Glycoside-containing extractive-containing crop stress resistance, yield increase and efficiency increase fertilizer and preparation method thereof

Abstract

This invention relates to the field of agricultural fertilizer technology and provides a crop stress-resistance, yield-increasing, and efficiency-enhancing fertilizer containing glycoside extracts and its preparation method. The fertilizer comprises the following raw materials in parts by weight: 4-10 parts of glycoside extracts, 10-15 parts of modified carboxymethyl cellulose, 3-7 parts of bacterial cellulose-chitosan carboxymethylated compound, and 50-70 parts of macro-element fertilizer base material. This invention forms a core layer by combining the glycoside extracts and modified carboxymethyl cellulose, and then chemically coating the surface of the core layer with bacterial cellulose-chitosan carboxymethylated compound, forming a double-layer protective microcapsule. This significantly improves the stability of glycosides in alkaline compound fertilizers and also has pH-responsive release characteristics, allowing the release of glycosides on demand in the acidic environment of the crop rhizosphere, effectively enhancing crop stress resistance and achieving increased crop yield and efficiency.

Description

Technical Field

[0001] This invention belongs to the field of agricultural fertilizer technology, and in particular relates to a crop stress-resistant, yield-increasing and efficiency-enhancing fertilizer containing glycoside extracts and its preparation method. Background Technology

[0002] Glycosides (such as saponins, flavonoid glycosides, iridoid glycosides, etc.) are a class of natural products with significant biological activity. They can induce systemic acquired resistance in plants and enhance the tolerance of crops to abiotic stresses such as drought and salinity, and have broad application prospects in the agricultural field.

[0003] However, the application of glycoside extracts in fertilizers faces a key challenge: poor chemical stability under alkaline conditions. Most commercially available compound fertilizers (especially those containing urea and diammonium phosphate) are alkaline, with pH values ​​typically between 8 and 10. The glycosidic bonds in glycoside molecules are easily hydrolyzed under alkaline conditions, and the phenolic hydroxyl groups are easily oxidized, leading to a significant decrease in their activity during fertilizer processing and storage.

[0004] In existing technologies, the main methods to solve this problem include physically mixing glycosides with carriers such as humic acid and cyclodextrin, or using coating technology for isolation. However, physical mixing cannot fundamentally solve the chemical attack of glycosides on alkaline environments. Furthermore, conventional coating materials themselves will swell or degrade under alkaline conditions, resulting in limited protective effects. Therefore, developing a technical solution that can effectively protect the activity of glycosides in alkaline fertilizer environments is of great practical significance. Summary of the Invention

[0005] This invention provides a crop stress-resistance, yield-increasing, and efficiency-enhancing fertilizer containing glycoside extracts and its preparation method, aiming to solve the technical problem that glycoside extracts are easily hydrolyzed and deactivated in alkaline compound fertilizers in the prior art.

[0006] The core inventive concept of this invention is to construct a dual-layer protection system consisting of an inner layer of encapsulation protection and an outer layer of physical barrier, with the inner and outer layers forming an integrated structure through chemical bonding.

[0007] The aminated cyclodextrin in the inner layer of modified carboxymethyl cellulose encapsulates glycoside molecules through host-guest interactions, achieving molecular-level protection of glycosides. Simultaneously, the three-dimensional cross-linked network formed by oxidized carboxymethyl cellulose and aminated cyclodextrin via Schiff base reaction enhances the structural stability of the core layer in alkaline environments. The carboxymethyl cellulose backbone is pH-sensitive, exhibiting a dense structure in alkaline environments and a contracted structure in acidic environments, thereby enabling the on-demand release of glycosides.

[0008] The outer bacterial cellulose-chitosan carboxymethyl compound, through carboxylation, introduces carboxyl groups that form amide bonds with the amino groups on the inner modified carboxymethyl cellulose, covalently linking them to the core surface to form an integrated protective shell. This outer material exhibits a dense structure in alkaline environments, effectively isolating the alkaline fertilizer environment as a physical barrier. In acidic environments, the inner structure shrinks, disrupting the integrity of the microcapsules and synergistically facilitating glycoside release. This integrated structure significantly improves the stability of glycosides in alkaline fertilizers while ensuring reliable on-demand release in acidic environments.

[0009] This invention is achieved by providing a crop stress-resistance, yield-increasing, and efficiency-enhancing fertilizer containing glycoside extracts, comprising the following raw materials in parts by weight: The mixture contains 4-10 parts of glycoside extract, 10-15 parts of modified carboxymethyl cellulose, 3-7 parts of bacterial cellulose-chitosan carboxymethyl compound, and 50-70 parts of macro-element fertilizer base material. Preferably, the macro-element fertilizer base material is a mixture of urea, diammonium phosphate, and potassium chloride in a mass ratio of 3:2:1, with a pH value of 8.5-9.5. The modified carboxymethyl cellulose is chemically bonded to oxidized carboxymethyl cellulose and aminated cyclodextrin via a Schiff base reaction, and has a dual function: the hydrophobic cavity of the aminated cyclodextrin includes glycoside molecules through host-guest interactions, achieving molecular-level protection of glycosides; at the same time, the three-dimensional cross-linked network structure formed by oxidized carboxymethyl cellulose and aminated cyclodextrin via the Schiff base reaction enhances the structural stability of the core layer in an alkaline environment and provides chemical bonding sites for the outer layer material.

[0010] The bacterial cellulose-chitosan carboxymethyl compound is a complex obtained by physically combining bacterial cellulose and chitosan and then modifying it with carboxymethylation. The carboxyl groups introduced by carboxymethylation can undergo amidation reaction with the amino groups on the inner modified carboxymethyl cellulose to form chemical bonds, thereby firmly connecting the outer layer to the surface of the core layer and forming an integrated protective shell.

