RU2541405C2 - Compound microfertiliser and method for production thereof - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to agriculture. A compound microfertiliser comprising boric acid, ammonium molybdate and potassium or sodium metasilicate, further includes, as an organic component which acts as a complexing agent, fullerenol obtained by direct catalytic oxidation of C₆₀ fullerene with an alkali, having the formula C₆₀(OH)_n1O_n2, where n1+n2=12-34, as well as calcium nitrate quadhydrate, potassium nitrate, potassium chloride, mono-substituted potassium phosphate, magnesium sulphate heptahydrate. All components are taken in a defined ratio. The method of producing the compound microfertiliser includes preparing a working solution by dissolving and mixing in tap water inorganic salts of macroelements and trace elements in the following sequence: calcium nitrate quadhydrate, potassium nitrate, potassium chloride, mono-substituted potassium phosphate, magnesium sulphate heptahydrate, potassium or sodium metasilicate, boric acid, ammonium molybdate to obtain a solution of macroelements and trace elements and adding aqueous fullerenol solution of the formula C₆₀(OH)_n1O_n2, where n1+n2=12-34, wherein pH of the working solution is 5.5-6.0.

EFFECT: invention enables to produce a compound water-soluble microfertiliser with growth-stimulating, phytoprotection and adaptogenic properties.

2 cl, 13 tbl

Description

The invention relates to the field of nanoindustry and agriculture and can find wide application in the cultivation of crops in field and regulated conditions.

For the intensification of production and the stable production of high yields of high-quality plant products in the Russian Federation, there is a need for agriculture to develop and introduce new environmentally friendly and highly effective preparations with complex positive effects on plants: stimulation, adaptogenic, phytoprotective. At the same time, the need to expand the scope of nanomaterials and introduce them into agriculture makes the development of drugs with the above properties based on them relevant.

Fullerenols nanomaterials are polyhydroxylated water-soluble derivatives of fullerenes, which are an allotropic modification of carbon and are characterized, in contrast to its other forms - diamond and graphite - by molecules that are strictly defined by molecular weight and properties. In relation to biological objects, such qualities of fullerenols as antioxidant properties, antiviral and antimicrobial activity, ability to penetrate through cell walls and biological membranes and at the same time serve as carriers of a number of biologically active substances to target cells have been identified to date. All this indicates the possibility of using these nanomaterials, in particular, in crop production to increase productivity and sustainability of crops.

Analogues - preparations based on fullerenols for use in crop production have not yet been created.

Organomineral micronutrient fertilizers can be considered as functional analogues containing organic compounds and complex macro-and micronutrients necessary for plant life as complexing agents.

Comprehensive microfertilizer and a method for its preparation are known, as set forth in the application for invention RU 2004100512, IPC 7 C05F 11/02, C05F / 3/00, claimed on 05.01.2004. Micronutrient fertilizer contains humic acids, microelements for plant nutrition, including copper sulfate, auxiliary substances - elements of plant mineral nutrition, including zinc sulfate, cobalt sulfate, ammonium molybdenum acid, and is characterized by an additional content of manganese sulfate, trilon B and organic adhesive, in the quality of which is used polyvinyl alcohol in a 5% solution at the ratio of components specified in the claims. Despite the positive effect of this microfertilizer on plants, its disadvantages include the absence of microelements in the composition of the microfertilizer that are important for plant life - boron and iron, and most importantly - silicon, whose compounds have phytoprotective properties, positively affect the metabolic processes of plants, contribute to an increase the effectiveness of mineral nutrition and increased resistance to stress factors.

A known method of stimulating plant growth (US Pat. RF No. 2088086, 6 IPC A01N 59/00, claimed 09.01.1992, publ. 08.27.1997), which consists in treating the seeds and watering the plants during the growing season with an aqueous solution containing 10 ^-6 -10 ^-4 mol / L hydrogen peroxide, 10 ^-6 -10 ^-5 g / ion of copper ions and 10 ^-6 -2 · 10 ^-6 mol / L of oxalic acid. The disadvantage is the absence of the main macronutrients and other trace elements important for plant life in the composition of the micronutrient fertilizer, the compounds of which possess phytoprotective and adaptogenic properties, positively affect the metabolic processes of plants, increase the efficiency of mineral nutrition and increase resistance to stress factors.

