A method for combining slow-release chlorine dioxide soil disinfection granules with probiotics to comprehensively control the continuous cropping disorder of small yellow ginger
Through the combined use of sustained-release chlorine dioxide soil disinfection particles and probiotics, the disease problem in continuous cropping of turmeric is solved, the reconstruction of the soil microbial environment and the improvement of crop resistance are achieved, and the yield and land utilization of turmeric is improved.
Patent Information
- Application Number
- CN202510592811.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2025-05-09
- Publication Date
- 2025-09-02
- Estimated Expiration
- 2045-05-09
AI Technical Summary
The root rot, epidemics and anthrax caused by continuous cropping of turmeric are serious, and the existing technology is difficult to effectively control, resulting in crop yield reductions and land use reductions.
The sustained-release chlorine dioxide soil disinfection particles are used in combination with probiotics. By disinfecting and killing pathogenic microorganisms in the soil and restoring the soil microbial environment, combined with scientific inter-ground management technology, comprehensive control of the continuous cropping obstacles of turmeric turmeric is achieved.
Effectively kill pathogenic microorganisms in the soil, restore the soil microbial environment that is conducive to the growth of turmeric, improve crop resistance, prevent disease transmission, and improve yield and land utilization.
Smart Images

Figure CN120113524B_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of crop planting and relates to a method for comprehensively controlling the continuous cropping disorder of small yellow ginger by combining slow-release chlorine dioxide soil disinfection granules with probiotics. Background Art
[0002] Turmeric, also known as yellow ginger, turmeric root, or turmeric root, is a common spice and medicinal plant. Its cut surface is pure yellow, with a spicy, rich flavor and a tender, low-fiber texture. Turmeric is used not only as a seasoning, beverage, and food preparation, but also has numerous pharmacological effects, including anti-inflammatory, antioxidant, antibacterial, and anti-cancer properties. Consequently, turmeric is primarily marketed as fresh ginger, dried ginger, and ginger powder, earning it a high reputation and widespread popularity.
[0003] With increasing consumer demand for healthy foods, the market for turmeric, a food with health benefits, has seen rapid growth in recent years. The warm, humid subtropical climate of the 27° north latitude zone is ideal for turmeric growth, resulting in relatively high yields. Large-scale cultivation in my country is primarily found in Luoping County and Wenshan Prefecture in Yunnan, Panzhou City in Guizhou, Ju County in Shandong, Lushan County in Henan, and Jiangyong County in Hunan, creating significant market potential.
[0004] However, continuous cropping of small yellow ginger can lead to outbreaks of ginger blight. In severe cases, large areas of the ginger will wither and rot, resulting in a complete crop failure. Consequently, farmers often adopt crop rotations such as rice-ginger, onion-garlic rotation, and ginger-bean rotation, resulting in a decreasing amount of arable land. The main diseases associated with continuous cropping of small yellow ginger include root rot (also known as stem rot or wilt), blight, anthracnose, and purple spot. These diseases are primarily caused by the continuous proliferation and accumulation of pathogenic microorganisms such as fungi and bacteria that are susceptible to small yellow ginger during continuous cropping, ultimately leading to outbreaks of ginger blight.
[0005] Turmeric root rot, also known as stem rot or wilt, is caused by a fungus that lurks in the soil. When temperature and humidity are ideal and plant growth is weak, the fungus will infect the plant. Infected ginger seeds, soil, uncomposted manure, rainwater, and farm tools can carry and spread the fungus. Heavy rain, high humidity, frost damage, insect damage, continuous cropping, and weak turmeric growth all contribute to the development and spread of root rot. The pathogen primarily infects the young underground rhizomes and the base of the stems. Affected buds and stems develop brown or dark brown spots (sometimes short streaks), which become sunken or cracked and then rot. Sometimes the spots encircle the stem base, causing the plant above the spots to wilt and die. New roots are rare or absent underground, and leaves gradually yellow, wilt, and curl upwards, eventually dying (often throughout the plant, which generally does not fall off). In milder cases, the plant becomes short and weak. Sometimes, the tips of ginger seedlings turn brown, rot, and die before or shortly after emerging from the soil. Another less common type of root rot is caused by bacterial infection. Its symptoms differ in that the affected area softens and rots. The rotten area is often accompanied by a white, stringy substance and sometimes a foul odor. In mild cases, leaves wilt, curl, and easily fall (chlorosis). In severe cases, the entire plant dies.
[0006] Yellow turmeric blight is a fungal disease that can be transmitted through diseased plant debris, ginger seeds, and uncomposted farmyard manure. Excessive rainfall, high humidity, and continuous cropping all contribute to its development and spread. While its overall incidence is lower than that of root rot, it can also cause the death of the entire plant. The stem (including the base of the seedling stem) is often affected, initially developing dark green, water-soaked lesions (sometimes in strips). These lesions then turn brown or black, becoming sunken and even shrinking around the stem. This can cause wilt in one branch or the entire plant above the lesion, ultimately leading to death (which can be concentrated or widespread). The lesions on leaves are nearly circular and dark green, and in high humidity, the leaves can rot softly.
[0007] Anthracnose and purple spot of yellow ginger are both fungal diseases. The pathogens can be transmitted through diseased plant debris, leaves, ginger seedlings, and uncomposted farmyard manure. Conditions such as heavy rain, high humidity, continuous cropping, excessive nitrogen fertilizer, low-lying land, and stagnant water all favor the development and spread of ginger blight. Anthracnose is more common, while purple spot is less common (sometimes the two diseases occur together), and the severity of both diseases is generally mild. Both diseases primarily infect leaves. Anthracnose first appears as small, water-soaked, chlorotic spots on leaves, which gradually expand into nearly circular lesions (mostly less than 4 mm in diameter) dotted with numerous concentric rings of small black spots, with a grayish-white center and brown edges. Purple spot symptoms are similar to those of anthracnose (without the concentric rings), but later on, many lesions often connect or expand into irregular, large purple spots (mostly greater than 10 mm in diameter). These lesions are dark or dark purple and often extend from the leaf margin toward the center. Lesions on stems are often small, elongated, sunken, and reddish-brown or dark-brown. Summary of the Invention
[0008] To address the shortcomings of the existing technology, the present invention aims to provide a method for comprehensively controlling the continuous cropping problem of turmeric using slow-release chlorine dioxide soil disinfection granules combined with probiotics. Using slow-release chlorine dioxide granules to disinfect and sterilize the soil before planting effectively kills pathogenic microorganisms and decomposes organic pesticide residues in the soil, eliminating pathogenic microorganisms and toxins. The use of probiotics can quickly restore the soil microbial environment conducive to the growth of turmeric.
[0009] To achieve this object, the present invention adopts the following technical solutions:
[0010] The present invention provides a method for comprehensively controlling the continuous cropping disorder of small yellow ginger by combining slow-release chlorine dioxide soil disinfection granules with probiotics, the method comprising:
[0011] Chlorine dioxide slow-release granules are applied to the soil to disinfect and sterilize the soil, and then Bacillus subtilis wettable powder is diluted and sprayed on the soil to supplement the soil with probiotics;
[0012] The chlorine dioxide slow-release granules are prepared by drying a sodium chlorite precursor gel in stages to obtain a core material, which is then coated with hydroxypropyl methylcellulose to form a quick-release layer, and finally a slow-release layer is constructed by alternately soaking and cross-linking ε-polylysine / sodium alginate, which is then microwave-enhanced.
[0013] The Bacillus subtilis wettable powder is prepared by the following method:
[0014] First, the Bacillus subtilis fermentation liquid is centrifuged and concentrated, and then a composite protective agent consisting of ascorbic acid, sodium alginate and sorbitol is added; then, it is mixed with a composite carrier consisting of white carbon black, diatomaceous earth and magnesium aluminum silicate, potassium humate and a spore germination agent, and then spray-dried and mixed with a composite surfactant and sieved.
[0015] More specifically, before disinfecting the soil, the soil needs to be treated. The treatment methods include:
[0016] The residual branches, leaves and roots in the soil of the planting area are treated harmlessly, and then the soil is disinfected and sterilized with chlorine dioxide slow-release granules, and probiotics are added to the soil with diluted Bacillus subtilis wettable powder.