[0011] Preferably, the raw materials include the following in parts by weight: 6-8 parts of glycoside extract, 11-14 parts of modified carboxymethyl cellulose, 4-6 parts of bacterial cellulose-chitosan carboxymethyl compound, and 55-65 parts of macro-element fertilizer base material.

[0012] Preferably, the raw materials include the following in parts by weight: 7 parts of glycoside extract, 12 parts of modified carboxymethyl cellulose, 5 parts of bacterial cellulose-chitosan carboxymethyl compound, and 60 parts of macro-element fertilizer base material.

[0013] Preferably, the glycoside extract includes at least one of ginsenoside, astragaloside, and geniposide.

[0014] Preferably, the modified carboxymethyl cellulose is prepared as follows: (1) Dissolve carboxymethyl cellulose and sodium periodate in water at a mass ratio of 1:0.2-0.4, and the mass ratio of carboxymethyl cellulose to water is 1:10-20. Adjust the pH to 3-4 and react at 20-30℃ in the dark for 3-5 hours. After the reaction is completed, add ethylene glycol to terminate the reaction, purify and dry to obtain oxidized carboxymethyl cellulose (aldehyde content is 0.5-1.2 mmol / g). (2) Dissolve cyclodextrin (preferably β-cyclodextrin) with epichlorohydrin and ethylenediamine in water at a mass ratio of 1:0.3-0.6:0.5-1.0, with the mass ratio of β-cyclodextrin to water being 1:3-8. React at 50-70℃ for 5-7 hours. After the reaction is complete, adjust the pH to neutral, precipitate and dry to obtain amino-substituted cyclodextrin (degree of substitution of 0.4-0.7). (3) Dissolve oxidized carboxymethyl cellulose and aminocyclodextrin in water at a mass ratio of 1:0.5-1.5, with a total solid content of 1-5%, adjust the pH to 6.5-7.5, chemically bond them at 35-40℃ through Schiff base reaction for 4-6 hours, and dry them to obtain modified carboxymethyl cellulose.

[0015] The three-dimensional cross-linked network formed by the Schiff base reaction works synergistically with the pH sensitivity of the carboxymethyl cellulose skeleton in an alkaline environment, further enhancing the structural stability of the core layer and providing dual protection for the long-term protection of the microcapsules in alkaline fertilizer environments.

[0016] Preferably, the preparation method of the bacterial cellulose-chitosan carboxymethyl compound is as follows: (1) Add bacterial cellulose and chitosan to a 0.5-2% acetic acid aqueous solution at a mass ratio of 1:0.5-1.5, and the mass ratio of bacterial cellulose to acetic acid aqueous solution is 1:20-50. Stir and compound at 20-30℃ for 1-3 hours, and freeze dry to obtain bacterial cellulose-chitosan complex. (2) Add the bacterial cellulose-chitosan complex and chloroacetic acid to a mixed solvent of isopropanol-water at a mass ratio of 1:0.5-1.0, add sodium hydroxide to adjust the pH to 8-10, react at 50-70℃ for 3-6 hours, neutralize with dilute hydrochloric acid after the reaction, filter, wash with 70-80% ethanol, and dry to obtain bacterial cellulose-chitosan carboxymethylated product.

[0017] The present invention also provides a method for preparing the above-mentioned crop stress-resistance and efficiency-enhancing fertilizer containing glycoside extracts, comprising the following steps: S1: Prepare all raw materials according to the proportions; S2: Glycoside extracts are mixed with modified carboxymethyl cellulose and granulated in a fluidized bed to obtain core particles; S3: Disperse bacterial cellulose-chitosan carboxymethylated compound in water, add an activator to activate it. The total mass of the activator is 1%-3% of the mass of bacterial cellulose-chitosan carboxymethylated compound. It is used to activate the carboxyl groups in the outer layer material, so that they undergo an amidation reaction with the amino groups on the surface of the core layer particles to achieve chemical bonding and obtain an activated emulsion. S4: Place the core layer particles in a fluidized bed and spray an activation emulsion to allow the bacterial cellulose-chitosan carboxymethyl compound to chemically bond with the surface of the core layer particles; S5: Drying to obtain double-layered protective microcapsules; S6: Mix the double-layer protective microcapsules with the base material of macro-element fertilizer and granulate to obtain the finished product.

[0018] Preferably, in S3, the activator is a mixture of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide, with a mass ratio of 2:1, and the total amount of activator added is 1%-3% of the mass of bacterial cellulose-chitosan carboxymethylated material; in S2, the inlet air temperature of fluidized bed granulation is 40-50℃, and the atomization pressure is 0.2-0.4MPa; in S4, the atomization pressure of spraying the activated emulsion is 0.3-0.5MPa, the spraying rate is 5-10mL / min, the fluidized bed temperature is 40-50℃, and the spraying time is 30-90 minutes.

[0019] Compared with the prior art, the embodiments of this application have the following main advantages: The crop stress-resistance, yield-increasing, and efficiency-enhancing fertilizer containing glycoside extracts provided by this invention utilizes modified carboxymethyl cellulose and bacterial cellulose-chitosan carboxymethylated compounds. A core layer is formed by chemically bonding the glycoside extracts and modified carboxymethyl cellulose through a Schiff base reaction. The bacterial cellulose-chitosan carboxymethylated compounds are then chemically coated onto the surface of the core layer, forming a double-layered protective microcapsule. The outer layer acts as a physical barrier, effectively isolating the alkaline fertilizer environment. The inner layer is pH-responsive; in the acidic rhizosphere environment, the structure shrinks due to carboxylation, allowing for the on-demand release of glycosides. The inner and outer layers are covalently linked by amide bonds, forming an integrated protective shell, significantly improving the stability of glycosides in alkaline fertilizers while ensuring the reliability of on-demand release in acidic environments. Attached Figure Description

[0020] Figure 1 This is a flowchart of the preparation method of crop stress-resistant, yield-increasing, and efficiency-enhancing fertilizer containing glycoside extracts provided by the present invention.