Closest to the claimed microfertilizer is a complex water-soluble microfertilizer according to the author's certificate of the USSR No. 743641, MKl. ² A01G 31/00, C05D 9/02, claimed 10.20.78, which we adopted as a prototype. This micronutrient fertilizer used for processing plants and intended for intensive cultivation of plants in protected ground contains 15 trace elements, including (in weight%) boric acid (0.004-0.01), cobalt chloride (0.001-0.003) and copper sulfate ( 0.001-0.003), and additionally includes potassium or sodium metasilicate (0.30-0.35) and trace elements: ferrous sulfate (0.02-0.06), aluminum sulfate (0.006-0.020), manganese sulfate (0.002- 0.008), zinc sulfate (0.001-0.004), potassium iodide (0.001-0.004), potassium bromide (0.001-0.004), ammonium molybdenum acid (0.00 1-0.003), sodium tungstate (0.0006-0.001), potassium chromate (0.0004-0.002) and ammonium vanadate (0.0004-0.001), and as a chelating agent nitric or citric acid, which is taken in the amount necessary to establish the reaction of the solution to a pH of 5.5-6.0.

The disadvantages of the prototype microfertilizers include a short shelf life of the drug (up to three months) without impairing its functionality, which is associated with the use of citric or nitric acids, which are actively consumed by microorganisms, as a complexing agent. In addition, the presence of these complexing agents in the prototype does not provide a high phytoprotective function of the drug against phytopathogenic microorganisms. The disadvantages of the prototype can also be attributed to the complexity of the trace element composition. In our previous studies, it was found that the number of trace elements can be reduced without compromising the effectiveness of microfertilizer, while its cost is reduced.

A known method of producing liquid humic fertilizer (RF Patent No. 2181710, C05F 11/02, C05F 3/00, claimed 09.08.2000, publ. 04/27/2002), which consists in the fact that the estimated amount of vermicompost is mixed with peat, treated with a solution of potassium hydroxide , the mixture is defended twice for 19-24 hours, then mixed with a set of trace elements, including copper and / or boron, and also zinc or magnesium, molybdenum, and / or cobalt or selenium, and / or silicon oxide. The disadvantage of this method is the duration and complexity of the process of preparing a solution containing humic acids.

There is also a method of obtaining complex micronutrient fertilizers, described in the description of the invention according to the above copyright certificate of the USSR No. 743641. The method consists in preparing two uterine component aqueous solutions of trace elements and potassium or sodium metasilicate, which are stored at room temperature in separate tanks. To prepare the mother liquor of trace elements, the salts thereof listed above (in the form of crystalline hydrates) are used in the amounts indicated in the prototype, which are dissolved in tap water, acidified by the addition of nitric or citric acid (5-10 g / l) to a pH of 2.5-3, 0. To prepare the mother liquor containing silicon, potassium or sodium metasilicate is dissolved in tap water to the level of SiO ₂ in the form of Si (OH) ₄ - 0.12-0.13 g / l. To prepare the working solution specified in the prototype, the mother liquor is mixed in tap water in an amount of 20-40 g / l.

This method is conditionally accepted by us as a prototype.

The disadvantages of the prototype method include the use of nitric or citric acid as a complexing agent, which does not provide high biological effectiveness of the drug. In addition, the need to prepare two mother liquors complicates the process of its production, making it more material intensive and costly.

The objective of this technical solution is to create a new integrated water-soluble microfertilizer with growth-promoting, phytoprotective and adaptogenic properties, as well as developing a method for its production, which will increase productivity and increase plant resistance to adverse environmental factors. The claimed biologically active micronutrient fertilizer can be used for pre-sowing seed treatment and foliar treatment of plants during the growing season.

