Effects of nano and ionized silicon on physiological and biochemical characteristics of potato (Solanum tuberosum L.)

The role of protecting and structure stabilizing effects of silicon (Si) has been demonstrated on different plant species. Still it has not been used in potato seed production under a soilless culture system. Furthermore, particle size is very important in particle adhesion and interactions with biological reactions. Therefore, the use of nano-Si particles may be more ecient than ionized -Si. For this purpose, a greenhouse experiment under a soilless culture system was performed as a randomized complete block design (RCBD) arranged in a factorial with three replications. In this study, Si concentration (distilled water (Control), 0.8, 1.6, 2.4, and 3.2 mmol Si L − 1 ) and Si type at two levels (nano and ionized Si-based in sodium silicate) were tested. The results revealed that foliar application of Si signicantly improved the net photosynthesis rate, water use eciency, mesophyll conductance, Chl a, Chl b, carotenoids, Chl a/b ratio, DPPH radical scavenging, total phenol, mean weight mini-tuber, and yield, whereas transpiration rate in Si-treated plants decreased. Moreover, the greatest positive inuence of Si was observed at 3.2 mmol L − 1 . The effect of Nano-Si was greater than ionized-Si at all Si concentrations. The results revealed that improved biochemical and photosynthetic characteristics of potato plantlet under Nano-Si treatments compared to ionized-Si treatments. However, these relations were not signicant under ionized treatment. This study indicated that the application of Si (nano and ionized) for potato growing and mini-tuber production has positive effects. Generally, under soilless culture system, Nano-Si have higher eciency than ionized-Si in mini-tuber production. Therefore, improvement of water use eciency was predictable. A positive effect of Si application on mesophyll conductance of potato leaves was also in agreement with Haghighi and Pessarakli (2013) [8] results in cherry tomato. Our results showed that all Si levels had a positive effect on mini-tuber yield. The ability of Si to increase yield production has been demonstrated in cucumber [5] and tomato [35]. According to this study, although net photosynthesis, pigment content, and yield measured in Si treatments were enhanced. These changes in nano-Si treated plants were more than ionized-Si. These results also indicated that potato leaves could foliar uptake of Si and nanoscale particles showed more eciency in response to this method. The higher inuence of nanoparticles may be due to unique characteristics [8, 12, 37] and facility uptake by leaf stomata because of their smaller size. These observations are in agreement with Tripathi et al. (2015) [12], who achieved the benecial inuence of nano-Si on growth and dry weight of Pisum sativum in normal and Cr toxicity. Siddiqui and Al-Whaibi (2014) [36] also conrmed that nano-Si increased the germination characteristics, which enhanced the seedling dry weight of tomato. However, Haghighi and Pessarakli (2013) [8] showed that although Si addition mitigated adverse effects of salinity in gas exchange parameters and dry weight of cherry tomato, no difference between root application of nano and bulk Si was observed. The comparison of silicon nanoparticles and silicate in Fenugreek by Nazaralian et al. (2017) [6] also indicated that the inuence of the added nanoparticles in nutrient solution declined over time. Moreover, the results of Abdel-Haliem et al. (2017) [37] showed that application of nano and ions Si in rice seedling under saline conditions increased growth, antioxidant activity, and biochemical traits such as soluble carbohydrates and amino acids, but the difference between particle sizes of Si was not noticeable.

Nanoparticles of sodium silicate produced in Central Lab of Ferdowsi University of Mashhad. At the elementary phase, 50 g of Na 2 SiO 3 (Sigma Aldrich, code number product: 307815, 99.9% purity, white color, and granule) were heated in an oven at 75°C for 5 h and was ground in a mixer mill (MM 400, Retsch, Germany) by 1680 rpm for 50 min with 1:10 of ratio sample to balls (w/w). Finally, bulk and milled particles size were measured with Particle Size Analyzer (PSA) (VASCO3, Cordouan Technologies, France, rangs of measurement 6µm to 1 nm) and Scanning Electron Microscope (SEM, model 1450VP, LEO, Germany, magni cation ranging from 20x to approximately 300000x, and 2 nm resolution). The average diameter of milled particles was 68 nm (Figs. 1 and 2).