[0021] Figure 2 This is a flowchart of the preparation method of modified carboxymethyl cellulose provided by the present invention.

[0022] Figure 3 This is a flowchart of the preparation method of bacterial cellulose-chitosan carboxymethylated compound provided by the present invention.

[0023] Figure 4 This is a bar chart comparing the glycoside retention rates of different treatments.

[0024] Figure 5 This is a bar chart showing the cumulative release of glycosides in soils under different treatments. Detailed Implementation

[0025] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs; the terminology used herein in the specification of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application; the terms "comprising" and "having," and any variations thereof, in the specification, claims, and foregoing drawings of this application are intended to cover non-exclusive inclusion. The terms "first," "second," etc., in the specification, claims, or foregoing drawings of this application are used to distinguish different objects, not to describe a particular order.

[0026] In this document, the term "embodiment" means that a particular feature, structure, or characteristic described in connection with an embodiment may be included in at least one embodiment of this application. The appearance of this phrase in various places throughout the specification does not necessarily refer to the same embodiment, nor is it a separate or alternative embodiment mutually exclusive with other embodiments. It will be explicitly and implicitly understood by those skilled in the art that the embodiments described herein can be combined with other embodiments.

[0027] Example 1 This invention provides a crop stress-resistance and efficiency-enhancing fertilizer containing glycoside extract, comprising the following raw materials in parts by weight: 4 parts of glycoside extract, 10 parts of modified carboxymethyl cellulose, 3 parts of bacterial cellulose-chitosan carboxymethyl compound, and 50 parts of macro-element fertilizer base material; wherein the glycoside extract is ginsenoside extract (content ≥20%).

[0028] The preparation method of the above-mentioned crop stress-resistance and efficiency-enhancing fertilizer containing glycoside extracts, such as... Figure 1 As shown, it includes the following steps: S1: Prepare all raw materials according to the proportions; S2: Glycoside extracts are mixed with modified carboxymethyl cellulose, and the inlet air temperature is controlled at 40℃ and the atomization pressure is 0.2MPa to obtain core layer particles; S3: Disperse bacterial cellulose-chitosan carboxymethylated compound in water, add 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide (mass ratio 2:1) as activators, the total mass of the activators is 1% of the mass of bacterial cellulose-chitosan carboxymethylated compound, stir at room temperature for 20 min to obtain activated emulsion; S4: Place the core layer particles in a fluidized bed, atomize at a pressure of 0.3 MPa, spray at a rate of 5 mL / min, and spray with an activation emulsion to allow the bacterial cellulose-chitosan carboxymethyl compound to chemically bond with the surface of the core layer particles; the fluidized bed temperature is 40℃, and the spraying time is 40 minutes. S5: After spraying, vacuum dry at 40℃ for 2 hours to obtain double-layer protective microcapsules; S6: Mix the double-layer protective microcapsules with the base material of macro-element fertilizer and granulate to obtain the finished product; granulation temperature ≤60℃.

[0029] In this embodiment, as Figure 2 As shown, the preparation method of the modified carboxymethyl cellulose is as follows: (1) Dissolve carboxymethyl cellulose and sodium periodate in water at a mass ratio of 1:0.2, with a mass ratio of carboxymethyl cellulose to water of 1:10. Adjust the pH to 3 and react at 20°C in the dark for 3 hours. After the reaction is completed, add ethylene glycol to terminate the reaction, purify and dry to obtain oxidized carboxymethyl cellulose. (2) β-cyclodextrin, epichlorohydrin and ethylenediamine were dissolved in water at a mass ratio of 1:0.3:0.5 and the mass ratio of β-cyclodextrin to water was 1:3. The reaction was carried out at 50°C for 5 hours. After the reaction was completed, the pH was adjusted to neutral and the precipitate was dried to obtain amino-modified cyclodextrin. (3) Oxidized carboxymethyl cellulose and aminocyclodextrin were dissolved in water at a mass ratio of 1:0.5, with a total solid content of 1%. The pH was adjusted to 6.5, and the mixture was chemically bonded by Schiff base reaction at 35°C for 4 hours. After drying, modified carboxymethyl cellulose was obtained.

[0030] In this embodiment, as Figure 3 As shown, the preparation method of the bacterial cellulose-chitosan carboxymethyl compound is as follows: (1) Add bacterial cellulose and chitosan to a 0.5% acetic acid aqueous solution at a mass ratio of 1:0.5, and the mass ratio of bacterial cellulose to acetic acid aqueous solution is 1:20. Stir and compound at 20°C for 1 hour, and freeze dry to obtain bacterial cellulose-chitosan complex. (2) The bacterial cellulose-chitosan complex and chloroacetic acid were added to the isopropanol-water mixed solvent (isopropanol:water = 80:20, volume ratio) at a mass ratio of 1:0.5. Sodium hydroxide was added to adjust the pH to 9. The reaction was carried out at 60°C for 4 hours. After the reaction was completed, the mixture was neutralized with dilute hydrochloric acid, filtered, washed with 75% ethanol, and dried to obtain bacterial cellulose-chitosan carboxymethylated product.

[0031] Example 2 This invention provides a crop stress-resistance and efficiency-enhancing fertilizer containing glycoside extracts, comprising the following raw materials in parts by weight: 5 parts glycoside extract, 11 parts modified carboxymethyl cellulose, 4 parts bacterial cellulose-chitosan carboxymethyl compound, and 53 parts macro-element fertilizer base material. The glycoside extract is astragaloside extract (content ≥20%).