This is achieved by the fact that a complex water-soluble micronutrient fertilizer containing boric acid, ammonium molybdenum acid, and potassium or sodium metasilicate additionally contains as an organic component the complexing agent - fullerenol obtained by direct catalytic oxidation of fullerene C ₆₀ with alkali, as well as calcium nitrate four-water, potassium nitrate, potassium chloride, potassium phosphate monosubstituted, magnesium sulphate heptahydrate in quantities (g / l of tap water):

calcium nitrate tetrahydrate 0.20-0.30 potassium nitrate 0,050-0,055 potassium chloride 0,020-0,025 monosubstituted potassium phosphate 0,050-0,055 magnesium sulfate heptahydrate 0.102-0.107 potassium or sodium metasilicate 0.002-0.003 boric acid 0.010-0.015 ammonium molybdenum acid 0.006-0.007

direct fullerenol

catalytic oxidation of fullerene C ₆₀ 0.006-0.025

alkali, composition C ₆₀ (OH) _n1 O _n2 , where

n1 + n2 = 12 ÷ 34

A method of obtaining complex micronutrient fertilizers involves preparing a working solution by dissolving and mixing inorganic salts of macro- and microelements in tap water in the following sequence: calcium nitrate tetrahydrate; potassium nitrate; potassium chloride; monosubstituted potassium phosphate; magnesium sulfate; potassium or sodium metasilicate; boric acid; ammonium molybdenum acid to obtain a solution of macro- and microelements and adding to it an aqueous solution of fullerenol obtained by direct catalytic oxidation of fullerene C ₆₀ with alkali, composition C ₆₀ (OH) _n1 O _n2 , where n1 + n2 = 12 ÷ 34, while the pH of the working solution equal to 5.5-6.0.

The significance of the features of the alleged invention is confirmed by the following.

The patent and scientific literature describes a large number of different methods for the synthesis of fullerenols.

Fullerenol C ₆₀ (OH) ₂₄ can be obtained by alkaline hydrolysis of a polybromosubstituted fullerene C ₆₀ Br ₂₄ (A. Djordjevic, M. Vojinovic-Miloradov, N. Petranovic et al. Synthesis and characterization of water-soluble biologically active C ₆₀ (OH) ₂₄ Archive of Oncology, 1997, 5 (3), 139-41). The disadvantage of this method is the need for synthesis and purification of the primary bromine derivative of fullerene composition C ₆₀ Br ₂₄ .

In an article by K. Kokubo, K. Matsubayashi, H. Tategaki et al. Facile Synthesis of Highly Water-Soluble Fullerenes More Than Half-Covered by Hydroxyl Groups. ACS Nano, 2008, 2 (2), 327-333) describes the process of producing fullerenols with different gross composition and structure, in particular C ₆₀ (OH) ₃₆ · 8H ₂ O and C ₆₀ (OH) ₄₀ · 9H ₂ O, in which the water-soluble fullerene derivative C ₆₀ -C ₆₀ (OH) ₁₂ served as the starting material. The disadvantage of this method is the need for the synthesis of the primary compound of composition C ₆₀ (OH) ₁₂ .

Known methods for producing fullerenols directly from fullerene C ₆₀ . The catalytic oxidation of fullerene C ₆₀ with alkali gave fullerenol C ₆₀ (OH) _26.5 (Li J., Takeuchi A., Ozawa M, Li X., Saigo K., Kitazawa K. C ₆₀ fullerol formation catalysed by quaternary ammonium hydroxide. J Chem. Soc. Chem. Commun., 1993, 1784-1785), as well as a mixture of polyhydroxylated C ₆₀ fullerenes with the general formula: C ₆₀ (OH) _nl O _n2 (ONa) _n3 , n1 + n2 + n3 = 12 ÷ 34 (K.N. Semenov, D.G. Letenko, N.A. Charykov, et al. Synthesis and identification of fullerenol obtained by direct oxidation. Zh. Prikl. Chemistry, 2010, vol. 83, 12, pp. 1948-1952 ) A later work (KN Semenov, NA Charykov, VA Keskinov. Fullerenol Synthesis and Identification. Properties of the Fullerenol Water Solutions. J. Chem. Eng. Data, 2011, 56, 230-239) showed that direct fullerenol catalytic oxidation of fullerene C ₆₀ with alkali can have the composition C ₆₀ (OH) _n1 O _n2 and C ₆₀ (OH) _n1 O _n2 (ONa) _n3 , where n1 + n2 + n3 = 12 ÷ 34.

