The demand for agricultural crops continues to escalate with the rapid growth of the population. Silica nanoparticles (SNPs) are beneficial for plant growth and production and can be used as nanopesticides, nanoherbicides, and nanofertilizers in agriculture. SNPs can be classified as porous or non-porous in structure and can be synthesized by chemical, physical, and biological methods. In agriculture, SNP can be sprayed on foliage or irrigated into the soil. SNPs can promote plant growth and development by increasing photosynthesis and nutrient uptake rates and enhancing plant resistance to environmental stress. In the future, SNPs will provide various solutions for the healthy growth of agricultural crops.
1. Introduction
The Food and Agriculture Organization (FAO) estimates that in 2050, the global population will increase to 9 billion, and global food production should increase by 70% to meet the growing population’s demand for food [1][2]. At present, biotic and abiotic stressors such as drought, extreme climate, salt, diseases, and pests cause crop loss worldwide. The influence of abiotic stresses on crop production causes an annual loss of crop yield of 51–82% [3]. To increase crop yield, farmers frequently use pesticides and fertilizers, creating a huge threat to the ecological environment. Therefore, environmentally friendly technologies should be developed to help plants overcome biotic and abiotic stresses and ensure optimum crop yield and agricultural sustainability.
Nanotechnology application in agriculture is an emerging interdisciplinary field, which plays a positive role in promoting plant growth and conferring stresses tolerance in plants and has a great potential for applications in agriculture [4][5][6]. Nanoparticles (NPs) are small particles with a size range of 1–100 nm. In comparison with bulk compounds, NPs exhibit different physical and chemical properties in terms of their surface, optical, thermal, and electrical properties [7]. NPs have unique physiological characteristics, large surface-area-to-weight ratios, and small sizes, which can increase their solubility and transportation speeds within plants [8]. Several nanomaterials such as Fe3O4, MgO, SiO2, and CeO2 are beneficial for plant growth, playing an important role in promoting seed germination, increasing plant resistance, degrading pesticide residues, and enhancing soil quality [9][10][11][12].
The hydrolyzed product of silica nanoparticles (SNPs) is monosilicic acid (H4SiO4) [13]. Silicon is the second most abundant element in the earth’s crust and plays a pivotal role in many biogeochemical processes. Silicon strengthens the physical barrier of plants through its deposition onto plant cell walls, thus promoting the ability of lodging tolerance and disease resistance [14]. The applications of silicon and SNPs reduce the oxidative stress response by priming defense reactions under biotic and abiotic stresses [15][16][17][18]. Moreover, SNPs have a small particle size and easily penetrate the plant cell wall and the organelles [19]. In comparison with bulk materials, NPs have a high surface-area-to-volume ratio, thus improving their reactivity and biochemical activity [20][21]. The SNPs’ accumulation in corn is 9.14% higher than for bulk silica [22]. Therefore, SNPs may be more effective than bulk silica in alleviating different adversity stresses [18][23][24][25].
2. Synthesis and Characteristics of SNPs
SNPs are synthesized via top-down and bottom-up approaches (Figure 1) [26][27]. Top-down strategies of SNPs mainly include mechanical and mechanochemical synthesis methods. The mechanical methods pulverize large solids via ball milling technology, while the mechanochemical approaches assist chemical reactions by mechanical pulverization [28]. The mechanochemical method involves the use of simple equipment at a low cost, and it could produce NPs in batches, but the produced NPs have a wide size range and uneven shape distribution, as well as contain a large amount of impurities [29]. The bottom-up syntheses of SNPs mainly include gas- and liquid-phase synthesis. Gas=phase synthesis has some drawbacks, such as the need for special equipment to produce films and the reaction chamber, and the emission of toxic gaseous by-products [30]. Liquid-phase synthesis covers precipitation, microemulsion, and solution-gel syn-thesis [31][32][33]. Solution-gel synthesis is one of the most common SNP synthesis methods. Stöber et al. (1986) reported tetraethylorthosilicate as the silicon source, ammonia as the catalyst, and different alcohol solutions as the solvent to synthesis SNPs with a particle size distribution of 0.05–2 μm [31]. Most mesoporous SNPs are synthesized by a modified Stöber’s method [34]. In addition, the biosynthesis of NPs by microorganisms, algae, and plant compounds is a green and eco-friendly technology [6][35].
Figure 1. Synthesis methods of nanoparticles (Figure created using BioRender [https://biorender.com/] 6 February 2022).