Preparation of nano and ionized solutions
For preparation of each concentration level (nano or ionized), Citogait (a nonionic surfactant, 100% alkyl aryl polyglycol ether, Zarnegaran Pars, Iran) was added at 0.2% (v/v) to 500 mL of particle solution and its pH was adjusted to 5 ± 0.1 with 0.01N HCl. Then, the solutions shacked at 250 rpm in darkness at 20°C for 2 h.

Providing plantlets
To prepare the potato plantlets (Agria cv.), stem segments free from pathogens (approximately 15 mm length with one leaf node) were grown in vitro by using MS medium with 3% sucrose and 0.7% agar . After subculture, the plantlets were grown in a culture room with 60 ± 5% RH, 16 h light/8 h dark period (approximately 400 µmol photons m − 2 s − 1 ) at 24 ± 2°C for 21 days. Afterward, each uniformed plantlet was gently washed with distilled water to remove agar and transplanted into a plastic pot (30 and 12 cm depth and diameter, respectively) lled with a 1:1:1 perlite, cocopite, and sand media. Fifty percent of growth medium was added in transplanting time and the rest was added after four weeks.

Experimental conditions
During the experiment, the mean of irradiance was approximately 1000 µmol photon m − 2 s − 1 with 14 h light/10 h dark photoperiod, and the maximum and minimum air temperatures were 26°C and 18°C, respectively. Mean relative humidity was also 40 ± 10%. Irrigation was applied equally (200 mL per plantlet) twice a week. The plantlets were nourished with 100 mL of complete Hoagland nutrient solution [23] once a week. The pH was measured with portable equipment and adjusted for 5.5 ± 0.1 using HCl and NaOH 2N solutions. To prevent the accumulation of salt every 15 days, 1200 mL of distilled water was added to each pot to wash the medium.
Mesophyll conductance (MC, mmol CO 2 m − 2 s − 1 ) was calculated as the net photosynthetic rate divided by the substomatal CO 2 concentration. Water use e ciency (WUE, µmol CO 2 mmol − 1 H 2 O) was calculated as the net photosynthesis rate divided by the transpiration rate [8]. To assess these variables, an average of eight fully developed potato leaves was measured from each replication.

Biochemical assay
One week after the second Si application, chlorophyll (Chl), carotenoids (Cart), total phenol and DPPH radical-scavenging were measured from the second youngest fully developed leaves.

Pigments
Chlorophyll a and b and carotenoids contents were extracted based on Arnon (1949) [24] method. Samples of 100 mg fresh leaves were homogenized with 80% methanol at 4°C in a micro-tube and centrifuged at 3000 g for 15 min at 4°C and put in the refrigerator for 24 h. Then, the upper extract absorbance was measured at 653, 666, and 470 nm with a UV/Vis spectrophotometer (JENEWAY, model 6305, UK). Chlorophyll content was calculated using the formula and expressed in mg per g fresh weight. The chlorophyll a/b ratio was also calculated as described by Arnon (1949) [24].

Total phenols
The total phenol content was determined according to the Folin-Ciocalteu reagent method proposed by Singleton and Rossi (1965) [25] with slight modi cation. Brie y, the alcoholic extract (20%, w/v) was diluted with distilled water and Folin-Ciocalteau was added to the mixture. After ve minutes, the sodium carbonate (20%, w/v) was added and the mixture was kept in the dark for 30 min. The absorbance was measured at 765 nm (JENWAY, model 6305, UK), and total phenols were expressed as mg of gallic acid per g fresh weight.

DPPH radical scavenging
The DPPH radical scavenging activity of leaf extracts was measured according to the modi ed Abe et al. (1998) [26] method. The alcoholic extract (20%, w/v) was mixed with alcoholic DPPH solution (8%, w/v). The reaction mixture was shaken vigorously and left to stand in darkness for 30 min and absorbance was measured at 517 nm (JENWAY, model 6305, UK). DPPH radical scavenging was expressed as mg of ascorbic acid per g fresh weight.

Harvest of mini-tuber
The economic yield, including the mean mini-tuber weight and yield per plant was measured after 95 days of transplanting.

Statistical analysis
The study was arranged in a pooled two factorial experiments design with six replications. The data were analyzed with SAS 9.1 (SAS, Institute Inc., NC).
Signi cant differences between the treatments were determined using Fisher's Least Signi cant Difference (FLSD) test at 0.05 probability level. Pearson correlation coe cient was also used to determine the correlation between traits.