In our case, fullerenol obtained by the direct catalytic oxidation of fullerene C ₆₀ with alkali of the composition C ₆₀ (OH) _n1 O _n2 , where n1 + n2 = 12 ÷ 34, was used as an organic component acting as a complexing agent.

A working solution of complex micronutrient fertilizers is prepared immediately before processing seeds and vegetative plants as follows: to a solution of macro- and microelements, inorganic salts of which are mixed in a diluted form immediately before processing plants, add an aqueous solution of fullerenol obtained by direct catalytic oxidation of fullerene C ₆₀ with alkali, composition C ₆₀ (OH) _n1 O _n2 where n1 + n2 = 12 ÷ 34 (hereinafter fullerenol).

Previous studies of the effect of fullerenol in various concentrations on plants showed that their minimum values, at which a positive effect is observed, judging by the reaction of the roots and shoots of seedlings after seed treatment, are in the range of 6-25 mg / l (Tables 1 and 2) . At lower concentrations, fullerenol does not have a significant effect on plants, at concentrations in the range of 25-100 mg / l - the effect of fullerenol mainly has a similar effect in strength, as at 25 mg / l, at concentrations above 150 mg / l - a decrease is observed monitoring plant growth indicators.

Table 1. The length of the roots and shoots of watercress seedlings when treating seeds with fullerenol (F) in various concentrations The concentration of f in water, mg / l Root Length (mm) % of control Shoot length (mm) % of control 500 mg / l f 65.8 ± 5.1 * 67.3 * 39.2 ± 2.3 104.3 100 mg / l f 80.6 ± 6.6 * 82.4 * 42 ± 2.5 * 111.7 * 50 mg / l f 98.5 ± 5.2 100.7 42.3 ± 1.2 * 112.5 * 25 mg / l f 105.9 ± 8.3 108.3 41.4 ± 1.5 * 110.1 * 10 mg / l f 114.4 ± 7.6 * 117 * 36.5 ± 1.9 97.1 5 mg / l f 118 ± 7.6 * 120.7 * 35.8 ± 1.4 95.2 1 mg / l f 94.2 ± 6.2 96.3 36.2 ± 1.6 96.3 0.01 mg / l f 97.3 ± 10.2 99.5 37.3 ± 1.8 99,2 control (water) 97.8 ± 7.1 one hundred 37.6 ± 1.8 one hundred Note: * - the value significantly differs from the control at a 5% significance level.

Table 2. Parameters of barley seedlings after 24 hours of exposure of roots in solutions of fullerenol (F) of various concentrations (% of control in water) The concentration of f in water, mg / l The rate of elongation of shoots,% (dl / dt _sh ) The rate of elongation of the roots,% (dl / dt _r ) Longitudinal elongation,% (δl) Transverse Elongation,% (δD / D) The hydraulic conductivity of the membranes,% (L _p ) The intra-root osmotic pressure,% (P) 1100 88 ± 5 * 61 ± 7 * 86 ± 5 * 122 ± 7 * 102 ± 12 142 ± 12 * 150 100 ± 4 121 ± 5 * 95 ± 5 118 ± 5 * 123 ± 12 * 128 ± 8 * 75 95 ± 4 126 ± 4 * 108 ± 3 * 111 ± 5 * 110 ± 10 126 ± 7 * fifty 94 ± 5 126 ± 6 * 112 ± 4 * 119 ± 6 * 120 ± 12 * 118 ± 6 * 25 95 ± 6 124 ± 3 * 114 ± 5 * 126 ± 7 * 134 ± 14 * 112 ± 7 * fourteen 96 ± 3 124 ± 4 * 119 ± 5 * 131 ± 7 * 150 ± 32 * 104 ± 8 7 90 ± 6 112 ± 4 * 112 ± 4 * 116 ± 5 * 120 ± 7 * 105 ± 10 3 96 ± 5 104 ± 5 101 ± 5 97 ± 5 107 ± 8 91 ± 9 0 (control) 100 ± 4 100 ± 3 100 ± 3 100 ± 5 100 ± 5 100 ± 8 Note: * - the value significantly differs from the control at a 5% significance level. Parameters dl / dt _sh - shoot elongation rate, mm / h; dl / dt _r — root elongation rate, mm / h; δl — longitudinal elongation, mm; δD / D — transverse elongation, mm; L _p - hydraulic conductivity of the membranes, m / (MPa s); P - intra-root osmotic pressure, MPa was evaluated according to the method described in (Ktitorova I.N., Skobeleva O.V. The decrease in the hydraulic conductivity of rhizoderm cell membranes with nitrate deficiency is associated with acidification at the root surface // Plant Physiology. 2008. T. 55. S.690-698)