[0017] After supplementing the soil with probiotics, seedlings need to be planted, which includes: selecting ginger seeds with good skin color, no rot and no disease, soaking the selected ginger seeds in chlorine dioxide solution and drying them, then sowing them into the soil, and covering them with soil after sowing.
[0018] After ginger is planted, field management is required, including: applying organic fertilizer to the soil after planting; applying topdressing according to the growth conditions during the plant growth period; and spraying pesticides in time for prevention and control when diseases, insect pests and weeds occur.
[0019] The method for comprehensively controlling the continuous cropping disorder of small yellow ginger provided by the present invention cleverly utilizes the physical characteristics of chlorine dioxide being in a gaseous state at room temperature and having a specific gravity greater than that of air. A water-absorbing reactive chlorine dioxide slow-release granules are prepared through a scientific formula. The chlorine dioxide slow-release granules are used to disinfect and sterilize the soil before planting, which can effectively kill pathogenic microorganisms in the soil and decompose organic pesticide residues in the soil, eliminating pathogenic microorganisms and toxins. The use of probiotics can quickly restore the soil microbial environment that is conducive to the growth of small yellow ginger. Soaking and detoxifying the seedlings with a chlorine dioxide solution can kill the disease microorganisms carried by the seedlings and avoid contaminating the planting soil. During the planting period, scientific and conventional inter-field planting management techniques are used to effectively control the continuous cropping disorder of small yellow ginger.
[0020] During the soil treatment process, the present invention spreads chlorine dioxide slow-release particles on the soil and mixes the particles with the soil through tillage. The chlorine dioxide slow-release particles quickly absorb moisture from the soil and air and gradually expand to form a three-dimensional network molecular structure. The absorbed moisture simultaneously causes chlorite and solid acid to ionize to generate freely movable chlorite and hydrogen ions. The chlorite and hydrogen ions react to generate chlorine dioxide gas molecules, which are bound within the network structure molecules and slowly released into the surrounding soil particles. Since chlorine dioxide has a greater specific gravity than air, the chlorine dioxide gas slowly sinks to the bottom of the soil particle layer and gradually accumulates. The accumulated chlorine dioxide gas molecules gradually kill microorganisms in the soil particle layer after contacting them, and gradually oxidize and decompose organic pesticide residues after contacting them. Due to its instability, the chlorine dioxide gas remaining in the soil eventually decomposes into chloride ions and oxygen, which is completely harmless to the environment.
[0021] The synergistic effect of the chlorine dioxide slow-release particles and probiotics in the present invention is aimed at repairing the continuous cropping problem of small yellow ginger. Through the multi-stage linkage mechanism of "chemical disinfection-biological reconstruction-ecological balance", it realizes the reconstruction of the soil microenvironment and the systematic improvement of crop resistance.
[0022] In the initial stages of soil remediation, chlorine dioxide slow-release granules precisely disinfect soilborne pathogens through a pH-responsive release mechanism. When locally acidified soils due to pathogen metabolism in continuously cropped soils, the core material of the chlorine dioxide slow-release granules rapidly responds by releasing chlorine dioxide. Its strong oxidizing properties rapidly kill pathogens such as Fusarium and Pythium, preventing them from infecting ginger roots. Simultaneously, probiotics (such as Bacillus subtilis), leveraging their stress-resistant spore form, survive the chlorine dioxide concentration gradient and colonize the "ecological niche" left by the disinfection. This temporal and spatial staggered disinfection and colonization design not only prevents accidental damage to probiotics by chemical agents, but also creates a window for probiotics to occupy their rhizosphere niche. Glucosamine, a progressive degradation product of chitosan in the core material, serves as a preferential carbon and nitrogen source for the probiotics, further accelerating vegetative germination and biofilm formation, allowing them to quickly establish a dominant community in the disinfected soil.
[0023] During the ecological reconstruction stage, the metabolic interaction between probiotics and chlorine dioxide slow-release particles forms a closed loop of material circulation. The chloride ion byproducts produced by chlorine dioxide disinfection are gradually converted into harmless chlorides under the action of the dehalogenase of probiotics, avoiding the aggravation of soil salinization; and the organic acids and polysaccharides secreted by probiotic metabolism can buffer the local pH fluctuations caused by the release of chlorine dioxide slow-release particles and maintain the stability of the rhizosphere microenvironment. More importantly, the systemic resistance signaling pathway activated by probiotics through the quorum sensing effect complements the physical protective barrier formed by chlorine dioxide disinfection - when pathogens try Figure 2 During the first infection, ginger plants accumulate disease-resistant substances such as phytoalexins and pathogenesis-related proteins in advance under the induction of probiotics, while the residual chlorine dioxide in the chlorine dioxide slow-release granules continues to inhibit the germination of pathogen spores. This dual chemical and biological interception mechanism significantly enhances the plant's sustained disease resistance.
[0024] During the long-term maintenance phase, slow-release chlorine dioxide granules and probiotics achieve a dynamic equilibrium through niche competition. The biofilm formed by probiotics in the rhizosphere not only physically blocks pathogens from reaching ginger roots, but also secretes antimicrobial lipopeptides (such as surfactant) that specifically inhibit the proliferation of residual pathogens. Chlorine dioxide slow-release granules, through a gradient release of sublethal concentrations of chlorine dioxide, continuously weaken the activity of pathogens without completely eliminating them. This "inhibition without killing" strategy avoids catastrophic damage to soil microbial diversity while providing continuous selective pressure for the competitive growth of probiotics. The synergistic effect of chitosan degradation products and probiotic metabolites also stimulates the secretion of secondary metabolites such as flavonoids from ginger roots, improving root architecture and enhancing nutrient absorption efficiency, thereby breaking the cycle of autotoxicity associated with continuous cropping problems.
[0025] It should be noted that the probiotics added to the soil in the present invention are microbial agents that promote plant growth, increase yield, and reduce losses. They can be any one or a combination of Bacillus subtilis, Bacillus megaterium, Bacillus gelatinous, and Bacillus licheniformis. Because chlorine dioxide is non-selective in killing microorganisms in the soil, probiotics are also killed during the soil disinfection process. The purpose of supplementing probiotics is to restore the healthy activity of soil microorganisms.
[0026] During the seedling planting process, the ginger seeds are soaked in a chlorine dioxide solution. While inactivating pathogens on the surface of the ginger seeds, its controlled oxidation induces a mild stress response in the epidermal cells of the ginger seeds, activating the gibberellin synthesis pathway in the ginger bud primordia, breaking the dormant state and accelerating meristem differentiation. Chlorine dioxide slow-release granules applied to the soil maintain an antibacterial concentration in the rhizosphere through continuous low-dose release. The two form a disinfection intensity gradient. The ginger seed treatment eliminates the initial source of infection (seed-borne bacteria), while the chlorine dioxide slow-release granules block the secondary infection pathway (soil-borne). This progressive disinfection strategy avoids the physiological damage to the seed buds caused by a single high-concentration treatment and prevents the damage to the probiotic community caused by continuous high-concentration disinfection in the soil. At the same time, the trace amounts of chlorine dioxide decomposition products (Cl⁻, O2) remaining after the ginger seeds are soaked and disinfected can serve as electron acceptors for probiotics, activating their redox metabolic pathways and promoting biofilm formation. When probiotics form dominant communities in the rhizosphere, the lipopeptide antibacterial substances they secrete and the chlorine dioxide released by the chlorine dioxide slow-release particles produce a synergistic antibacterial effect - chlorine dioxide destroys the integrity of the pathogen cell membrane, and the probiotic antimicrobial peptides penetrate the damaged area to inhibit the activity of intracellular enzymes. The dual effects increase the inactivation efficiency of pathogens carried by the ginger seeds by 2 to 3 times.
[0027] During the field management process, the three-phase coupling of soil, crops and microorganisms is used to systematically eliminate the obstacles to continuous cropping. The humic acid-microorganism complex system in the organic mature fertilizer system can effectively activate the mineralization of soil organic matter. Its colloidal properties work together with the extracellular polysaccharides of probiotics to form a stable granular structure, which creates a loose space for root expansion while retaining water and fertilizer. The dynamic topdressing strategy accurately regulates nutrient supply according to the metabolic rhythm of the plant. High nitrogen in the seedling stage promotes the construction of photosynthetic organs, and increased potassium in the swelling stage accelerates the transport of assimilates to ginger pieces by regulating the osmotic pressure gradient. The mechanical stress induced by inter-tillage and soiling triggers the roots to secrete phenolic acids, which selectively inhibit pathogens and promote the proliferation of probiotics.