SNPs could be classified as porous or nonporous in structure. The synthesis method of SNPs significantly affects their structure with variations in particle size, shape, pore size, and dissolution rate, which influence their application and manner in organisms [34][36]. The size of SNPs is usually governed via adjusting the pH of the reaction solution in the solution-gel method [31]. The particle size and shape of the SNPs greatly impact their cellular uptake and distribution in organisms [37][38]. However, previous studies on the influence of the shape and size of SNPs on organisms have mostly focused on the animal field. In contrast, there are relatively few studies in the plant field. The porosity of Stöber silica could be controlled by adjusting the ratio of water; in conditions of a high ratio of water to TEOS, SNPs with smooth particle surfaces were obtained. In contrast, rough particle surfaces with micropores were synthesized [39]. The type of surfactant added in the liquid phase synthesis process could change the pore size of SNPs [34]. The longer chain lengths of surfactants cause SNPs to have larger pores, and those surfactants with shorter chain lengths cause SNPs to have smaller pores [40]. Pore SNPs are usually used in the delivery of pesticides or herbicides in agriculture. The pores’ size and number of SNPs will affect their degradation rate, which is essential for effective drug delivery [41]. The dissolution rate of SNPs was accelerated as the increase of porosity increased [42]. The dissolution rate of SNPs in plants impacts their effectiveness. Fast-dissolving SNPs could increase plant biomass and fruit yield [11]. Furthermore, in the process of preparing SNPs, some compounds such as (3-aminopropyl) triethoxysilane, oligochitosan, and amino acids could also be added to the synthesis of functionalized SNPs [11][43][44]. For instance, after oligochitosan–nanosilica application, the resistance of chili plants to anthracnose disease rises significantly when compared to single nanosilica treatment [44]. At present, there is a lack of in-depth research about the influence of SNPs synthesis methods on the absorption and distribution of SNPs in plants, plant growth, and stress resistance. In addition, the release behavior of different SNPs (porous, non-porous, surface modification, etc.) in plants needs to be further studied.
3. Absorption and Transmission of SNPs in Plants
In agriculture, SNPs can be applied by spraying on the leaves or directly into the root. The SNPs applied by the foliar application can enter the leaves and be transported to different parts through the cuticular or stomata (Figure 2). The transport path of solutes via the cuticle has two routes: one is the lipophilic pathway for non-polar solutes via diffusion and penetration, and the other is the hydrophilic pathway for polar solutes via water pores (the effective diameter of these pores is 0.6–0.8 nm) [45][46][47]. In addition, the hydrophilic substances are transported via stomatal pores in the stomatal pathway. However, the unique geometric structure and physiological function of the stomata is complex, and the actual size exclusion limit of the pores penetrated by nanomaterials is still unclear. Hu et al. (2020) investigated SNPs in the guard cells of leaves after spraying SNPs (18 nm) for 3 h [48]. Similarly, SNPs (54 ± 7 nm) could enter the air spaces of the leaf via the stomata and the outer edge of the cell walls [18]. After nanomaterials enter leaves, they could trans-locate from leaves back to the roots via the phloem [49][50]. In the roots, nanomaterials could form complexes with carrier proteins or root exudates [51]. These complexes can pass through the root cell wall, enter plant cells through intracellular phagocytosis, or directly penetrate the cytoplasmic membrane and then disperse in the cytoplasm [52][53][54][55]. Moreover, nanomaterials can also be transported from the roots to shoots through the xylem [54][56]. Furthermore, the active mode of silicon uptake from roots to shoots via specific transporter proteins includes transport protein (Lsi1), transport protein (Lsi2), and transport protein (Lsi6) [14][57]. SNPs enter the root through the transporter Lsi1 [54][58]. However, the concentration of SNPs application does not affect the expression of the Lsi1 gene in plants. Therefore, SNPs enter the plant body mainly through extra mass infiltration [59]. In addition, the expression of silicon transported genes Lsi1 and Lsi2 in rice treated with SNPs increases under salt stress [25]. Moreover, OsLsi1 is a Si-transporting aquaporin (AQP), which was upregulated by Si supplementation, and the AQP could establish the link between Si and molecular signaling [60].
Figure 2. Schematic diagram of the transportation of nanomaterials in the plant (figure created using BioRender [https://biorender.com/] 6 February 2022).
The accumulation and absorption of nanomaterials in plants differ, and the process mainly depends on the type of plant, chemical composition, and the size of nanomaterials [51][61]. Slomberg and Schoenfisch (2012) reported different sizes of SNPs (14, 50, and 200 nm) that could enter Arabidopsis roots, but the accumulation of SNPs in root cells decreases with the increase of SNP size [62]. The efficient transport of nanomaterials into guard cells, extracellular space, and chloroplasts is related to the size and charge of the nanomaterials [48]. Cui et al. (2017) applied different particle sizes (19, 48, and 202 nm) of SNPs to treat rice cell suspension cultures under chromium stress and found that SNPs with small particle sizes had viable rice cells in the suspension [24]. Similarly, the bactericidal effect of SNPs on Pseudomonas aeruginosa also increases with the decrease of its particle size [63].