Inorganic salts are used to prepare a solution of macro- and microelements, which are dissolved in tap water in the sequence and amount shown in Table 3, after which an aqueous solution of fullerenol in concentrations of 6-25 mg / l of the solution is added to the macro- and microelement solution.

Moreover, the amount of each substance containing macro- and microelements is experimentally justified and selected to enhance the positive effect on fullerenol plants. It is shown that at a lower concentration of macro- and microelements, the effectiveness of micronutrient based on fullerenol decreases, with a higher concentration it does not significantly differ from that observed in the indicated range.

Table 3. The content of macro- and microelements in the working solution of biologically active micronutrient fertilizers based on fullerenol Substance name The amount of substance, g / l tetrahydrate calcium nitrate, 0.20-0.30 potassium nitrate 0,050-0,055 potassium chloride 0,020-0,025 monosubstituted potassium phosphate 0,050-0,055 magnesium sulfate heptahydrate 0.102-0.107 potassium or sodium metasilicate 0.002-0.003 boric acid 0.010-0.015 ammonium molybdenum acid 0.006-0.007 fullerenol 0.006-0.025

In this case, the pH of the working solution is 5.5-6.0.

The working solution is prepared immediately before processing the plants and can be stored at room temperature for a week.

To prove the technical result achieved by the proposed micronutrient fertilizer and the method of its production, experiments were conducted to establish the effectiveness of its action.

Under regulated conditions favorable for plant growth and development, when the manifestation of additional means of influence on the plant is least effective, the proposed microfertilizer with foliar treatment of barley, cucumber, and lettuce plants provided an increase in their biomass relative to the control (foliar treatment with water) by 8%, 29%, and 39%, respectively, and relative to the prototype - by 4%, 4% and 15%, respectively (table 4).

Table 4. Plant biomass under controlled conditions during foliar micronutrient treatment based on fullerenol (F) Option of non-root treatment of plants The mass of the vegetative aerial part mg % of control Barley (baking period) Water (control) 5500 ± 260 one hundred F-based microfertilizer 5930 ± 480 108 Prototype 5700 ± 350 104 Cucumber (fruiting period) Water (control) 655.3 ± 56.1 100 ± 9 F-based microfertilizer 845.7 ± 56.7 * 129.2 ± 9 * Prototype 812.4 ± 64.3 * 123.9 ± 8 * Salad (15 days from sowing seedlings) Water (control) 163.9 ± 12.3 100 ± 8 F-based microfertilizer 228.7 ± 20.3 * 139.5 ± 9 * Prototype 198.6 ± 13.9 * 121.2 ± 8 * Note: * - the value significantly differs from the control at a 5% significance level.

Non-root exposure to microfertilizer based on fullerenol contributed to an increase in the yield of tomato fruits by 17%, cucumber - by 28% relative to the control (water treatment) and by 7% and 9% - relative to the prototype (Tables 5 and 6).