[0028] As a preferred technical solution of the present invention, the disinfection and sterilization treatment steps include:
[0029] Level the soil and apply chlorine dioxide slow-release granules to the soil within 10 to 15 days before planting the seedlings. Apply 6 to 8 kg of chlorine dioxide slow-release granules per mu of soil. Till the soil once within 2 hours after application to mix the soil with the chlorine dioxide slow-release granules. The application amount of chlorine dioxide slow-release granules can be 6.0 kg, 6.2 kg, 6.4 kg, 6.6 kg, 6.8 kg, 7.0 kg, 7.2 kg, 7.4 kg, 7.6 kg, 7.8 kg or 8.0 kg within 10 days, 11 days, 12 days, 13 days, 14 days or 15 days before planting the seedlings, but is not limited to the listed values. Other values not listed within this numerical range are also applicable.
[0030] In some optional examples, the steps of supplementing probiotics include:
[0031] After the soil has been disinfected and sterilized for 6 to 10 days, the Bacillus subtilis wettable powder is diluted with water and sprayed on the soil. 3 to 5 kg of Bacillus subtilis wettable powder is applied per mu of soil. The soil is plowed once within 2 to 3 hours after the spraying is completed to allow the Bacillus subtilis solution to penetrate deep into the soil. The application amount of the Bacillus subtilis wettable powder can be 3.0 kg, 3.2 kg, 3.4 kg, 3.6 kg, 3.8 kg, 4.0 kg, 4.2 kg, 4.4 kg, 4.6 kg, 4.8 kg or 5.0 kg, but is not limited to the listed values. Other values not listed within this numerical range are also applicable.
[0032] It should be noted that the harmless treatment adopted in the present invention is disclosed in the prior art, and the present invention does not make specific requirements or special limitations thereon. Exemplarily, the operating steps of the harmless treatment include:
[0033] Remove the stumps infected by soil-borne viruses that year and the broken branches and rotten leaves scattered on the ground, and landfill or incinerate the collected stumps and broken branches and leaves.
[0034] The optional steps for landfill treatment include:
[0035] The collected branches, leaves and roots are buried in a 1~2m deep pit, which is then filled and compacted. 8~10cm thick quicklime is sprinkled on the compacted soil surface, and then 10~15cm thick soil is covered on the quicklime.
[0036] As a preferred technical solution of the present invention, the chlorine dioxide slow-release granules are prepared by the following method:
[0037] (1) Sodium chlorite, an acidic activator, and deionized water are mixed, polyacrylic acid and chitosan are added, and the mixture is stirred to obtain a precursor gel, and the precursor gel is allowed to stand and dried to obtain core material particles;
[0038] (2) mixing the core material particles with the hydroxypropyl methylcellulose solution and then dropping the mixture into a coagulation bath to form gel beads, wherein the gel beads are allowed to crosslink in the coagulation bath and then dried to obtain intermediate particles;
[0039] (3) The intermediate particles are alternately immersed in ε-polylysine and sodium alginate solutions multiple times to obtain coated particles; then, the intermediate particles are immersed in a genipin solution for heating and cross-linking, and microwave-enhanced to obtain the chlorine dioxide slow-release particles.
[0040] More specifically, the chlorine dioxide slow-release granules are prepared by the following method:
[0041] (1) Sodium chlorite, an acidic activator, and deionized water are uniformly mixed to obtain a precursor solution; polyacrylic acid and chitosan are added to the precursor solution, and the mixture is mixed and stirred at low temperature to obtain a precursor gel; the precursor gel is placed in a low-temperature environment and allowed to stand for a period of time, and then the precursor gel after standing is dried in stages to obtain core material particles;
[0042] (2) uniformly mixing the core material particles obtained in step (1) with the hydroxypropyl methylcellulose solution to obtain an intermediate solution; dripping the intermediate solution into a coagulation bath through a sharp hole device to form gel beads, the gel beads being allowed to stand in the coagulation bath for a period of time to be cross-linked and solidified to form a quick-release layer on the surface of the core material particles, and the gel beads being removed and dried to obtain intermediate particles;
[0043] (3) Alternately immersing the intermediate particles obtained in step (2) in an ε-polylysine solution and a sodium alginate solution for several times to obtain coated particles, immersing the coated particles in a genipin solution, mixing, stirring, and heating to cause a cross-linking reaction, thereby forming a sustained-release layer on the surface of the intermediate particles to obtain composite particles; and subjecting the composite particles to stage-by-stage microwave enhancement to obtain the chlorine dioxide sustained-release particles.
[0044] The chlorine dioxide slow-release particles prepared by the present invention achieve precise regulation of the chlorine dioxide release rate and dynamic adaptation to the soil microenvironment requirements through a multi-layer progressive coating structure and precise process control, providing a complete solution from rapid disinfection to long-term protection for the management of continuous cropping obstacles of small yellow ginger.
[0045] During the core material preparation stage, the present invention adopts the low-temperature cross-linking technology of polyacrylic acid-chitosan composite gel to form a nano-scale network structure under precise temperature control of 4-6°C. The sodium chlorite and the acidic activator are stably isolated through the gradient temperature drying and negative pressure dehydration process, and the chemical inertness retention rate during the storage period reaches more than 99%. The core of the core material is formed by a physical mixture of sodium chlorite and the acidic activator in a mass ratio of 3:1 to 5:1. The two are spatially isolated by the composite gel network formed by polyacrylic acid and chitosan to avoid premature reaction and form the underlying architecture of the sustained-release system. Under low-temperature stirring conditions, the carboxylic acid functional groups of polyacrylic acid and the amino groups of chitosan form a three-dimensional gel network through hydrogen bonds and electrostatic effects. Through the combination of gradient temperature drying and negative pressure dehydration process, the gel network is dehydrated and shrunk to form a dense barrier layer, so that the water content of the core material is controlled below 3%, ensuring the chemical inertness of sodium chlorite during the storage period.
[0046] The core material serves as the core unit for the generation of chlorine dioxide. Its polyacrylic acid-chitosan composite gel achieves intelligent isolation and release of reactants through the dynamic balance of intermolecular forces. During the storage stage, the carboxylic acid functional groups of polyacrylic acid and the amino groups of chitosan form a dense network through electrostatic cross-linking and hydrogen bonding, separating sodium chlorite and acidic activators in different micro-regions to ensure chemical inertness. When the pH value of the soil environment drops below 5.5, the protonation of the carboxylic acid functional groups breaks the electrostatic balance, resulting in a weakening of the electrostatic interaction. The deprotonation of the chitosan amino groups further weakens the hydrogen bonds, causing the composite gel network to directional swell, opening the reactant contact channel and triggering the in situ generation of chlorine dioxide. The uniqueness of the core material lies in the pH threshold characteristic of its swelling behavior - release is initiated only when the environment is acidified to a specific range, avoiding ineffective losses caused by non-specific reactions.
[0047] The present invention coats the core material with a quick-release layer approximately 100-150 μm thick composed of hydroxypropyl methylcellulose using a sharp-pore coagulation bath technique. This quick-release layer acts as an environmental response "trigger," accelerating the activation of the core material through the swelling and disintegration of the hydroxypropyl methylcellulose gel. When the quick-release layer comes into contact with soil moisture, its methoxy groups hydrolyze to form carboxymethyl functional groups, triggering a surface charge reversal and a sudden change in osmotic pressure. This process causes the gel network in the quick-release layer to rapidly absorb water and expand. The resulting mechanical stress is sufficient to disrupt the barrier between sodium chlorite and the acidic activator in the core material, while simultaneously forming microchannels that accelerate the penetration of external H⁺ into the core material. The quick-release layer's function lies not only in its own disintegration and release, but also in its dual effects of structural destruction and ion guidance, forcing a lowering of the core material's microenvironmental pH, rapidly crossing the swelling threshold and achieving a rapid initiation of release kinetics. Furthermore, the porous scaffold structure formed by the swelling product of the hydroxypropyl methylcellulose provides a directional path for subsequent gas diffusion, preventing the impact of localized high concentrations on the soil microbial community.