[0032] The preparation method of the above-mentioned crop stress-resistance and efficiency-enhancing fertilizer containing glycoside extracts, such as... Figure 1 As shown, it includes the following steps: S1: Prepare all raw materials according to the proportions; S2: Glycoside extracts are mixed with modified carboxymethyl cellulose, and the inlet air temperature is controlled at 43℃ and the atomization pressure is 0.25MPa to obtain core layer particles; S3: Disperse bacterial cellulose-chitosan carboxymethylated compound in water, add 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide (mass ratio 2:1) as activators, the total mass of activators is 1.5% of the mass of bacterial cellulose-chitosan carboxymethylated compound, stir at room temperature for 22 min to obtain activated emulsion; S4: Place the core layer particles in a fluidized bed, atomize at a pressure of 0.35 MPa, spray at a rate of 6 mL / min, and spray with an activation emulsion to chemically bond the bacterial cellulose-chitosan carboxymethyl compound to the surface of the core layer particles; the fluidized bed temperature is 43℃, and the spraying time is 45 minutes. S5: After spraying, vacuum dry at 43℃ for 2.5 hours to obtain double-layer protective microcapsules; S6: Mix the double-layer protective microcapsules with the base material of macro-element fertilizer and granulate to obtain the finished product; granulation temperature ≤60℃.

[0033] In this embodiment, as Figure 2 As shown, the preparation method of the modified carboxymethyl cellulose is as follows: (1) Dissolve carboxymethyl cellulose and sodium periodate in water at a mass ratio of 1:0.25, with a mass ratio of carboxymethyl cellulose to water of 1:12. Adjust the pH to 3.2 and react at 22°C in the dark for 3.5 hours. After the reaction is completed, add ethylene glycol to terminate the reaction, purify and dry to obtain oxidized carboxymethyl cellulose. (2) β-cyclodextrin, epichlorohydrin and ethylenediamine were dissolved in water at a mass ratio of 1:0.4:0.6 and the mass ratio of β-cyclodextrin to water was 1:4. The reaction was carried out at 55°C for 5.5 hours. After the reaction was completed, the pH was adjusted to neutral and the precipitate was dried to obtain amino-modified cyclodextrin. (3) Oxidized carboxymethyl cellulose and aminocyclodextrin were dissolved in water at a mass ratio of 1:0.7, with a total solid content of 2%. The pH was adjusted to 6.8, and the mixture was chemically bonded by Schiff base reaction at 36°C for 4.5 hours. The mixture was then dried to obtain modified carboxymethyl cellulose.

[0034] In this embodiment, as Figure 3 As shown, the preparation method of the bacterial cellulose-chitosan carboxymethyl compound is as follows: (1) Add bacterial cellulose and chitosan to 0.8% acetic acid aqueous solution at a mass ratio of 1:0.7. The mass ratio of bacterial cellulose to acetic acid aqueous solution is 1:28. Stir and compound at 22℃ for 1.5 hours, freeze dry to obtain bacterial cellulose-chitosan complex. (2) The bacterial cellulose-chitosan complex and chloroacetic acid were added to an isopropanol-water mixed solvent (isopropanol:water = 80:20) at a mass ratio of 1:0.6. Sodium hydroxide was added to adjust the pH to 9.5. The reaction was carried out at 65°C for 4.5 hours. After the reaction was completed, the mixture was neutralized with dilute hydrochloric acid, filtered, washed with 75% ethanol, and dried to obtain bacterial cellulose-chitosan carboxymethylated product.

[0035] Example 3 This invention provides a crop stress-resistance and efficiency-enhancing fertilizer containing glycoside extracts, comprising the following raw materials in parts by weight: 7 parts glycoside extract, 12 parts modified carboxymethyl cellulose, 5 parts bacterial cellulose-chitosan carboxymethyl compound, and 60 parts macro-element fertilizer base material. The glycoside extract is geniposide (content ≥90%).

[0036] The preparation method of the above-mentioned crop stress-resistance and efficiency-enhancing fertilizer containing glycoside extracts, such as... Figure 1 As shown, it includes the following steps: S1: Prepare all raw materials according to the proportions; S2: Glycoside extracts are mixed with modified carboxymethyl cellulose and granulated in a fluidized bed. The inlet air temperature is controlled at 45℃ and the atomization pressure is 0.3MPa to obtain core layer particles. S3: Disperse bacterial cellulose-chitosan carboxymethylated compound in water, add 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide (mass ratio 2:1) as activators, the total mass of the activators is 2% of the mass of bacterial cellulose-chitosan carboxymethylated compound, stir at room temperature for 25 min to obtain activated emulsion; S4: Place the core layer particles in a fluidized bed, atomize at a pressure of 0.4 MPa, spray at a rate of 8 mL / min, and spray with an activation emulsion to chemically bond the bacterial cellulose-chitosan carboxymethyl compound to the surface of the core layer particles; the fluidized bed temperature is 45℃, and the spraying time is 50 minutes. S5: After spraying, vacuum dry at 45℃ for 3 hours to obtain double-layer protective microcapsules; S6: Mix the double-layer protective microcapsules with the base material of macro-element fertilizer and granulate to obtain the finished product; granulation temperature ≤60℃.

[0037] In this embodiment, as Figure 2 As shown, the preparation method of the modified carboxymethyl cellulose is as follows: (1) Dissolve carboxymethyl cellulose and sodium periodate in water at a mass ratio of 1:0.3, with a mass ratio of carboxymethyl cellulose to water of 1:15. Adjust the pH to 3.5 and react at 25°C in the dark for 4 hours. After the reaction is completed, add ethylene glycol to terminate the reaction, purify and dry to obtain oxidized carboxymethyl cellulose. (2) β-cyclodextrin, epichlorohydrin and ethylenediamine were dissolved in water at a mass ratio of 1:0.45:0.75 and the mass ratio of β-cyclodextrin to water was 1:5.5. The reaction was carried out at 60°C for 6 hours. After the reaction was completed, the pH was adjusted to neutral and the precipitate was dried to obtain amino-modified cyclodextrin. (3) Oxidized carboxymethyl cellulose and aminocyclodextrin were dissolved in water at a mass ratio of 1:1.0, with a total solid content of 3%. The pH was adjusted to 7.0, and the mixture was chemically bonded by Schiff base reaction at 38°C for 5 hours. After drying, modified carboxymethyl cellulose was obtained.