Table 5. Tomato productivity in foliar treatment of plants with microfertilizer based on fullerenol (F) Option of non-root treatment of plants Number of fruits, pcs / plant The average weight of one fruit, g. The mass of fruits, g / plant. Fruit harvest kg / m % of control Water (control) 8.2 ± 0.5 55 ± 4.7 451 ± 50.5 9.9 ± 0.6 one hundred F-based microfertilizer 9.4 ± 0.6 * 62.0 ± 5.4 * 580 ± 54.5 * 11.6 ± 0.9 * 117 * Prototype 8.5 ± 0.6 58 ± 6.8 493 ± 58.4 10.8 ± 0.9 109 Note: * - the value significantly differs from the control at a 5% significance level. Table 6. Cucumber productivity in foliar treatment of plants with micronutrient fertilizers based on fullerenol (F) Option of non-root treatment of plants The mass of fruits, g / plant. Fruit harvest kg / m ² % of control Water (control) 1308.9 ± 100.8 10.5 ± 0.6 one hundred F-based microfertilizer 1678.7 ± 109.3 * 13.4 ± 0.9 * 128 * Prototype 1532.9 ± 104.9 * 12.3 ± 0.9 * 117 * Note: * - the value significantly differs from the control at a 5% significance level.

Under the natural conditions of the microfield experiment, foliar treatment of watercress and leaf lettuce plants with microfertilizer based on fullerenol caused an increase in their biomass by 63% and 46% relative to the control (non-root treatment with water) and 15% and 11% relative to the prototype (Table 7) .

Table 7. Mass of watercress and leaf lettuce during foliar treatment of plants with microfertilizer based on fullerenol (F) in the field Foliar treatment of plants Wet weight g / plant % of control Watercress Water 4.8 ± 0.4 100 ± 4 F-based microfertilizer 7.8 ± 0.4 * 163 ± 9 * Prototype 6.8 ± 0.4 * 142 ± 6 * Salad Water 125.3 ± 7.4 100 ± 6 F-based microfertilizer 183.2 ± 7.4 * 146 ± 9 * Prototype 164.4 ± 8.2 * 131 ± 8 * Note: * - the value significantly differs from the control (in the corresponding solution without f) at a 5% significance level

The positive effect of the proposed microfertilizer based on fullerenol is determined by the complex of beneficial microfertilizer properties, namely: the ability to bind free radicals (antioxidant properties), to serve as a carrier of nutrients in plants, to intensify the biosynthesis of chlorophylls and other compounds, etc.

On the example of studying changes in the concentration of nitrous oxide (a source of free radicals) in a nutrient solution, it was shown that UV-B irradiation of plants causes an increase in its concentration by 48% to 0.99 ppm (Table 8). The foliar treatment of barley plants with micronutrient fertilizers based on fullerenol provides a significant decrease (by 16%) in the concentration of nitrous oxide in the nutrient solution relative to the control under favorable and stressful conditions, completely eliminating the effect of oxidative stress caused by UV-B irradiation.

Table 8. Concentrations of nitrous oxide in the nutrient solution during foliar feeding of barley with micronutrient fertilizer based on fullerenol (F) under favorable conditions and when plants are irradiated with UV-B radiation (dose 20 kJ / m ² ) Non-root treatment option Nitrous oxide ppm % of control Favorable conditions Water (control) 0.67 one hundred F-based microfertilizer 0.56 * 83.6 * UV-B irradiation of plants The control 0.99 * 147.8 * F-based microfertilizer 0.56 * 83.6 * * - the value significantly differs from the control at a 5% significance level

It was revealed that under thermal stress, when the roots of plant seedlings after their pre-exposure in a solution of macro- and microelements included in the proposed microfertilizer, as well as in a micronutrient solution based on fullerenol, were exposed to a 10-minute heating at 40-42 ° C, negative the effect of this stress on the growth of roots and seedlings decreased significantly (by 12–16%) (Table 9).

Table 9. The effect of micronutrient fertilizers based on fullerenol (F) on wheat seedlings under heat stress (in% of the control, the control being plants grown under favorable conditions on a solution of macro- and micronutrients that are part of the proposed micronutrient) Experience Options Biophysical parameters The elongation rate of shoots dl / dt _sh ,% The rate of elongation of the roots, dl / d _tr ,% Longitudinal elongation, δl,% Control and stress 77 ± 8 14 ± 5 67 ± 4 F + stress microfertilizer 93 ± 6 26 ± 5 80 ± 5

It was shown that under the influence of salt stress in the root habitat in control plants of barley and wheat grown on a solution of macro- and microelements that are part of micronutrient fertilizers based on fullerenol, a sharp inhibition of root growth was observed, associated with a decrease in the longitudinal elongation of the roots δl and less pronounced inhibition shoot growth (table 10). The pre-exposure of plants in a micronutrient solution based on fullerenol mainly completely neutralized the negative effect of subsequent salt stress on plant seedlings. The main reason for accelerating the growth of the roots of barley and wheat in the presence of fullerenol-based micronutrient fertilizers is an increase in the longitudinal elongation of the roots in the growth zone δl.