[0048] The present invention further coats the quick-release layer with a sustained-release layer formed by alternating layers of ε-polylysine and sodium alginate, and forms a "dense-loose" layered structure through gradient microwave treatment. The surface of the sustained-release layer is a dense area with a pore size of less than 10nm. The surface of the sustained-release layer is formed by high-frequency microwave-induced genipin cross-linking of sodium alginate. The formed covalent cross-linked network has high chemical stability and will not undergo significant protonation or conformational changes due to changes in the environmental pH value. At the same time, the surface of the sustained-release layer forms a highly oriented molecular chain arrangement during the high-frequency microwave treatment process. The intermolecular forces are mainly covalent bonds and strong hydrogen bonds, and the proportion of electrostatic interactions is extremely low. This rigid network mainly based on covalent cross-linking only undergoes weak changes when the pH value fluctuates. The sustained-release layer can swell and shrink, so its pore structure can still maintain nanoscale dimensional stability, which can always serve as a basic barrier to limit the risk of sudden release of chlorine dioxide gas; the inner layer of the sustained-release layer is a loose area with a pore size in the range of 50~100nm. The dynamic adjustment mechanism of the pore size in the loose area is mainly based on the electrostatic cross-linking effect between ε-polylysine and sodium alginate. When the pH decreases, the amino group of ε-polylysine is protonated, and the electrostatic attraction with the carboxylate of sodium alginate is weakened, and the electrostatic repulsion between the molecular chains is enhanced, resulting in the expansion of the interlayer spacing of the alternately immersed layers, forming submicron pore channels. When the pH increases, the amino group is deprotonated to restore the electrostatic attraction, the molecular chains are stacked tightly again, and the interlayer spacing of the alternately immersed layers shrinks to the nanoscale. In the loose area, the covalent cross-linked network formed by genipin acts as a stable skeleton, ensuring the reversible change of the pore channels of each layer without causing structural collapse, while the dynamic balance of the electrostatic interaction between ε-polylysine and sodium alginate gives the loose area a "molecular spring" effect - the acidic environment increases the pores in the loose area, and the neutral environment triggers the pores in the loose area to shrink, thereby achieving the adaptation of the pore size of the loose area to pH fluctuations and accurately controlling the release rate of chlorine dioxide.
[0049] The synergistic mechanism of the core material, immediate-release layer, and sustained-release layer is essentially a cascade amplification and dynamic equilibrium process of pH signals. When organic acids (such as acetic acid and propionic acid) produced by pathogenic bacteria in the soil acidify the soil environment's pH, this triggers swelling of the immediate-release layer, further causing a sharp drop in the pH of the core material's microenvironment, forming a positive feedback loop: the immediate-release layer disintegrates, accelerating H⁺ penetration → the core material swells and releases reactants → chlorine dioxide is generated, lowering the environmental pH → further promoting the decomposition of the residual structure of the immediate-release layer. At the same time, the porosity of the sustained-release layer continues to expand as the soil pH decreases, forming a positive correlation between the release rate and the degree of acidification. That is, the higher the degree of soil acidification, the faster the chlorine dioxide release rate, and conversely, the lower the degree of soil acidification, the slower the chlorine dioxide release rate. When the disinfection reaction causes the soil pH to rise, a reverse regulation mechanism kicks in: the pores in the slow-release layer shrink, limiting the escape of chlorine dioxide gas. The core material's swelling decreases, slowing the reaction rate between sodium chlorite and the acidic activator. The remaining porous structure in the quick-release layer maintains a stable local pH by adsorbing excess Cl⁻. This "trigger-response-feedback" closed-loop control system precisely matches the chlorine dioxide release curve with the pathogen's metabolic activity curve, rapidly suppressing peak pathogen proliferation while preventing damage to the soil ecosystem caused by continued high-concentration release. Ultimately, this achieves a synergistic effect of highly effective disinfection and microecological reconstruction.
[0050] As a preferred technical solution of the present invention, in step (1), the mass ratio of sodium chlorite to the acidic activator is 1:(1-1.2), for example, it can be 1:1.0, 1:1.02, 1:1.04, 1:1.06, 1:1.08, 1:1.1, 1:1.12, 1:1.14, 1:1.16, 1:1.18 or 1:1.2, but is not limited to the listed values, and other values not listed within the numerical range are also applicable.
[0051] In some optional examples, the volume ratio of the total mass of the sodium chlorite and the acidic activator to the deionized water is (10~12)g:100mL, for example, it can be 10g:100mL, 10.2g:100mL, 10.4g:100mL, 10.6g:100mL, 10.8g:100mL, 11g:100mL, 11.2g:100mL, 11.4g:100mL, 11.6g:100mL, 11.8g:100mL or 12g:100mL, but is not limited to the listed values, and other values not listed within this numerical range are also applicable.
[0052] In some optional examples, the acidic activator includes citric acid or tartaric acid.
[0053] In some optional examples, the mass ratio of the polyacrylic acid to the chitosan is (3~5):1, for example, it can be 3.0:1, 3.2:1, 3.4:1, 3.6:1, 3.8:1, 4.0:1, 4.2:1, 4.4:1, 4.6:1, 4.8:1 or 5.0:1, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
[0054] The present invention specifically limits the mass ratio of polyacrylic acid to chitosan to (3-5):1. The carboxylic acid functional groups of polyacrylic acid and the amino groups of chitosan form a dynamic cross-linked network through electrostatic attraction. In a neutral environment, the moderate ionization of polyacrylic acid (approximately 30% of the carboxylic acid functional groups are deprotonated) and the protonated amino groups of chitosan form a stable charge balance, creating a nanoscale isolation structure that effectively separates sodium chlorite and the acidic activator into different microdomains. When the pH value of the core material's microenvironment decreases, the carboxylic acid functional groups of polyacrylic acid accelerate protonation, sharply reducing the electrostatic cross-linking strength, while the deprotonation of the chitosan amino groups further weakens the hydrogen bond network. These dual effects cause the gel network to rapidly swell, expanding the pore channels to the critical contact size of sodium chlorite and the acidic activator, triggering the reaction between the sodium chlorite and the acidic activator. The design of slightly excessive polyacrylic acid ensures that the gel preferentially dissociates electrostatic cross-links rather than hydrogen bond networks during the swelling process, which not only ensures the explosive growth of the swelling rate when the pH is triggered, but also maintains the integrity of the gel skeleton through residual hydrogen bonds, avoiding excessive swelling that leads to disordered diffusion of sodium chlorite and acidic activators. At the same time, the appropriate amount of chitosan allows it to partially dissolve under acidic conditions, and the resulting cationic fragments can adsorb anionic interferents in the soil, maintaining the pH stability of the reaction microenvironment. This synergistic mechanism at the molecular level enables the core material to not only stably store sodium chlorite and acidic activators for a long time, but also to be accurately activated and released on demand under external pH stimulation, forming the core power foundation of the intelligent sustained-release system.
[0055] When the amount of polyacrylic acid exceeds the upper limit of the range specified in this invention, the excess carboxylic acid functional groups cannot be fully neutralized by the amino groups of chitosan during storage, resulting in an excessively loose gel network due to electrostatic repulsion. This loose structure makes it difficult to effectively isolate sodium chlorite from the acidic activator, and slow pre-reactions (such as partial oxidation of chlorite to form chlorate) are likely to occur during storage. During pH-triggered release, the rapid protonation of the excess carboxylic acid functional groups triggers an "avalanche" swelling—the gel porosity expands to over 60% in a very short period of time. Direct contact between the sodium chlorite particles and the acidic activator results in an uncontrolled reaction rate, leading to a burst of chlorine dioxide release (over 80% release within 1 hour). This sudden release not only wastes the active ingredient, but also, high concentrations of chlorine dioxide can damage soil microbial communities.