[0038] In this embodiment, as Figure 3 As shown, the preparation method of the bacterial cellulose-chitosan carboxymethyl compound is as follows: (1) Add bacterial cellulose and chitosan to a 1.2% acetic acid aqueous solution at a mass ratio of 1:1.0. The mass ratio of bacterial cellulose to acetic acid aqueous solution is 1:35. Stir and compound at 25°C for 2 hours, and freeze dry to obtain bacterial cellulose-chitosan complex. (2) The bacterial cellulose-chitosan complex and chloroacetic acid were added to an isopropanol-water mixed solvent (isopropanol:water = 80:20) at a mass ratio of 1:0.7. Sodium hydroxide was added to adjust the pH to 9.5. The reaction was carried out at 70°C for 5 hours. After the reaction was completed, the mixture was neutralized with dilute hydrochloric acid, filtered, washed with 75% ethanol, and dried to obtain bacterial cellulose-chitosan carboxymethylated product.

[0039] Example 4 This invention provides a crop stress-resistance and efficiency-enhancing fertilizer containing glycoside extracts, comprising the following raw materials in parts by weight: 8 parts glycoside extracts, 13 parts modified carboxymethyl cellulose, 6 parts bacterial cellulose-chitosan carboxymethyl compound, and 65 parts macro-element fertilizer base material. The glycoside extract is ginsenoside extract (content ≥20%).

[0040] The preparation method of the above-mentioned crop stress-resistance and efficiency-enhancing fertilizer containing glycoside extracts, such as... Figure 1As shown, it includes the following steps: S1: Prepare all raw materials according to the proportions; S2: Glycoside extracts are mixed with modified carboxymethyl cellulose and granulated in a fluidized bed. The inlet air temperature is controlled at 47°C and the atomization pressure is 0.35 MPa to obtain core layer particles. S3: Disperse bacterial cellulose-chitosan carboxymethylated compound in water, add 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide (mass ratio 2:1) as activators, the total mass of the activators is 2.5% of the mass of bacterial cellulose-chitosan carboxymethylated compound, stir at room temperature for 28 min to obtain activated emulsion; S4: Place the core layer particles in a fluidized bed, atomize at a pressure of 0.45 MPa, spray at a rate of 9 mL / min, and spray with an activation emulsion to chemically bond the bacterial cellulose-chitosan carboxymethyl compound to the surface of the core layer particles; the fluidized bed temperature is 47℃, and the spraying time is 55 minutes. S5: After spraying, vacuum dry at 47℃ for 3.5 hours to obtain double-layer protective microcapsules; S6: Mix the double-layer protective microcapsules with the base material of macro-element fertilizer and granulate to obtain the finished product; granulation temperature ≤60℃.

[0041] In this embodiment, as Figure 2 As shown, the preparation method of the modified carboxymethyl cellulose is as follows: (1) Dissolve carboxymethyl cellulose and sodium periodate in water at a mass ratio of 1:0.35, with a mass ratio of carboxymethyl cellulose to water of 1:18. Adjust the pH to 3.8 and react at 28°C in the dark for 4.5 hours. After the reaction is completed, add ethylene glycol to terminate the reaction, purify and dry to obtain oxidized carboxymethyl cellulose. (2) β-cyclodextrin, epichlorohydrin and ethylenediamine were dissolved in water at a mass ratio of 1:0.5:0.9 and the mass ratio of β-cyclodextrin to water was 1:7. The reaction was carried out at 65°C for 6.5 hours. After the reaction was completed, the pH was adjusted to neutral and the precipitate was dried to obtain amino-modified cyclodextrin. (3) Oxidized carboxymethyl cellulose and aminocyclodextrin were dissolved in water at a mass ratio of 1:1.2, with a total solid content of 4%. The pH was adjusted to 7.2, and the mixture was chemically bonded by Schiff base reaction at 39°C for 5.5 hours. After drying, modified carboxymethyl cellulose was obtained.

[0042] In this embodiment, as Figure 3 As shown, the preparation method of the bacterial cellulose-chitosan carboxymethyl compound is as follows: (1) Add bacterial cellulose and chitosan to a 1.5% acetic acid aqueous solution at a mass ratio of 1:1.2. The mass ratio of bacterial cellulose to acetic acid aqueous solution is 1:42. Stir and compound at 28°C for 2.5 hours, and freeze dry to obtain bacterial cellulose-chitosan complex. (2) The bacterial cellulose-chitosan complex and chloroacetic acid were added to the isopropanol-water mixed solvent (isopropanol:water = 80:20, volume ratio) at a mass ratio of 1:0.8. Sodium hydroxide was added to adjust the pH to 9.5. The reaction was carried out at 68°C for 5.5 hours. After the reaction was completed, the mixture was neutralized with dilute hydrochloric acid, filtered, washed with 75% ethanol, and dried to obtain bacterial cellulose-chitosan carboxymethylated product.

[0043] Example 5 This invention provides a crop stress-resistance and efficiency-enhancing fertilizer containing glycoside extracts, comprising the following raw materials in parts by weight: 10 parts glycoside extract, 15 parts modified carboxymethyl cellulose, 7 parts bacterial cellulose-chitosan carboxymethyl compound, and 70 parts macro-element fertilizer base material. The glycoside extract is astragaloside extract (content ≥20%).