Table 10. The effect of micronutrient fertilizers based on fullerenol (F) on seedlings of barley and wheat under salt stress (in% of control *) Parameters of seedlings Barley Wheat Root exposure conditions Root Exposure Conditions The control Control and stress F-based micro fertilizer and stress The control Control and stress F-based micro fertilizer and stress The elongation rate of shoots dl / dt _sh ,% 100 ± 5 71 ± 7 * 81 ± 8 * 100 ± 5 78 ± 8 * 95 ± 8 The rate of elongation of the roots, dl / dt _r ,% 100 ± 6 31 ± 5 * 135 ± 13 * 100 ± 6 53 ± 4 * 101 ± 8 Longitudinal elongation, δl,% 100 ± 4 60 ± 5 * 105 ± 6 100 ± 4 72 ± 6 * 90 ± 7 Note: * "control" - the roots in the solution of macro- and microelements that are part of micronutrient fertilizers; "control and stress" - the roots of a solution of macro- and microelements + 4.4 g NaCl / l solution; "F-based microfertilizer and stress" - the roots in the working microfertilizer based on F + 4.4 g NaCl / l solution.

The introduction of fullerenol-based micronutrient fertilizers into the root habitat and foliar treatment of plants with them contributed to a significant increase in the content of basic macroelements and their mobile forms in plants, as well as in the content of protein nitrogen.

Thus, non-root treatment of plants with micronutrient fertilizers based on fullerenol provides an increase in their aerial parts of the gross nitrogen content by 30%, phosphorus - by 43%, potassium - by 15%, non-protein nitrogen - by 62%, protein nitrogen - by 27%, nitrate nitrogen - by 20%, ammonium nitrogen - by 49% (Table 11). An increase in the content of chlorophyll pigments in plant leaves was also noted, namely: the content of chlorophyll a increases by 7% (trend), while chlorophyll b - by 25%, the sum of chlorophyll a and b - by 14%, which indicates the activation of biosynthesis and in general, metabolism in plants (table 12).

Table 11. Gross content of the main macroelements and various forms of nitrogen in the aerial part of the salad during foliar treatment of plants with micronutrient fertilizers based on fullerenol (F) Non-Root Processing Options Substance content Nitrogen,% A.W. Phosphorus A.S. Potassium,% a.s.w. Non-protein nitrogen,% a.s.w. Protein nitrogen,% a.s.w. Ammonium nitrogen,% a.s.w. Nitrate nitrogen, mg / kg Solution of macro and micro elements (control) 2.04 0.28 5.61 0.196 1.84 0 401.0 F-based microfertilizer 2.65 * 0.40 * 6.43 * 0.317 * 2.33 * 0,049 * 482.0 * * - the value significantly differs from the control at a 5% significance level; "a.s.v." - absolutely dry matter

Table 12. The content of carbon- and nitrogen-containing substances in the aerial part of the salad during foliar feeding of plants with micronutrient fertilizer based on fullerenol (F) Non-Root Processing Options Substance content Monosahara,% a.s.w. Disahara,% a.s.w. Sum of sugars Lignin% A.S. Chlorophyll, mg / 100 g. Chlorophyll b, mg / 100 g. The amount of chlorophyll mg / 100 g Carotenoids, mg / 100 g The solution of macro - and trace elements (control) 8.6 9.26 17.86 5.64 12.38 7.03 19.40 6.01 F-based microfertilizer 10.85 * 5.58 * 16,43 4.39 * 13.27 8.80 * 22.07 * 6.25 * - the value significantly differs from the control at a 5% significance level; "a.s.v." - absolutely dry matter

It was also shown that when micronutrient fertilizers based on fullerenol are introduced into the soil substitute, there is an increase in the transport of nitrate nitrogen, as well as mobile forms of phosphorus and potassium in plants (Table 13). Moreover, the nitrate content in plant products does not exceed the MPC (Hygienic requirements for safety and nutritional value of food products. SanPiN 2.3.2.1078-01 ", 06.11. 2001).