[0056] When the amount of chitosan used exceeds the upper limit of the range defined in the present invention, the overly dense amino positive charges form a rigid cross-linked network with polyacrylic acid, compressing the porosity of the composite gel to below 10%. Although the storage stability is improved, the overly dense network seriously hinders the pH response efficiency of the core material. When the pH value of the environment decreases, the deprotonation rate of the chitosan amino group lags behind the protonation rate of polyacrylic acid, resulting in insufficient swelling power, insufficient contact area between chlorite and H⁺, and too low a reaction rate. At the same time, the hydrophobic crystalline region of excess chitosan will also hinder water penetration, further delaying the response time of the pH value, and ultimately resulting in insufficient and delayed release of chlorine dioxide, which cannot meet the initial rapid disinfection needs.
[0057] In some optional examples, the ratio of the total mass of the polyacrylic acid and the chitosan to the mass of the sodium chlorite is (1.3-1.5):1, for example, it can be 1.3:1, 1.32:1, 1.34:1, 1.36:1, 1.38:1, 1.4:1, 1.42:1, 1.44:1, 1.46:1, 1.48:1 or 1.5:1, but is not limited to the listed values, and other unlisted values within this numerical range are also applicable.
[0058] In some optional examples, the temperature of mixing and stirring the precursor solution, polyacrylic acid and chitosan is 4~6°C, for example, it can be 4.0°C, 4.2°C, 4.4°C, 4.6°C, 4.8°C, 5.0°C, 5.2°C, 5.4°C, 5.6°C, 5.8°C or 6.0°C, but is not limited to the listed values, and other unlisted values within this numerical range are also applicable.
[0059] In some optional examples, the mixing and stirring speed of the precursor solution, polyacrylic acid and chitosan is 200~300rpm, for example, it can be 200rpm, 210rpm, 220rpm, 230rpm, 240rpm, 250rpm, 260rpm, 270rpm, 280rpm, 290rpm or 300rpm, but is not limited to the listed values, and other unlisted values within this numerical range are also applicable.
[0060] In some optional examples, the mixing and stirring time of the precursor solution, polyacrylic acid and chitosan is 50~60min, for example, it can be 50min, 51min, 52min, 53min, 54min, 55min, 56min, 57min, 58min, 59min or 60min, but is not limited to the listed values, and other unlisted values within this numerical range are also applicable.
[0061] In some optional examples, the precursor gel is placed in a low-temperature environment of 3~5℃ and allowed to stand for 2~3h, wherein the standing temperature may be 3.0℃, 3.2℃, 3.4℃, 3.6℃, 3.8℃, 4.0℃, 4.2℃, 4.4℃, 4.6℃, 4.8℃ or 5.0℃, and the standing time may be 2.0h, 2.1h, 2.2h, 2.3h, 2.4h, 2.5h, 2.6h, 2.7h, 2.8h, 2.9h or 3.0h, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
[0062] It should be noted that the drying method adopted in the present invention is staged drying, including a first drying stage, a second drying stage and a third drying stage performed in sequence.
[0063] In some optional examples, the drying temperature of the first drying stage is 48~52°C, for example, it can be 48°C, 48.5°C, 49°C, 49.5°C, 50°C, 50.5°C, 51°C, 51.5°C or 52°C, but is not limited to the listed values, and other unlisted values within this numerical range are also applicable.
[0064] In some optional examples, the drying pressure in the first drying stage is -0.08~-0.1MPa, for example, it can be -0.08MPa, -0.082MPa, -0.084MPa, -0.086MPa, -0.088MPa, -0.09MPa, -0.092MPa, -0.094MPa, -0.096MPa, -0.098MPa or -0.1MPa, but is not limited to the listed values, and other unlisted values within this numerical range are also applicable.
[0065] In some optional examples, the drying time of the first drying stage is 3 to 4 hours, for example, it can be 3.0 hours, 3.1 hours, 3.2 hours, 3.3 hours, 3.4 hours, 3.5 hours, 3.6 hours, 3.7 hours, 3.8 hours, 3.9 hours or 4.0 hours, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
[0066] In some optional examples, the drying temperature of the second drying stage is 53~57°C, for example, it can be 53°C, 53.5°C, 54°C, 54.5°C, 55°C, 55.5°C, 56°C, 56.5°C or 57°C, but is not limited to the listed values, and other unlisted values within this numerical range are also applicable.
[0067] In some optional examples, the drying pressure of the second drying stage is -0.1~-0.12MPa, for example, it can be -0.1MPa, -0.102MPa, -0.104MPa, -0.106MPa, -0.108MPa, -0.11MPa, -0.112MPa, -0.114MPa, -0.116MPa, -0.118MPa or -0.12MPa, but is not limited to the listed values, and other unlisted values within this numerical range are also applicable.
[0068] In some optional examples, the drying time of the second drying stage is 2 to 3 hours, for example, it can be 2.0 hours, 2.1 hours, 2.2 hours, 2.3 hours, 2.4 hours, 2.5 hours, 2.6 hours, 2.7 hours, 2.8 hours, 2.9 hours or 3.0 hours, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
[0069] In some optional examples, the drying temperature of the third drying stage is 38~42°C, for example, it can be 38°C, 38.5°C, 39°C, 39.5°C, 40°C, 40.5°C, 41°C, 41.5°C or 42°C, but is not limited to the listed values, and other unlisted values within this numerical range are also applicable.
[0070] In some optional examples, the drying pressure in the third drying stage is 0.1 MPa.
[0071] In some optional examples, the drying time of the third drying stage is 1 to 2 hours, for example, it can be 1.0h, 1.1h, 1.2h, 1.3h, 1.4h, 1.5h, 1.6h, 1.7h, 1.8h, 1.9h or 2.0h, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
[0072] The present invention adopts a staged drying process and constructs a multi-scale coordinated sustained-release structural system inside the core material by gradually regulating the hydrogen bond reconstruction, electrostatic crosslinking and phase separation behavior of the gel network.
[0073] The core function of the first drying stage is to achieve ordered solidification of the gel network. Low temperatures (48-52°C) suppress the thermal motion of the polymer chains, allowing polyacrylic acid and chitosan to form a temporary three-dimensional network through hydrogen bonding, thereby fixing the extended conformation of the molecular chains. A negative pressure environment (-0.08-0.1 MPa) reduces the energy required for water molecules to escape, encouraging the smooth migration of free water in gaseous form along the pre-set nanopores and avoiding capillary stress concentration caused by rapid liquid water removal. This synergistic mechanism of "low-temperature-induced alignment and negative pressure-guided dehydration" avoids capillary stress concentration caused by rapid liquid water evaporation, ensures the uniformity and directionality of the primary pore structure, reduces the water content to 60%, and simultaneously forms a primary network skeleton with a uniform pore size distribution.
[0074] The key to the second drying stage lies in inducing nanoscale phase separation. When the temperature rises to 53-57°C, the thermal motion of the polyacrylic acid segments increases, partially ionizing the carboxylic acid groups and forming electrostatic crosslinks with the protonated amino groups (-NH⁺) of chitosan. At this point, increasing the negative pressure to -0.1-0.12 MPa accelerates the removal of bound water. The water migration path is restricted by the electrostatic crosslinking network, forcing microphase separation between the polyacrylic acid-rich and chitosan-rich phases. The polyacrylic acid phase shrinks to form hydrophobic microdomains of 50-80 nm (encapsulating the sodium chlorite), while the chitosan phase forms hydrophilic microdomains of 30-50 nm (encapsulating the acidic activator). A 2-3 nm transition layer forms at the interface between the two phases, where unionized -COOH groups dynamically connect to the chitosan acetylamino groups through hydrogen bonds. At this stage, the water content drops to 30%.
[0075] The purpose of the third drying stage is to strengthen the permanent cross-linked network and eliminate internal stress. The slow evaporation of residual water under normal pressure provides time for the polymer chains to restructure. The electrostatically cross-linked network gradually eliminates internal stress during thermal relaxation, ultimately forming a "core-shell" structure that combines rigidity and flexibility. The rearrangement of the chitosan molecular chains forms a dense surface layer, while the polyacrylic acid-dominated internal network retains moderate elasticity. This structural property enables the core material to withstand environmental humidity fluctuations during long-term storage and quickly respond to pH changes to initiate release after application.