[0044] The preparation method of the above-mentioned crop stress-resistance and efficiency-enhancing fertilizer containing glycoside extracts, such as... Figure 1 As shown, it includes the following steps: S1: Prepare all raw materials according to the proportions; S2: Glycoside extracts are mixed with modified carboxymethyl cellulose and granulated in a fluidized bed. The inlet air temperature is controlled at 50°C and the atomization pressure is 0.4 MPa to obtain core layer particles. S3: Disperse bacterial cellulose-chitosan carboxymethylated compound in water, add 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide (mass ratio 2:1) as activators, the total mass of the activators is 3% of the mass of bacterial cellulose-chitosan carboxymethylated compound, stir at room temperature for 30 min to obtain activated emulsion; S4: Place the core layer particles in a fluidized bed, atomize at a pressure of 0.5 MPa, spray at a rate of 10 mL / min, and spray with an activation emulsion to chemically bond the bacterial cellulose-chitosan carboxymethyl compound to the surface of the core layer particles; the fluidized bed temperature is 50℃, and the spraying time is 60 minutes. S5: After spraying, vacuum dry at 50℃ for 4 hours to obtain double-layer protective microcapsules; S6: Mix the double-layer protective microcapsules with the base material of macro-element fertilizer and granulate to obtain the finished product; granulation temperature ≤60℃.

[0045] In this embodiment, as Figure 2 As shown, the preparation method of the modified carboxymethyl cellulose is as follows: (1) Dissolve carboxymethyl cellulose and sodium periodate in water at a mass ratio of 1:0.4, with a mass ratio of carboxymethyl cellulose to water of 1:20. Adjust the pH to 4 and react at 30°C in the dark for 5 hours. After the reaction is completed, add ethylene glycol to terminate the reaction, purify and dry to obtain oxidized carboxymethyl cellulose. (2) β-cyclodextrin, epichlorohydrin and ethylenediamine were dissolved in water at a mass ratio of 1:0.6:1.0 and the mass ratio of β-cyclodextrin to water was 1:8. The reaction was carried out at 70°C for 7 hours. After the reaction was completed, the pH was adjusted to neutral and the precipitate was dried to obtain amino-modified cyclodextrin. (3) Oxidized carboxymethyl cellulose and aminocyclodextrin were dissolved in water at a mass ratio of 1:1.5, with a total solid content of 5%. The pH was adjusted to 7.5, and the mixture was chemically bonded by Schiff base reaction at 40°C for 6 hours. After drying, modified carboxymethyl cellulose was obtained.

[0046] In this embodiment, as Figure 3 As shown, the preparation method of the bacterial cellulose-chitosan carboxymethyl compound is as follows: (1) Add bacterial cellulose and chitosan to a 2% acetic acid aqueous solution at a mass ratio of 1:1.5. The mass ratio of bacterial cellulose to acetic acid aqueous solution is 1:50. Stir and compound at 30°C for 3 hours, and freeze dry to obtain bacterial cellulose-chitosan complex. (2) The bacterial cellulose-chitosan complex and chloroacetic acid were added to the isopropanol-water mixed solvent (isopropanol:water = 80:20, volume ratio) at a mass ratio of 1:1.0. Sodium hydroxide was added to adjust the pH to 10. The reaction was carried out at 70°C for 6 hours. After the reaction was completed, the mixture was neutralized with dilute hydrochloric acid, filtered, washed with 75% ethanol, and dried to obtain bacterial cellulose-chitosan carboxymethylated product.

[0047] Comparative Example 1 Seven parts of glycoside extract were directly mixed with 60 parts of macro-element fertilizer base material and granulated without adding modified carboxymethyl cellulose and bacterial cellulose-chitosan carboxymethyl compound. Other conditions were the same as in Example 3.

[0048] Comparative Example 2 Formula: 7 parts glycoside extract, 12 parts modified carboxymethyl cellulose, and 60 parts macro-element fertilizer base.

[0049] Preparation method: Glycoside extracts are mixed with modified carboxymethyl cellulose and granulated in a fluidized bed to obtain microcapsules. These microcapsules are then directly mixed with macro-element fertilizer base materials and granulated without adding outer layer materials.

[0050] Comparative Example 3 Formula: 7 parts glycoside extract, 5 parts bacterial cellulose-chitosan carboxymethyl compound, and 60 parts macro-element fertilizer base.

[0051] Preparation method: Glycoside extracts are mixed with bacterial cellulose-chitosan carboxymethyl compounds and granulated in a fluidized bed to obtain microcapsules. These microcapsules are then directly mixed with macro-element fertilizer base materials and granulated without adding inner layer materials.

[0052] Comparative Example 4 Formula: 7 parts glycoside extract, 12 parts unmodified carboxymethyl cellulose, 5 parts bacterial cellulose-chitosan carboxymethyl compound, and 60 parts macro-element fertilizer base.

[0053] Preparation method: Glycoside extracts were mixed with unmodified carboxymethyl cellulose and granulated to obtain core particles. Bacterial cellulose-chitosan carboxymethyl compound was then activated and sprayed onto the core particles for chemical bonding. Other conditions were the same as in Example 3.

[0054] Comparative Example 5 Formula: 7 parts glycoside extract, 12 parts modified carboxymethyl cellulose, 5 parts physical mixture of bacterial cellulose and chitosan (mass ratio 1:1), and 60 parts macro-element fertilizer base material.

[0055] Preparation method: Glycoside extracts and modified carboxymethyl cellulose were mixed and granulated to obtain core particles. Then, a physical mixture of bacterial cellulose and chitosan (without composite modification) was activated and sprayed to coat the core particles. Other conditions were the same as in Example 3.

[0056] Comparative Example 6 Formula: 7 parts glycoside extract, 12 parts modified carboxymethyl cellulose, 5 parts bacterial cellulose-chitosan carboxymethyl compound, and 60 parts macro-element fertilizer base material.