The enrichment of plants with phosphorus, potassium, nitrogen at the root and, especially, at non-root treatment of plants with micronutrient fertilizers based on fullerenol is an important positive effect and, when used in agricultural production, will reduce the dose burden on fertilizer agroecosystems.

Table 13. The gross content of the main macroelements and various forms of nitrogen in the aerial part of the salad when microfertilizers based on fullerenol (F) are introduced into the soil substitute on the basis of high peat low decomposition Non-Root Processing Options Substance content Nitrogen,% A.W. Phosphorus,% a.s.w. Potassium,% a.s.w. Non-protein nitrogen,% a.s.w. Protein nitrogen,% a.s.w. Ammonium nitrogen,% a.s.w. Nitrate nitrogen, mg / kg Crude ash,% a.s.w. Water (control) 1.87 0.24 4.89 0.168 1.70 0 493 15.44 F-based microfertilizer 2.0 * 0.32 * 5.01 0.224 1.78 * 0 1,031.0 * 15.28 * - the value significantly differs from the control at a 5% significance level; "a.s.v." - absolutely dry matter

Thus, the results of evaluating the effectiveness of the developed microfertilizer based on fullerenol on plants under controlled and field conditions show that microfertilizer has growth-stimulating, phytoprotective antioxidant and adaptogenic properties, provides increased assimilation of mineral nutrients by plants by enhancing their transport to plants and activating processes metabolism in plants.

The examples of the application of the developed microfertilizer based on fullerenol for foliar and root treatment of plants in controlled and field conditions show its advantage over the prototype and indicate its higher efficiency compared to it.

The advantage of the developed microfertilizer based on fullerenol in comparison with the prototype also lies in the fact that there is no need to prepare mother liquors, all microfertilizer components are solid and dissolve in tap water in the sequence shown in table 3 for preparing the working solution immediately before processing the crops.

Claims (2)

1. A complex micronutrient fertilizer containing boric acid, ammonium molybdenum acid, and potassium or sodium metasilicate, characterized in that it additionally contains fullerenol obtained by direct catalytic oxidation of fullerene C ₆₀ with alkali as an organic component that performs the functions of a complexing agent (composition C ₆₀ ( OH) _n1 O _n2, where nl + n2 = 12 ÷ 34, as well as calcium chetyrehvodny nitrate, potassium nitrate, potassium chloride, potassium dihydrogen phosphate, magnesium sulfate heptahydrate in an amount (g / l vodoprov discharge of water):
calcium nitrate tetrahydrate 0.20-0.30 potassium nitrate 0,050-0,055 potassium chloride 0,020-0,025 monosubstituted potassium phosphate 0,050-0,055 magnesium sulfate heptahydrate 0.102-0.107 potassium or sodium metasilicate 0.002-0.003 boric acid 0.010-0.015 ammonium molybdenum acid 0.006-0.007 fullerenol obtained by direct catalytic oxidation of fullerene C ₆₀ 0.006-0.025
alkali, composition C ₆₀ (OH) _n1 O _n2 ,
where nl + n2 = 12 ÷ 34 2. The method of obtaining complex micronutrient fertilizer according to claim 1 includes the preparation of a working solution by dissolving and mixing inorganic salts of macro- and microelements in tap water in the following sequence: calcium nitrate tetrahydrate; potassium nitrate; potassium chloride; monosubstituted potassium phosphate; magnesium sulfate; potassium or sodium metasilicate; boric acid; ammonium molybdenum acid to obtain a solution of macro- and microelements and adding to it an aqueous solution of fullerenol obtained by direct catalytic oxidation of fullerene C ₆₀ with alkali, composition C ₆₀ (OH) _n1 O _n2 , where nl + n2 = 12 ÷ 34, while the pH of the working solution equal to 5.5-6.0.