[0076] Through the synergistic effect of staged drying, the core material forms a "core-shell" functional structure. The hydrophobic pores of the polyacrylic acid phase store sodium chlorite, while the hydrophilic nanopores of the chitosan phase encapsulate the acidic activator. The dynamic hydrogen-bonding network in the transition layer acts as a pH-responsive switch. When the ambient pH decreases, hydrogen bonds dissociate, expanding the pores in the transition layer and allowing H⁺ to penetrate the activator microdomains. Simultaneously, the carboxylic acid groups of the polyacrylic acid protonate, weakening electrostatic crosslinks. The main pores rapidly expand, exposing sodium chlorite particles and allowing them to participate in the reaction. This core material structure exhibits a three-stage chlorine dioxide release characteristic: in the initial stage (0-30 minutes), the transition layer responds rapidly, releasing 50% of the total chlorine dioxide for instant disinfection. In the mid-stage (1-24 hours), the main pores rapidly expand, releasing 40% of the total chlorine dioxide, maintaining an effective bactericidal concentration. In the late stage (24-120 hours), the chitosan crystals slowly dissolve, releasing the remaining 10% of chlorine dioxide, extending the protection period.
[0077] As a preferred technical solution of the present invention, in step (2), the ratio of hydroxypropyl methylcellulose to deionized water is (3-5) g:100 mL, for example, it can be 3.0 g:100 mL, 3.2 g:100 mL, 3.4 g:100 mL, 3.6 g:100 mL, 3.8 g:100 mL, 4.0 g:100 mL, 4.2 g:100 mL, 4.4 g:100 mL, 4.6 g:100 mL, 4.8 g:100 mL or 5.0 g:100 mL, but is not limited to the listed values, and other values not listed within the numerical range are also applicable.
[0078] In some optional examples, the mass ratio of the core material particles to the hydroxypropyl methylcellulose solution is 1:(5~7), for example, it can be 1:5.0, 1:5.2, 1:5.4, 1:5.6, 1:5.8, 1:6.0, 1:6.2, 1:6.4, 1:6.6, 1:6.8 or 1:7.0, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
[0079] The present invention specifically limits the mass ratio of the core material particles to the hydroxypropyl methylcellulose solution to 1:(5-7). The hydroxypropyl methylcellulose molecular chains are flexibly connected via β-1,4 glycosidic bonds, forming an "anchor-stretch" conformation on the core material surface: the methoxy hydrophobic segments embed within the core material's polyacrylic acid hydrophobic microdomains, while the hydroxypropyl hydrophilic segments extend outward to form a hydration barrier. When the mass ratio of the core material particles to the hydroxypropyl methylcellulose solution is within the specified range, the hydroxypropyl methylcellulose molecular chains form a continuous, dense, nanoscale coating on the core material surface through hydrogen bonding and hydrophobic interactions. This ensures sufficient stretching of the molecular chains to form a defect-free immediate-release layer while preventing entanglement and hardening caused by excessive chain congestion. More importantly, during the drying process, the shrinkage stress of the hydroxypropyl methylcellulose and the core material's anti-shrinkage strength form a moderate balance. This mass ratio range minimizes the difference between the shrinkage stress of the hydroxypropyl methylcellulose gel layer and the core material's anti-shrinkage strength, preventing interfacial delamination and the integrity of the immediate-release layer from being compromised.
[0080] When the amount of core material particles exceeds the upper limit of the range defined in the present invention, the mechanical balance between the quick-release layer and the core material will be broken. When the hydroxypropyl methylcellulose solution is not sufficient to completely infiltrate the surface of the core material, the molecular chains are forced to form a "bridge" structure between the core materials rather than a continuous film layer. This incomplete coating will lead to two problems: first, the mechanical strength of the hydroxypropyl methylcellulose bridge area between the core materials is much lower than that of the continuous film layer, causing the quick-release layer to be easily damaged by shear force, resulting in the exposure of the core material and the sudden release of the active ingredient; second, the exposed core material surface preferentially swells when it comes into contact with moisture, resulting in local stress concentration, forcing the quick-release layer to tear from the defect, thereby causing the release kinetics of chlorine dioxide to degenerate from the designed sustained-release mode to disordered release, completely losing the sustained-release function.
[0081] When the amount of hydroxypropyl methylcellulose exceeds the upper limit of the range defined by the present invention, it will cause the quick-release layer to be overloaded. Excessive hydroxypropyl methylcellulose molecular chains are stacked on the surface of the core material to form an ultra-thick gel layer. Although its dense structure can improve the mechanical strength, it seriously hinders the exchange of sodium chlorite in the core material with external water / protons. The hydrophobic methoxy groups of excess hydroxypropyl methylcellulose form an overly strong diffusion barrier. Even after hydration and expansion, the pore size of the gel network is still too small, far below the migration requirements of chlorite ions. This will also lead to two problems: first, the contact between the acidic activator and sodium chlorite in the core material is excessively delayed, and the reaction start-up time is greatly extended, which cannot meet the needs of rapid disinfection; second, the swelling of the thicker quick-release layer will squeeze the pore structure of the core material, forcing some unreacted sodium chlorite to be permanently embedded in the composite gel network of the core material, causing the effective ingredient to be retained and fail. What is more serious is that the rigid quick-release layer formed by the excessive amount of hydroxypropyl methylcellulose after drying will inhibit the pH-responsive swelling of the core material, making the intelligent release mechanism designed for the sustained-release layer completely ineffective.
[0082] In some optional examples, a mixed solution of core material particles and hydroxypropyl methylcellulose solution is dropped into a coagulation bath through a sharp hole device, and the aperture of the sharp hole device is 0.8~1.2mm, for example, it can be 0.8mm, 0.85mm, 0.9mm, 0.95mm, 1mm, 1.05mm, 1.1mm, 1.15mm or 1.2mm, but it is not limited to the listed values, and other unlisted values within this numerical range are also applicable.
[0083] In some optional examples, the coagulation bath is an ethanol aqueous solution of calcium chloride, wherein the volume fraction of ethanol in the ethanol aqueous solution is 70-80%, for example, it can be 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79% or 80%, but is not limited to the listed values, and other unlisted values within this numerical range are also applicable.
[0084] In some optional examples, the ratio of calcium chloride to ethanol aqueous solution in the coagulation bath is (10~12) g:100 mL, for example, it can be 10 g:100 mL, 10.2 g:100 mL, 10.4 g:100 mL, 10.6 g:100 mL, 10.8 g:100 mL, 11 g:100 mL, 11.2 g:100 mL, 11.4 g:100 mL, 11.6 g:100 mL, 11.8 g:100 mL or 12 g:100 mL, but is not limited to the listed values, and other unlisted values within this numerical range are also applicable.
[0085] In some optional embodiments, the temperature of the coagulation bath is 20~30℃, for example, it can be 20℃, 21℃, 22℃, 23℃, 24℃, 25℃, 26℃, 27℃, 28℃, 29℃ or 30℃, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
[0086] In some optional examples, the immersion time of the gel balls in the coagulation bath is 5 to 10 minutes, for example, it can be 5.0 minutes, 5.5 minutes, 6.0 minutes, 6.5 minutes, 7.0 minutes, 7.5 minutes, 8.0 minutes, 8.5 minutes, 9.0 minutes, 9.5 minutes or 10.0 minutes, but it is not limited to the listed values, and other values not listed within the numerical range are also applicable.
[0087] The present invention specifically limits the immersion time of the gel beads in the coagulation bath to 5 to 10 minutes. In the coagulation bath, calcium ions and the hydroxyl groups on the hydroxypropyl methylcellulose molecular chains form a three-dimensional network structure through ionic crosslinking. When the immersion time is within the range of 5 to 10 minutes, it ensures that the calcium ions fully react with the gel surface to form a dense crosslinked cortex, and avoids the structural rigidification caused by deep excessive crosslinking. When the immersion time is less than 5 minutes, the crosslinking reaction will be incomplete, and a loose and porous structure will be formed on the surface of the quick-release layer. During the water absorption and swelling stage, it will disintegrate prematurely due to insufficient mechanical strength, triggering a sudden release of chlorine dioxide, resulting in a waste of effective ingredients and possibly impacting the soil microbial community. If the immersion time exceeds 10 minutes, it will cause excessive penetration of calcium ions into the interior of the gel, forming a dense crosslinked layer, which will not only hinder the subsequent coating process of the sustained-release layer, but will also significantly reduce the water absorption and swelling capacity of the quick-release layer, delay the start-up time of the core material reaction, and weaken the initial disinfection effect.
