-sized. These are fixed and small nanoparticles where thin films are deposited under conditions that are generate atomic scale porosity, colloids, and free nanoparticles with various morphologies. The box-shaped grapheme (BSG) Nanostructure is an example of 3-D Nanomaterial (Buzea et al., 2007). The structures having no dimensions confined to the Nano scales are called three dimensional structures or bulk nanostructured materials. In to dimensional structures, two of the dimensions are not confined to the Nano scales e.g. Nano films or Nano layers and Nano coating. In one dimensional structures, one dimension is not confined to the Nano scale e.g. nanotubes, Nano rods and Nanowires. In zero dimensional structure, all dimension are confined to Nano scale e.g. nanoparticles. SOURCES OF NANOPARTICLES The nanoparticles (NPs) may be produced naturally, incidentally or can be engineered as described below. i. Natural NPs: The biological systems often feature natural and functional nanomaterial. The structure of foraminifera and viruses (protein and capsid), the wax crystals covering a lotus leaf, spider silk, some butterfly wings, scales, horny materials like skin, claws, beaks, feathers, horns, hair, paper, cotton, nacre, coral and even our bone matrix are all natural organic nanomaterial (Houghton, 2005; Kanti and Karthika, 2016). Natural source of nanoparticles include combustion products forests fires, volcanic ash, ocean spray and

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radioactive decay of radon gas. Natural nanomaterial can also be formed through weathering processes of metal or anion-containing rocks as well as at acid mine drainage sites. ii. Incidental NPs: Nanoparticles may be produce incidentally as a byproduct of mechanical or industrial processes. The source of incidental nanoparticles include vehicle engine exhausts, welding fumes, combustion processes from domestic solid fuel heating (Rogers et al., 2005). For instance, the class of nanomaterial called fullerenes are generated by burning gas, biomass. Incidental atmospheric nanoparticle is referred to as ultrafine particles which are unintentionally produced during an intentional operation. iii. Engineered NPs: These have been deliberately engineered and manufactured by humans to have certain required properties such as carbon black and titanium oxide nanoparticle. These are useful in biomedical field as well as commercial products like sunscreen, cosmetics (Aitken et al., 2004). PROPERTIES OF NANOPARTICLE Various physico-chemical properties such as large surface area, mechanically strong, optically active and chemically reactive make NPs unique and suitable applicants for various applications (Singh et al., 2010). Some of their important properties are: i. Physical properties: Nanoparticles consist of three layers including surface layer, the shell layer, and the core. The surface layer usually consists of a variety of molecules such as metal ion, surfactants and polymers. Nanoparticles may contain a single material or may be consists of a combination of several materials. Nanoparticles can exists as suspensions, colloids, or dispersed aerosols depending on their chemical and electromagnetic properties (Hoshino et al., 2004). Nanoparticles are very small in size due to which quantum effects arise and hence nanoparticles have astonishing optical properties (Yin et al., 2005). Nanoparticles have wonderful diffusion properties particularly at high temperature because of the high surface area to volume ratio. The large total surface area also increases the stability suspension (Lee et al., 1999). The properties of

nanoparticles are dependent on their size. For instance, copper nanoparticles are smaller than 50nm are super hard material and do not exhibit the properties of malleability of bulk copper. ii. Electronic and optical properties: The optical and dent to greater extent. For instance, no electronic properties of NPs are inter-deepened metals NPs have size dependent optical properties and exhibit a strong UV-visible extinction band that is not present in the spectrum of the bulk metal. This extinction band results when the incident photon frequency is constant with the collective excitation of the conduction electrons and is known as the Localized Surface Plasmon Resonance (Zhang and Wang, 2017). iii. Magnetic properties: Magnetic NPs are of great curiosity for investigators from an electric range of disciplines, which include heterogeneous catalysis, biomedicines, magnetic fluids, data storage magnetic resonance imaging (MRI), and environmental remediation such as water decontamination. The literature revealed that NPs perform best when the size is less than critical value, i.e. 10-20nm (Reiss and Hutten, 2005). iv. Mechanical properties: The distinct mechanical properties of NPs allow for novel applications in many important fields such as surface engineering, nanofabrication and nanomanufacturing. Different mechanical parameters such as elastic modules, hardness, stress and strain, adhesion and friction can be surveyed to know the exact mechanical nature of NPs (Guo et al., 2014). SYNTHESIS OF NANOPARTICLES Generally, metallic and semiconductor nanoparticles are synthesized and stabilized by using various methods such as chemical reduction, electrochemical techniques and photochemical reactions in reverse micelles (Chandra et al., 2006; Vigneshwaran et al., 2007). The chemical synthesis of nanomaterial has several occupational exposure hazards like carcinogenicity, genotoxicity, cytotoxicity and general toxicity (Mukherjee et al., 2008). Consumption of nontoxic chemicals of environmentally benign solvent and of renewable materials are some of the key issues that merit important consideration in a green

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synthesis strategy (Yadav et al., 2016). Synthesis of metals and semiconductor nanoparticles is enormous and expending area due to their potential applicability in various areas such as electronics, chemistry, and energy and medicine development (Salouti and Faghri Zonooz, 2017). Use of biomaterials in synthesis of nanoparticles is quite novel leading to truly green chemistry which provide advancement over chemicals and physical methods as it is cost effective and environment friendly, easily scaled up for

large scale synthesis and in this methods there is no need to use high pressure, energy, temperature and toxic chemicals (Saxena et al., 2010; Ponarulselvam et al., 2012). Mainly the methods of synthesis of nanoparticles are characterized into two classes including Top-down approach and Bottom-up approach. These approaches are further divided into various subclasses based on the operation, rxn condition and adopted protocols (Iravani, 2011).