[0057] Preparation method: Modified carboxymethyl cellulose and bacterial cellulose-chitosan carboxymethyl compound are physically mixed and then granulated together with glycoside extracts to form microcapsules in one step without layering spraying and chemical bonding. Then, it is mixed with macro-element fertilizer base material and granulated.

[0058] Effect verification test Experiment 1: Glycoside Retention Rate Test Test method: Each fertilizer sample was aged for 30 days in a constant temperature and humidity chamber at 50℃ and 90% relative humidity. The content of glycoside extracts was determined by high performance liquid chromatography (HPLC), and the retention rate was calculated. Retention rate (%) = (content after aging / initial content) × 100%. Each sample was tested in triplicate, and the average value was taken.

[0059] The test results are shown in Table 1 below: Results analysis: The retention rates of Examples 1-5 were between 90.2% and 90.8%, which were significantly higher than those of the comparative examples (42.9%-79.5%).

[0060] The retention rate of Comparative Example 1 (uncoated) was only 42.9%, indicating that unprotected glycosides are easily hydrolyzed in an alkaline environment.

[0061] The retention rates of Comparative Example 2 (inner layer only) and Comparative Example 3 (outer layer only) were 75.5% and 72.5%, respectively, indicating that the effect of a single protective layer is limited.

[0062] The retention rate of Comparative Example 4 (without inner layer modification) was 58.5%, significantly lower than that of Example 3 (90.8%), demonstrating that the inclusion effect of aminocyclodextrin and the Schiff base crosslinking network in the inner layer material are crucial for glycoside protection.

[0063] The retention rate of Comparative Example 5 (unmodified outer layer) was 64.0%, which was significantly lower than that of Example 3, demonstrating that the carboxymethylation modification and chemical bonding of the outer layer material are indispensable for achieving the protective effect in alkaline environments.

[0064] The retention rate of Comparative Example 6 (physical mixing and one-step coating) was 69.5%, which was lower than that of Example 3 (90.8%). This shows that the bilayer structure formed by the layered chemical bonding of the present invention is significantly better than that of simple physical mixing.

[0065] Experiment 2: Release Characteristics Test in Soil Test method: Each fertilizer sample was buried in standard soil (pH 6.8, moisture content 20%) and incubated at a constant temperature of 25℃. Soil glycoside content was measured periodically, and the cumulative release rate was calculated. Cumulative release rate (%) = (release amount / total content) × 100%. Each sample was tested in triplicate, and the average result was taken.

[0066] The test results are shown in Table 2 below: Results analysis: The release rates of Examples 1-5 at each time point were significantly lower than those of the comparative examples; the release of Comparative Examples 1-5 was too rapid, with a release rate of 42.5%-78.2% after 3 days; the release rate of Comparative Example 6 (physical mixing and one-step encapsulation) was between that of Examples and Comparative Examples 1-5, but was still significantly higher than that of all Examples.

[0067] Experiment 3: pH Response Test Test method: The microcapsules of each embodiment were placed in buffer solutions at pH 7.0, 6.0, and 5.0, respectively, and incubated at 25°C. The cumulative release rate was measured after 7 days. Each sample was tested in triplicate, and the average value was taken.

[0068] The test results are shown in Table 3 below: Results analysis: All examples showed pH responsiveness, with the release rate increasing as the pH decreased.

[0069] Experiment 4: Pot Experiment Experimental Design: Maize (variety: Zhengdan 958) was used as the test crop. Pot cultivation (30cm diameter, 8kg soil per pot) was employed, with two treatments: normal irrigation (control) and drought stress (irrigation stopped for 7 days). Each treatment was treated with equal amounts of nitrogen-containing fertilizers from Example 3 and Comparative Examples 1-6 (equivalent to 40kg / mu in the field per pot); each treatment was replicated in 5 pots. After the drought stress period, leaf superoxide dismutase (SOD) activity, peroxidase (POD) activity, and malondialdehyde (MDA) content were measured. Yield was determined after harvest.

[0070] The test results are shown in Table 4 below: Results analysis: The stress resistance and yield of all embodiments were significantly better than those of the control pairs.

[0071] Experimental Example 1: Verification of the stability of microcapsule structures The microcapsules of Example 3 and Comparative Example 6 (physical mixing and one-step encapsulation) were placed in a buffer solution at pH 9.0 and shaken at 50°C for 24 hours. The morphological changes of the microcapsules were observed. The results showed that the microcapsules of Example 3 remained intact and spherical without significant damage; while the microcapsules of Comparative Example 6 showed partial rupture and leakage of contents. These results indicate that the integrated structure formed through chemical bonding significantly improves the structural stability of the microcapsules in an alkaline environment, providing more reliable protection for glycosides.

[0072] Experimental Example 2: Infrared Spectroscopic Characterization Infrared spectroscopy analysis was performed on modified carboxymethyl cellulose, bacterial cellulose-chitosan carboxymethyl compound, and the bilayer protective microcapsules prepared in Example 3 (using KBr pellet method, scanning range 4000-400 cm⁻¹). -1 ).

[0073] The results showed that modified carboxymethyl cellulose at 1645 cm⁻¹ -1 The characteristic absorption peak of the Schiff base bond (-C=N-) appears at 1655 cm⁻¹; in addition to retaining the above-mentioned characteristic peak of the Schiff base bond in the infrared spectrum of the double-layer protected microcapsule, a characteristic absorption peak of the Schiff base bond also appears at 1655 cm⁻¹. -1 and 1550 cm -1 The characteristic absorption peaks of amide I and amide II bands appear at 1730 cm⁻¹, indicating the presence of amide bonds (-CO-NH-). -1The absorption peak intensity near the outer layer material decreased significantly, indicating that the carboxyl groups of the outer layer material and the amino groups of the inner layer material successfully underwent an amidation reaction, forming a covalent bond.