Gas exchange parameters
Silicon particle size (P) signi cantly affected net photosynthetic rate (Pn), Mesophyll conductance (MC), and water use e ciency (WUE) in potato plantlets, but no signi cant effect was observed on transpiration rate (Tr) and substomatal CO 2 concentration (Ci) ( Table 1). Whereas, silicon concentration levels (C) showed a signi cant effect on all measured gas exchange parameters. A signi cant interaction between P and C was also observed on Pn, Ci, MC and WUE (Table 1). Table 1 Analysis of variance for the effect of particle size and Si concentration levels on gas exchange parameters, pigment contents, biochemical traits, and tuber yi greenhouse conditions. Foliar application of nano-Si and ionized-Si improved the net photosynthetic rate, mesophyll conductance, and water use e ciency ( Table 2). The increasing Si concentrations, increased net photosynthesis rate, but the different sizes of Si had no similar effects. Net photosynthesis rate was signi cantly increased (P ≤ 0.05) by 23.84% in nano-Si treated plants compared with ionized-Si particles at 1.6 mmol Si L − 1 whereas in other concentration levels, the different between Si particle sizes was not signi cant. In nano and ionized Si treatments, the highest Pn of leaves was observed at 3.2 mmol Si L − 1 level, as 36.54% and 33.02% increment compared with control, respectively ( Table 2). Although the interaction between particle size and Si concentration level was not signi cant on leaf transpiration rate (Table 1), transpiration rate distinctively decreased by increasing Si concentration in tuberization stage, and all Si concentration levels, a signi cant difference with control was recorded (P < 0.05) (Table 3). Furthermore, the highest value of transpiration rate was also obtained at 3.2 mmol Si L − 1 level with an increase of 38.06% compared with control (Table 4). Table 2 Interaction effects of the Si particle size (P) and Si concentration levels (C) on the net photosynthetic rate (Pn), substomatal CO2 concentration (Ci), mesophyll conductance (MC) and water use e ciency (WUE) of potato plantlet leaves at tuberization stage. The presented values are the means ± standard deviation from six replications (n = 6). LSD: The least signi cant difference at P < 0.05. The presented values are the means ± standard deviation from twelve data (n = 12). LSD: The least signi cant difference at P < 0.05. Table 4 Interaction effects of the Si particle size (P) and Si concentration levels (C) on the Chlorophyll a (Chl a), chlorophyll b (Chl b), DPPH radical scavenging and total phenol of potato plantlet leaves at tuberization stage. The presented values are the means ± standard deviation from six replications (n = 6). LSD: The least signi cant difference at P < 0.05.

Please insert Tables 2 and 3 near hear
The foliar application of nano and ionized silicon levels imposed different effects on substomatal CO 2 concentration. For instance at 2.4 and 3.2 mmol Si L − 1 , the substomatal CO 2 concentration increased signi cantly compared with control (P < 0.05), and the highest amount was observed at 2.4 mmol nano-Si L − 1 with a difference of 25.06% compared with control. The highest effect of ionized-Si particle size was also observed at 3.2 mmol Si L − 1 with an increase of 10.89% compared to control ( Table 2). The application of nano and ionized Si levels changed the mesophyll conductance and the in uence of 3.2 mmol ionized-Si L − 1 , with an increase of 19.97%, was signi cant compared with control treatment, whereas other ionized-Si levels did not have a signi cant effect on mesophyll conductance of potato leaves. At 1.6 and 3.2 mmol nano-Si L − 1 , the mesophyll conductance showed a signi cant difference of 17.79% and 33.96% compared to control, respectively. The highest mesophyll conductance of both Si sizes was observed in 3.2 mmol Si L − 1 ( Table 2).
Similar to the results of net photosynthetic rate, either ionized or nano Si application improved the water use e ciency of potato and these changes differed under the in uence of the particle size. The signi cant effect of ionized particles on WUE was observed with the increase of 56.59% and 124.03% compared with control at 2.4 and 3.2 mmol Si L − 1 levels, respectively. The whole nano-Si levels had a signi cant effect on the WUE of potato leaves at the tuberization stage and by increasing concentration WUE changes were more noticeable. Furthermore, the in uence of nanoparticles was signi cantly higher than ionized particles at both 1.6 and 2.4 mmol Si L − 1 levels, but this difference was not signi cant in the highest concentration level (Table 2).