[0088] In some optional examples, the drying temperature of the gel beads is 40~45°C, for example, it can be 40°C, 40.5°C, 41°C, 41.5°C, 42°C, 42.5°C, 43°C, 43.5°C, 44°C, 44.5°C or 45°C, but is not limited to the listed values, and other unlisted values within this numerical range are also applicable.
[0089] As a preferred technical solution of the present invention, in step (3), ε-polylysine is dissolved in a phosphate buffer solution with a pH value of 6 to 6.5 to obtain the ε-polylysine solution, for example, the pH value can be 6.0, 6.05, 6.1, 6.15, 6.2, 6.25, 6.3, 6.35, 6.4, 6.45 or 6.5, but is not limited to the listed values, and other values not listed within the numerical range are also applicable.
[0090] In some optional examples, the ratio of ε-polylysine to phosphate buffer is (2~3) g:100 mL, for example, it can be 2.0 g:100 mL, 2.1 g:100 mL, 2.2 g:100 mL, 2.3 g:100 mL, 2.4 g:100 mL, 2.5 g:100 mL, 2.6 g:100 mL, 2.7 g:100 mL, 2.8 g:100 mL, 2.9 g:100 mL or 3.0 g:100 mL, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
[0091] In some optional examples, sodium alginate is dissolved in an acetate buffer solution with a pH value of 5.5 to 6 to obtain the sodium alginate solution, for example, 5.5, 5.55, 5.6, 5.65, 5.7, 5.75, 5.8, 5.85, 5.9, 5.95 or 6, but is not limited to the listed values, and other values not listed within the numerical range are also applicable.
[0092] In some optional examples, the ratio of sodium alginate to acetate buffer is (2~3) g:100 mL, for example, it can be 2.0 g:100 mL, 2.1 g:100 mL, 2.2 g:100 mL, 2.3 g:100 mL, 2.4 g:100 mL, 2.5 g:100 mL, 2.6 g:100 mL, 2.7 g:100 mL, 2.8 g:100 mL, 2.9 g:100 mL or 3.0 g:100 mL, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
[0093] In some optional examples, the single immersion time of the intermediate particles in the ε-polylysine solution is 2 to 3 minutes, and the soaked intermediate particles are rinsed with deionized water after the single immersion. The intermediate particles are soaked in the ε-polylysine solution for a total of 3 to 5 times, wherein the single immersion time can be 2.0 minutes, 2.1 minutes, 2.2 minutes, 2.3 minutes, 2.4 minutes, 2.5 minutes, 2.6 minutes, 2.7 minutes, 2.8 minutes, 2.9 minutes or 3.0 minutes, and the number of immersions can be 3 times, 4 times or 5 times, but is not limited to the listed values, and other values not listed within this numerical range are also applicable.
[0094] In some optional examples, the single immersion time of the intermediate particles in the sodium alginate solution is 2 to 3 minutes, and the soaked intermediate particles are rinsed with deionized water after the single immersion. The intermediate particles are immersed in the sodium alginate solution for a total of 3 to 5 times, wherein the single immersion time can be 2.0 minutes, 2.1 minutes, 2.2 minutes, 2.3 minutes, 2.4 minutes, 2.5 minutes, 2.6 minutes, 2.7 minutes, 2.8 minutes, 2.9 minutes or 3.0 minutes, and the number of immersions can be 3 times, 4 times or 5 times, but is not limited to the listed values, and other values not listed within this numerical range are also applicable.
[0095] In some optional examples, the ratio of genipin to deionized water in the genipin solution is (0.4~0.5) g:100 mL, for example, it can be 0.4g:100mL, 0.41g:100mL, 0.42g:100mL, 0.43g:100mL, 0.44g:100mL, 0.45g:100mL, 0.46g:100mL, 0.47g:100mL, 0.48g:100mL, 0.49g:100mL or 0.5g:100mL, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
[0096] In some optional examples, the mixing and stirring speed of the coated particles in the genipin solution is 50~100rpm, for example, it can be 50rpm, 55rpm, 60rpm, 65rpm, 70rpm, 75rpm, 80rpm, 85rpm, 90rpm, 95rpm or 100rpm, but is not limited to the listed values, and other unlisted values within this numerical range are also applicable.
[0097] In some optional examples, in step (3), the heating temperature of the coated particles when immersed in the genipin solution is 45-50°C, for example, it can be 45°C, 45.5°C, 46°C, 46.5°C, 47°C, 47.5°C, 48°C, 48.5°C, 49°C, 49.5°C or 50°C, but is not limited to the listed values, and other values not listed within the numerical range are also applicable.
[0098] In some optional examples, the immersion time of the coated particles in the genipin solution is 50 to 55 minutes, for example, it can be 50 minutes, 50.5 minutes, 51 minutes, 51.5 minutes, 52 minutes, 52.5 minutes, 53 minutes, 53.5 minutes, 54 minutes, 54.5 minutes or 55 minutes, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
[0099] It should be noted that the microwave enhancement method adopted in the present invention is staged microwave enhancement, including a first microwave enhancement stage and a second microwave enhancement stage performed sequentially.
[0100] In some optional examples, the microwave power in the first microwave enhancement stage is 300~350W, for example, it can be 300W, 305W, 310W, 315W, 320W, 325W, 330W, 335W, 340W, 345W or 350W, but is not limited to the listed values, and other unlisted values within this numerical range are also applicable.
[0101] In some optional examples, the microwave time of the first microwave enhancement stage is 1 to 2 minutes, for example, it can be 1.0 min, 1.1 min, 1.2 min, 1.3 min, 1.4 min, 1.5 min, 1.6 min, 1.7 min, 1.8 min, 1.9 min or 2.0 min, but is not limited to the listed values, and other unlisted values within this numerical range are also applicable.
[0102] In some optional examples, the microwave power of the second microwave enhancement stage is 400~450W, for example, it can be 400W, 405W, 410W, 415W, 420W, 425W, 430W, 435W, 440W, 445W or 450W, but is not limited to the listed values, and other unlisted values within this numerical range are also applicable.
[0103] In some optional examples, the microwave time of the second microwave enhancement stage is 2 to 3 minutes, for example, it can be 2.0 minutes, 2.1 minutes, 2.2 minutes, 2.3 minutes, 2.4 minutes, 2.5 minutes, 2.6 minutes, 2.7 minutes, 2.8 minutes, 2.9 minutes or 3.0 minutes, but is not limited to the listed values, and other values not listed within the numerical range are also applicable.
[0104] The present invention utilizes a phased microwave-enhanced process to create a gradient structure within the sustained-release layer: a dense outer layer and a loose inner layer. In the first microwave-enhanced stage, a high-frequency alternating electric field preferentially excites the amino groups at the ends of the ε-polylysine molecular chains. These highly polarized chains align in the direction of the electric field, forming a dense layered structure through electrostatic attraction with the carboxylic acid groups of sodium alginate. During this stage, the non-thermal effect of the microwaves promotes rapid diffusion of the genipin crosslinker into the surface layer, where its epoxy groups undergo a ring-opening reaction with the hydroxyl groups of the sodium alginate. This creates a dense covalently crosslinked network within the surface layer of the sustained-release layer at a depth of 0-5 μm, reducing porosity. In the subsequent second microwave-enhanced stage, increased microwave power increases energy penetration, making the carboxylic acid groups of the sodium alginate backbone the primary polarization targets. The intense molecular chain vibrations partially dissociate electrostatic binding sites in the deeper layers of the sustained-release layer (5-20 μm). Simultaneously, genipin, aided by thermal effects, diffuses and crosslinks inward, forming a loose region with an increasing porosity gradient. This staged energy loading mode achieves spatial regulation of the material's cross-linking degree through differences in dielectric response. The dense cortical area acts like a "molecular sieve" to limit the initial burst release, while the loose inner area acts as a "buffer pool" to maintain the continuous release of chlorine dioxide.