Figure 1: Top-down method for synthesis of nanoparticles. i. Top-down synthesis: In this method, destructive approach is employed (Figure 1). This method refers to slicing or successive cutting of a bulk material into a nano-sized particle. Top-down refers to the traditional workshop or micro fabrication method where tools are used to cut, mill and shape material into desired shape and order. Starting from larger molecule in solid state, which decomposed into smaller units and then these are converted into suitable nanoparticles. Example of this method is grinding or milling, physical vapor deposition and other decomposition techniques (Iravani, 2011). This approach is used to synthesize coconut shell

(CS) NPs. The milling method was employed for this purpose and the raw coconut shell powders finely milled for different interval of times, with the help of ceramic balls and a well-known planetary mill. They showed the effect of milling time on the overall size of the nanoparticles through different characterization techniques. It was determined that with the time increase the NPs crystallite size decreased. The SEM results were also in an agreement with the x-ray pattern, which also indicate the particle size decreased with the time (Wanget al., 2015). The powerful laser irradiations generate well-uniform NPs having good oxygen vacancies (Zhou et al., 2016).

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Figure 2: Bottom-up approach for synthesis of nanoparticles. ii. Bottom-up synthesis: This approach is employed in reverse as NPs are formed from relatively simple substance; therefore this approach is also called building up approach (Fig. 2). Example of this case is sedimentation and reduction techniques. It includes sol gel, green synthesis, spinning and biochemical synthesis (Iravani, 2011). In the sol-gel processing method, there are two types of components viz., ‘sol’ which is a colloidal suspension of solid particles in a liquid and ‘gel’ which are polymers containing liquids. Thus, this process includes the creation of ‘sols’ in the liquid that lead to the formation of a network of a discrete particles or network polymers by the connection of sol particles (Mogilevsky et al., 2014). Hydrolysis and condensation are the typical steps of sol-gel process, in which the former uses water to disintegrate the bonds of the precursor that is also the first step in formation of Nanomaterial after which excess water is removed to determine the final structure of the material. For instance, ZnO NPs were synthesized by this method using Zinc acetate dehydrates and as the precursor triethanolamine (Dinca et al., 2016; Singh et al., 2020). Well-uniform spherical shaped Au Nano spheres with Nano crystalline have been synthesized via laser irradiation top-down technique (Liu et al., 2015a,b).

iii. Biomimetic synthesis: Biomimetic is an interdisciplinary field in which principles from engineering, chemistry and biology are applied to the synthesis of materials and synthetic systems that have functions that mimic biological processes (Singh et al., 2020; Singh et al., 2021c). Biomimetic refers to human made processes that imitate nature and applying biological principles for material formation (Fig. 3). The art and science of designing and building biomimetic apparatus is also k/as bio mimicry because they mimic biological systems (Prathna et al., 2010). One of the primary processes in biomimetic involves bio reduction (Fig. 3). Initially bacteria were used to synthesize nanoparticles and this was later succeeded with the use of fungi, actinomycetes and more recently plants (Li et al., 2011). Microbes are produce nanoparticles as part of their metabolism and therefore can be used for a no of applications. Nanoparticles are more popular in various fields of research and are useful in detection of various diseases in the form of their early and fast detection. The bacteria Escherichia coli are to be used in synthesizing silver nanoparticles and helps in efficient digestion (Guru Nathan et al., 2011).

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Figure 3: Biomimetic approach for synthesis of nanoparticles. APPLICATIONS OF NANOPARTICLES IN AGRICULTURE Agriculture is always the backbone of many developing countries. In agriculture the main reason to use fertilizers is to give full-fledged macro and micro nutrients which usually soil lacks. There are 35-40% of crop productivity depends upon fertilizers but some of the fertilizers affect plant growth directly. World agriculture cropping system is intensively using large amount of fertilizers, pesticides, herbicides to gain more production of crop (Singh et al., 2019). The amount of chemical fertilizers cause many problems like environment pollution (soil, water, air pollution), decrease quality of food material, disease insect, soil degradation, deficiency of micronutrient in soil etc. Therefore these problems are challenge to feed the growing population of the world (Ghaly, 2009). To overcome all these drawbacks a smart way (nanotechnology) can be of the source (Rani et al., 2018b). For solving these problems in crop production nano-fertilizers, pesticides and