Biochemical traits
The silicon particle size (P) signi cantly affected chlorophyll a (Chl a), chlorophyll b (Chl b), and carotenoids (Cart) content of potato leaves, but no signi cant effect was observed on chlorophyll a/b ratio (Chl a/b), the capacity of DPPH radical scavenging and total phenol content. Si concentration levels (C) showed a signi cant effect on all measured biochemical traits. Although the interaction between P and C was not signi cant on chlorophyll a/b ratio and carotenoids content, these effects were signi cant in the other biochemical characteristics as well ( Table 1).
The application of ionized-Si particles had no signi cant effect on chlorophyll a and b content, whereas the foliar application of nano-Si levels improved chlorophyll a and b contents in potato leaves. At 2.4 and 3.2 mmol nano-Si L − 1 levels, chlorophyll a content was increased by 17.90% and 28.13% compared with control, respectively (Table 4). Furthermore, the highest signi cance of chlorophyll a content was recorded at 3.2 mmol nano-Si L − 1 . The signi cant in uences of nanoparticles on chlorophyll b content were observed by 11.52, 13.90, and 17.29 % at 1.6, 2.4, and 3.2 mmol Si L − 1 compared with control, respectively. There was no signi cant difference between mentioned nano-Si levels ( Table 4). Foliar application of 3.2 mmol Si L − 1 enhanced the chlorophyll a/b ratio compared with control in potato leaves, whereas the in uence of other Si treatments was not signi cant on this ratio ( Table 4). The results showed that the carotenoids content of potato leaves was higher by 6.25% under nano-Si application than ionized-Si (Table 5). In potato plantlets treated with 2.4 mmol Si L − 1 , carotenoids content was also signi cantly higher compared with control (P < 0.05), whereas other Si treatments was not effective (Table 3). The presented values are the means ± standard deviation from thirty data (n = 30). LSD: The least signi cant difference at P < 0.05.  (Table 4).
The effect of both particle sizes on total phenol content at 0.8 mmol Si L − 1 , were not signi cant. The highest in uence of ionized observed at 1.6 mmol Si L − 1 by 18.99% difference compared with control but, ionized-Si concentration increased to more than 1.6 mmol Si L − 1 , phenol content decreased (Table 4).
Increasing concentration of nano-Si particles also improved the total phenol content of potato leaves and the highest total phenol content was observed at 2.4 and 3.2 mmol nano-Si L − 1 by 36.24% and 42.79% difference compared with control, respectively ( Table 4). The difference between 2.4 and 3.2 mmol nano-Si L − 1 levels was also not signi cant. The total phenol content of nanoparticle treated plants was signi cantly higher than ionized at 3.2 Si mmol L − 1 (Table 4).

Mini-tuber yield
The silicon particle size (P) was signi cantly effective on the mean of mini-tuber weight (TW) and mini-tuber yield (TY) ( Table 1). Silicon concentration levels (C) also showed a signi cant effect on mini-tuber yield, but their sole and interaction effects were not signi cant on the mean mini-tuber weight. In comparison with the ionized-Si treatment, the nano-Si signi cantly increased the mean of mini-tuber weight (Table 5), and a similar result was observed in the mini-tuber yield ( Table 5). The potato mini-tuber yield signi cantly improved by increasing the Si concentration levels, and all Si treatments showed a signi cant difference with control (P < 0.05). These changes increased by increasing Si levels and the highest mini-tuber yield was observed at 3.2 mmol Si L − 1 (Table 3).
Please insert Table 5 near hear

Correlation results
The correlations among the different characteristics were calculated using Pearson's correlation coe cients ( Table 6). As shown in Table 6, mini-tuber yield was positively and signi cantly correlated with Pn (P < 0.01), WUE (P < 0.001), Chl a (P < 0.001), Chl b (P < 0.05), Chl a/b ratio (P < 0.05), scavenging DPPH radical (P < 0.01) and total phenol (P < 0.01) in nano-Si treatments and negative signi cant relationship was observed between mini-tuber yield and Tr (P < 0.01). In ionized-Si treatment, mini-tuber yield was positively and signi cantly correlated with WUE (P < 0.05) and Chl a (P < 0.05). The Tr in both nano-Si and ionized-Si treatments showed negative relationship with other measuring characteristics.