[0074] It should be noted that, for the sake of simplicity, the foregoing embodiments are all described as a series of actions. However, those skilled in the art should understand that the present invention is not limited to the described order of actions, as some steps may be performed in other orders or simultaneously according to the present invention. Furthermore, those skilled in the art should also understand that the embodiments described in the specification are preferred embodiments, and the actions and modules involved are not necessarily essential to the present invention.

[0075] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit the scope of protection of the invention. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on these embodiments, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art can still combine, add, delete, or otherwise adjust the features of the various embodiments of the present invention according to the circumstances without conflict or creative effort, thereby obtaining different technical solutions that do not fundamentally depart from the concept of the present invention. These technical solutions also fall within the scope of protection of the present invention.

Claims

1. A crop stress resistance, yield and efficiency increasing fertilizer containing glycoside extract, characterized in that, Including the following ingredients by weight: 4-10 parts of glycoside extract, 10-15 parts of modified carboxymethyl cellulose, 3-7 parts of bacterial cellulose-chitosan carboxymethyl compound, and 50-70 parts of macro-element fertilizer base material. The modified carboxymethyl cellulose is chemically bonded to oxidized carboxymethyl cellulose and aminocyclodextrin via a Schiff base reaction; The bacterial cellulose-chitosan carboxymethyl compound is a complex obtained by physically combining bacterial cellulose and chitosan and then modifying it with carboxymethylation.

2. The glynoside-containing extractive crop stress resistance, yield and efficiency increasing fertilizer of claim 1, characterized in that, It includes the following raw materials in parts by weight: 6-8 parts of glycoside extract, 11-14 parts of modified carboxymethyl cellulose, 4-6 parts of bacterial cellulose-chitosan carboxymethyl compound, and 55-65 parts of macro-element fertilizer base material.

3. The crop stress resistance, yield and efficiency increasing fertilizer containing glycoside extracts according to claim 2, characterized in that, The raw materials include the following by weight: 7 parts glycoside extract, 12 parts modified carboxymethyl cellulose, 5 parts bacterial cellulose-chitosan carboxymethyl compound, and 60 parts macro-element fertilizer base material.

4. The crop stress resistance, yield and efficiency increasing fertilizer containing glycoside extracts according to claim 1, characterized in that, The glycoside extract includes at least one of ginsenosides, astragalosides, and gardenosides.

5. The crop stress resistance, yield and efficiency increasing fertilizer containing glycoside extracts according to claim 1, characterized in that, The modified carboxymethyl cellulose is prepared as follows: (1) Carboxymethyl cellulose is reacted with sodium periodate in water to obtain oxidized carboxymethyl cellulose; (2) Cyclodextrin is reacted with epichlorohydrin and ethylenediamine to obtain amino-modified cyclodextrin; (3) Oxidized carboxymethyl cellulose and aminocyclodextrin are chemically bonded in water at a mass ratio of 1:0.5-1.5 to obtain modified carboxymethyl cellulose.

6. The crop stress resistance, yield and efficiency increasing fertilizer containing glycoside extracts according to claim 5, characterized in that, In step (1), the reaction temperature is 20-30℃, the reaction time is 3-5 hours, and the pH is 3-4; in step (2), the reaction temperature is 50-70℃, and the reaction time is 5-7 hours; in step (3), the chemical bonding temperature is 35-40℃, the reaction time is 4-6 hours, and the pH is 6.5-7.

5.

7. The crop stress resistance, yield and efficiency increasing glyn-containing extractive-containing fertilizer according to claim 1, characterized in that, The preparation method of the bacterial cellulose-chitosan carboxymethyl compound is as follows: (1) Bacterial cellulose and chitosan were compounded in an acidic aqueous solution at a mass ratio of 1:0.5-1.5 and dried to obtain a bacterial cellulose-chitosan complex; (2) The bacterial cellulose-chitosan complex was reacted with chloroacetic acid in an alkaline aqueous solution to carry out a carboxymethylation reaction to obtain bacterial cellulose-chitosan carboxymethylated product.

8. The crop stress resistance, yield and efficiency increasing fertilizer containing glycoside extracts according to claim 7, characterized in that, In step (1), the acidic aqueous solution is a 0.5-2% acetic acid solution, the composite temperature is 20-30℃, and the drying is done by freeze drying; in step (2), the mass ratio of bacterial cellulose-chitosan complex to chloroacetic acid is 1:0.5-1.0, the reaction temperature is 50-70℃, the reaction time is 3-6 hours, and the pH of the reaction system is 8-10.

9. A method for preparing the crop stress resistance, yield and efficiency increasing fertilizer containing glycosides extract according to any one of claims 1-8, characterized in that, Includes the following steps: S1: Prepare all raw materials according to the proportions; S2: Glycoside extracts are mixed with modified carboxymethyl cellulose and granulated in a fluidized bed to obtain core particles; S3: Disperse bacterial cellulose-chitosan carboxymethyl compound in water, add an activator to activate it, and obtain an activated emulsion; S4: Place the core layer particles in a fluidized bed and spray an activation emulsion to allow the bacterial cellulose-chitosan carboxymethyl compound to chemically bond with the surface of the core layer particles; S5: Drying to obtain double-layered protective microcapsules; S6: Mix the double-layer protective microcapsules with the base material of macro-element fertilizer and granulate to obtain the finished product.

10. The method of claim 9, wherein the preparation method of the crop stress resistance, yield and efficiency increasing fertilizer containing glycosides is characterized in that, In S3, the activator is a mixture of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide, and the total amount of activator added is 1%-3% of the mass of bacterial cellulose-chitosan carboxymethylated material; in S2, the inlet air temperature of fluidized bed granulation is 40-50℃, and the atomization pressure is 0.2-0.4MPa; in S4, the atomization pressure of spray activation emulsion is 0.3-0.5MPa, and the spraying rate is 5-10mL / min.

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