herbicides may active tool in agriculture for better pest and nutrient management because these nano-material having more penetration capacity, surface area to avoid residues in environment (Fig. 4) (Pramanik, et al., 2020). Zinc sulfide (or zinc sulphide) is a white color, soluble in water, an inorganic compound with chemical formula of ZnS. This is main form of zinc found in nature, where it mainly occurs as the mineral sphalerite (Bradley et al., 2007). Although this mineral is usually black because of various impurities, the pure material is white, and it is widely used as a pigment. In its synthetic form, zinc sulphide can be transparent, and it is used as a window for visible optics and infrared optics. Zinc sulphide nanoparticles (ZnS-NPs) are used in an increasing number of industrial products. In the past two decades, ZnS-NPs have become one of the most popular Meta oxides nanoparticles in biological applications due to their excellent biocompatibility, economic and low toxicity.

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Figure 4: Multifaceted applications of nanotechnology in agriculture. Nano-fertilizer is any product that is made with nanoparticles or use nanotechnology to improve nutrient efficiency. Nano-fertilizers are the important tools in agriculture to improve crop growth, yield and quality parameters with increase nutrient use efficiency, reduce wastage of fertilizers and cost of cultivation. A Nano-fertilizer is any product that is made with Nano-particles or uses Nanotechnology to improve nutrient efficiency. Nano-fertilizers facilitate slow and steady release of nutrients and thereby reduce the loss of nutrients and enhance the nutrient use efficiency. Nano-fertilizers increase crop growth upto optimum concentrations further increase in concentration may inhibit the crop growth due to toxicity of nutrient (Hidoto et al., 2017). Nano-fertilizers provide more surface area for different metabolic reaction in the plant which increase rate of photosynthesis and produce more yield of crop. It also prevents plant from different biotic and abiotic stress. The Nano-fertilizers have higher surface area it is mainly due to very less size of particles which provide more site to facilitate different metabolic process in the plant system result production of more photosynthesis (Biswas and Kumar, 2021). These nano fertilizers particle size are less than the pore size of roots and leaves of the plant

which increase penetration into the plant and improve uptake of nutrient use efficiency of the nano fertilizer (Lin and Xing, 2007). Thus the fertilizers encapsulated in nanoparticles will increase availability and uptake of nutrient to the crop plant (Liscano et al., 2000). The findings of Benzon et al., (2015) indicated that, the number of reproductive tillers, panicles and total spikelet’s were significantly affected by the application of conventional fertilizer and its combination with nano fertilizer in rice field. Nano-fertilizer may have synergistic effect on the conventional fertilizer for better nutrient absorption by plants cells resulting to optimal growth. These suggest that nano fertilizer can either provide nutrients for the plant or aid in the transport or absorption of available nutrients resulting in better crop growth. Related study by Liu and Lal (2014) revealed similar findings in soybean after application of hydroxyapatite phosphorus nanoparticles (NPs) of 16nm in size. The data assessment revealed that growth rate was increased by 33% using phosphorus NPs in a greenhouse experiment. Taheri et al., (2015) conducted an experiment to investigate the effects of ZnO in mineral poor soils of corn cropland system. Corn (SC704) seeds were cultivated with zinc oxide

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nanoparticles (ZnO-NPs) treatment, which increased the plant growth, leaf area and dry weight significantly than the normal control (Ciceka nd Cakirlar, 2002). A field experiment for Zea mays was carried out by Moaveni and Kheiri (2011) using a factorial complete randomized block design with four replications during 2010-2011) to study the effect of Titanium oxide nanoparticles (TiO2-NPs). The results showed that the higher number of corn in each plant with increased maize dry weight with highest corn yield in the field treated to TiO2-NPs. CONCLUSIONS The nanoparticles have great potentials to improve crop growth, yield and quality parameters with increase nutrient use efficiency, reduce wastage of fertilizers and cost of cultivation. These facilitate slow and steady release of nutrients and thereby reduce the loss of nutrients and enhance the nutrient use efficiency. The nanoparticles are able to convert poorly soluble, poorly absorbed and labile biologically active substance into promising deliverable drugs. The large amount of fertilizers, pesticides, herbicides to achieve more production of crop but using more amounts of chemical fertilizers causes many problems like environment pollution. The use of nano-fertilizers, nano-pesticides and nano-herbicides in agriculture can be promising for better pest and nutrient management because these nano-materials having more penetration capacity, surface area to avoid residues in environment. Further research and developments are required in the practical applications of nanoparticles for the sustainable development of agriculture, food security and mankind. Acknowledgement Authors are immensely appreciative to Professor & Head, Department of Biotechnology, Maharishi Markandeshwar (Deemed to be University), Mullana-Ambala (HR), India for facilities and critical suggestions during research compilation.

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How to cite this article: Anjali, Singh R., Indu Sharma I., Sharma P., Gupta M., Singhal P., Goyal S., Yadav M., Upadhyay S.K. (2021). Nanoparticles and Nanotechnology: From Source, Properties, Types, Synthesis to Multifaceted Functional Potential in Agriculture. Bio-Science Research Bulletin, 37(1), 23-34.