Please insert table 6 near hear 4 Discussion
In this experiment, the foliar application of silicon concentrations enhanced gas exchange parameters, pigment contents, antioxidant capacity, and mini-tuber yield of potato which are consistent with previous reports regarding the bene cial in uences of Si supplementation on antioxidant activities, growth and yield of other crops including cucumber [5], barley [27], soybean [29,30], banana [14] and tomato [8].
In this study, the increasing Pn and pigment content was apparent at concentrations above 1.6 mmol L − 1 of both Si sizes. These results were in agreement with studies on tomato, cucumber, and soybean which indicated the positive in uence of Si supplement on the Pn and Chl content of leaves in hydroponic conditions [5,8,30]. Furthermore, our results indicated that DPPH radical scavenging was clearly increased by Si particles in the tuberization stage of potato. There might be numerous mechanisms involved in the in uence of silicon on net photosynthesis however, an increase in antioxidant capacity as a result of Si induction may be the possible mechanism. Feng et al. (2010) [10] showed that Si could promote net photosynthesis, which is related to the individual role of Si in protecting photosynthesis apparatus from ROS damages. Furthermore, in similar previous reports it was proposed that silicon helps to improve the stability of cell plasma membranes [29], the integrity (thylakoids, grana lamellae) and function of chloroplast [8, 9,10] and following that the electron transport chain in thylakoid membranes for the production of ATP and NADPH will be protected against ROS [9] by promoting antioxidant system for detoxifying reactive oxygen species [10,30]. Our results also showed that total phenol content in potato leaves was enhanced signi cantly by Si at above 0. reported that the application of 3.6 mM Si stimulated phenolic acids and avonoids in rose (Rosa hybrida). They suggested that Si can promote the expansion of genes encoding enzymes and transcript levels in the phenylpropanoid pathways compared with untreated Si plants. Phenolic components can impress plant development via lignin and pigment biosynthesis or accumulation in the subepidermal layers of plant tissues [30] and the up-regulation biosynthesis of phenols in chloroplasts could enhance radiation intercept in leaves [31]. So, increasing phenol content induced by Si has in uenced the structure, function, and protection system of potato leaves, especially in the chloroplast. Since increase of DPPH radical scavenging and total phenols content under the in uence of silicon was simultaneously accompanied with improvement in photosynthetic pigments, the probable conclusion can be that partial increasing concentration of photosynthesis pigments (chlorophyll a and b) may depend on maintaining ultrastructure and orderliness of chloroplast or improving of chlorophyll biosynthetic pathways as a consequence of Si-related up-regulation of antioxidant system and phenol components.
Several previous reports have shown silicon can regulate the activities of main photosynthetic enzymes of Calvin cycle [5,11]. Adatia and Bestford (1986) [5] reported that the Si addition to nutrient solution enhanced carboxylase activity (RubisCO) of cucumber leaves under normal conditions. Similar ndings were reported for barley [27] and Spartina densi ora [11] under saline and Cu toxicity stresses. Silicon application increased the activity of phosphoenol pyruvate carboxylase in wheat under drought conditions [32]. Hence it seems that in this experiment, part of the Si in uence has been linked with activity regulation of key enzymes in non-photochemical photosynthetic processes. Moreover, up-regulation endogenous phytohormones such as GAs, IAA, and cytokines in Sitreated plants as reported for mango under drought stress [33] or GA 1 in soybean leaves under normal hydroponically conditions [28] mentioned in previous studies. In conclusion, it is likely that enhance of chlorophyll content and Pn were correlated with an increase of growth regulators in Si-treated potato leaves.
Results of this study indicated that by increasing Si concentration, Chl b content was signi cantly increased at 1.6 and carotenoids increased at 3.2 mmol L − 1 of Si. The Chl b and carotenoids are considered as an antenna and auxiliary pigments for Chl a reaction centers. Therefore, an increase in carotenoids and Chl b can be helpful for the absorption of light energy for electron transport photosystems in Chl a [34]. It is possible to suggest a positive role of Si in controlling photoinhibition of potato leaves. Since the absorption spectrum of Chl a and Chl b are different, it seems that an increase in the Chl a/b ratio can determine the quality of light-harvesting by leaf. Moreover, the nding of Kitajima and Hogan (2003) veri ed that improvement of Chl a/b accompanied by an increase in the electron transport rate in reaction centers of Chl a and rubisco carboxylation capacity which are in agreement with our results that shown a positive correlation between Pn with Chl a and Chl a/b in two scales of Si particle treatments (Table 6).
Based on this study results, an increase of Pn was simultaneously accompanied with decrease of Tr in Si-treated leaves at the tuberization growth stage.
Nevertheless, the Gs was not affected by Si treatments (Tables 1 and 2). If the limitation of Tr was due to stomatal closure, there should be a decrease in Ci.
However, Ci had a slight increase in Si-treated leaves with 2.4 and 3.2 mmol L − 1 . Therefore, the decrease in Tr may be due to nonstomatal restrictions which are in agreement with the results reported for S. densi ora [11] (Mateos-Naranjo et al. 2015) and tomato [35] treated with Si under salinity stress in greenhouse conditions. Various studies have described that by applying of silicon, the silica cuticle double layer was formed on the leaf epidermis which may reduce water loss through the cuticles of plants [11,14,36]. Although, the cuticular transpiration rate is lower than the stomatal transpiration rate, it can perform an important role in leaf water loss. Therefore, it seems that the decrease of Tr in Si-treated potato leaves most likely has been due to the reduction of cuticular Tr. Asmar et al. (2013) [14] suggested that the Si accumulation in epidermal tissue can have a positive effect on water relations in leaves during acclimatization under humidity changes in greenhouse conditions. Moreover, physical strength caused by Si deposition may develop mechanical protection to infection pathogens in crop leaves [18]. Therefore, it seems that foliar application of Si particles can be useful for the growth and health of potato plantlets are transferred to soilless culture. Our results also indicated that stomatal conductance did not change (Table 1) and it has not limited the CO 2 diffusion into substomata chamber or CO 2 assimilation in chloroplasts. Accordingly, an increase of Pn with Si may associate with the photosynthetic enzymatic process and chloroplast function.
Overall, silicon particles levels improved water use e ciency. Previous studies are in agreement with these results indicated that Si can enhance water use e ciency at the normal conditions in tomato [8,36]. Our results showed that a decrease in transpiration rate was accompanied by an increase of Pn in Sitreated leaves. Therefore, improvement of water use e ciency was predictable. A positive effect of Si application on mesophyll conductance of potato leaves was also in agreement with Haghighi and Pessarakli (2013) [8] results in cherry tomato. Our results showed that all Si levels had a positive effect on minituber yield. The ability of Si to increase yield production has been demonstrated in cucumber [5] and tomato [35].
According to this study, although net photosynthesis, pigment content, and yield measured in Si treatments were enhanced. These changes in nano-Si treated plants were more than ionized-Si. These results also indicated that potato leaves could foliar uptake of Si and nanoscale particles showed more e ciency in response to this method. The higher in uence of nanoparticles may be due to unique characteristics [8, 12,37] [37] showed that application of nano and ions Si in rice seedling under saline conditions increased growth, antioxidant activity, and biochemical traits such as soluble carbohydrates and amino acids, but the difference between particle sizes of Si was not noticeable.
Stomatal uptake can be a main pathway for the foliar uptake of mineral nutrients and other solutes [34] (Taiz et al., 2015), which can not able to penetrate through the surface of the epidermal cells. There are very ne pores with a diameter on a nanoscale on adaxial and abaxial leaf surface which are called ectodesmota with an approximate density of 10 10 per cm − 2 leaf area. Moreover, inside of this pores are covered with polygalacturonic acids, which only allow positive particles to enter [38] (Marschner 1995). It can be concluded that since in our study silicon solutions were acidic (pH = 5) and ectodesmota diameter was nanoscale, it seems that the high in uence of nano-Si treatments may be due to an increase of their foliar uptake via ectodesmota in potato leaves.

Conclusion
In this study, foliar application of Si particles imposed a remarkably positive role in the improving of photosynthetic, biochemical characteristics, and minituber yield of potato. Moreover, the nanoparticles was more effective than ionized-Si in many measured traits. As a result, it could be recommended that Si application improve the safety and tuber propagation of potato plantlets in soilless culture conditions. To maximize the in uence of Si treatment, the use of nanoparticles will be a proper strategy. Figure 1 The result of particle size analyzer (PSA) nano Si particles.