[0105] The pore gradient structure of the sustained-release layer regulates the release of chlorine dioxide in three aspects: first, the nanoscale pores (<10nm) in the dense cortical zone limit the free diffusion of chlorine dioxide molecules through the size exclusion effect, controlling the release amount in the initial 30 minutes to less than 30% of the total load, thereby avoiding the damage of high-concentration chlorine dioxide shock to the soil microbial community; second, the gradient pores (20-100nm) in the loose inner zone form a directional diffusion path through capillary adsorption. When the soil pH value decreases, the dynamic expansion of porosity greatly increases the diffusion coefficient of chlorine dioxide, and the release rate of chlorine dioxide is positively correlated with the acidity of the environment; third, a diffusion barrier is formed at the interface between the dense and loose zones. When the soil pH value rises, the low permeability of the dense zone is restored first, while the loose zone still maintains some open channels, making the release rate of chlorine dioxide exhibit a "soft landing" characteristic, extending the effective action time to more than 120 hours. This structure creates a negative feedback loop between the chlorine dioxide release curve and the metabolic activity of pathogens, namely: active bacterial flora leads to a decrease in pH → expansion of the pores in the sustained-release layer → increased chlorine dioxide release → disinfection and inhibition of bacterial flora → pH value rises → chlorine dioxide release rate falls, ultimately achieving a precise match between chlorine dioxide release and sterilization requirements.
[0106] If microwave intensification is completely eliminated, the mass transfer limitations of the traditional thermal cross-linking process cause the cross-linking reaction to be concentrated on the surface layer, while the delayed heat transfer within the layer forms a loose amorphous structure. Upon contact with moisture, the surface cross-linked network of this sustained-release layer rapidly swells and ruptures, and the loose structure of the inner layer cannot form an effective diffusion resistance, resulting in the rapid release of chlorine dioxide within 1 hour and the complete loss of its sustained-release function. If only a single microwave intensification is used, the uniform loading of electric field energy will lead to isotropic cross-linking of the material. When the microwave power is fixed, the difference in dielectric loss between the surface and inner layers is smoothed out, and the genipin cross-linker is randomly distributed due to the lack of gradient diffusion dynamics, ultimately forming a sustained-release layer with uniform porosity. When this structure encounters fluctuations in soil pH, the porosity of the membrane layer changes synchronously across the entire region, the chlorine dioxide release rate fluctuates violently, and adaptive regulation of release kinetics is impossible.
[0107] As a preferred technical solution of the present invention, the Bacillus subtilis wettable powder is prepared by the following method:
[0108] (i) centrifuging and concentrating the Bacillus subtilis fermentation broth to a spore concentration of ≥1×10¹¹ CFU / g, adding a composite protective agent, wherein the composite protective agent comprises ascorbic acid, sodium alginate, and sorbitol, and mixing to obtain a composite fermentation broth;
[0109] (ii) mixing white carbon black, diatomaceous earth and magnesium aluminum silicate to form a composite carrier, and mixing the composite fermentation liquid, potassium humate and a spore germination agent to obtain a mixed material, wherein the spore germination agent comprises L-alanine, inosine and fructose;
[0110] (iii) spray drying the mixture to obtain probiotic powder, mixing the probiotic powder with a composite surfactant, and then sieving and drying the mixture. The composite surfactant is composed of aliphatic polyoxyethylene ether and polysorbate 80.
[0111] More specifically, the Bacillus subtilis wettable powder is prepared by the following method:
[0112] (i) The Bacillus subtilis fermentation broth was centrifuged and concentrated to a spore concentration of ≥1×10 11 CFU / g, adding a composite protective agent to the Bacillus subtilis fermentation broth and mixing them evenly to obtain a composite fermentation broth; wherein the composite protective agent consists of ascorbic acid, sodium alginate and sorbitol;
[0113] (ii) mixing white carbon black, diatomaceous earth and magnesium aluminum silicate to obtain a composite carrier, and uniformly mixing the composite carrier, the composite fermentation liquid obtained in step (i), potassium humate and a spore germination agent to obtain a mixed material, wherein the spore germination agent comprises L-alanine, inosine and fructose;
[0114] (iii) spray-drying the mixture to obtain probiotic powder, and uniformly mixing the probiotic powder and a composite surfactant, sieving, and drying to obtain the Bacillus subtilis wettable powder; wherein the composite surfactant is composed of an aliphatic polyoxyethylene ether and polysorbate 80.
[0115] The present invention provides a preparation method of a Bacillus subtilis wettable powder, and constructs a full-chain synergistic system from bacterial protection to function activation through a multi-component synergistic mechanism.
[0116] Ascorbic acid, sodium alginate, and sorbitol in the composite protective agent form a triple synergistic protection mechanism. Ascorbic acid binds to the hydrophobic area on the spore surface through phenolic hydroxyl groups to construct antioxidant microdomains. Its reduction potential matches the activity of endogenous enzymes in the spores, effectively scavenging free radicals and reducing oxidative stress damage. In addition, its carboxylic acid functional group forms hydrogen bond anchoring with spore surface proteins to prevent membrane lipid peroxidation caused by high temperature. Sodium alginate, relying on the entanglement characteristics of linear polysaccharide chains, forms a temperature-responsive hydrated gel layer on the bacterial surface through a calcium ion-mediated "egg-box" structure. When drying, it releases bound water to form a vapor buffer layer to protect the spore core. After cooling, the hydrogen bond network is reorganized to maintain the elasticity of the cortex. Sorbitol is embedded in the membrane phospholipid layer to replace water molecules to maintain membrane fluidity, and dynamically couples with sodium alginate to regulate osmotic pressure balance. When the external osmotic pressure increases, sorbitol triggers the extension of the sodium alginate chain to increase the porosity. When the external osmotic pressure is stable, the rigid skeleton restricts the migration of sorbitol. The steric hindrance, energy transfer and conformational response of ascorbic acid, sodium alginate and sorbitol form a dynamic protection network, achieving synergistic effects of antioxidant, thermal buffering and osmotic regulation, significantly improving spore processing tolerance and germination activity.
[0117] The synergistic effect of silica, diatomaceous earth, magnesium aluminum silicate, and potassium humate in the composite carrier achieves efficient bacterial loading and functional enhancement. The silica's mesoporous network (2-5 nm) achieves nanoscale anchoring through hydrogen bonding between surface silanol groups and hydrophobic proteins from Bacillus subtilis spores. Its high surface area (>300 m² / g) provides dense loading sites for the bacteria, while the diatomaceous earth's macroporous structure (50-200 nm) forms gas exchange channels through capillary action, maintaining low-level respiratory metabolism in the dormant spores. The two, through pore hierarchy, create a complementary "mesoporous anchoring-macroporous permeability" structure, which prevents mechanical damage to the bacteria while providing pathways for the diffusion of metabolic products. The layered structure of magnesium aluminum silicate forms an intercalated complex through electrostatic attraction between the positive charges on its edges and the negative charges on the carrier surface. Its expandable interlayer spacing (0.8-1.2 nm) expands under wet conditions, forming an ion buffer zone that dynamically adsorbs competing cations such as Ca⁺ and Na⁺ in the soil, preventing electrostatic instability of the carrier-bacteria complex. The aromatic ring structure of potassium humate directionally binds to the hydrophobic region of the spore surface through π-π stacking. Its carboxylic acid functional groups form coordination bonds with the silanol groups of silica, creating an "organic-inorganic" hybrid bridge at the carrier-bacteria interface. This not only enhances physical adsorption strength but also maintains the electronic balance of the microenvironment surrounding the spores through the redox activity of the quinone group. This allows the bacteria to remain metabolically inert during drying and storage, while rapidly activating their functional expression in the soil environment, achieving a dual breakthrough in survival rate and bioactivity.
[0118] The synergistic effect of L-alanine, inosine and fructose in the spore germination agent achieves efficient germination of spores. L-alanine, as a specific ligand for the GerA receptor, triggers the reconstruction of the transmembrane proton gradient after binding to the germination receptor in the spore cortex, activates the PrkC kinase signaling pathway, and promotes the conversion of cortical hydrolases (from a dormant state to an active conformation, initiating the directional hydrolysis of cortical peptidoglycan. Inosine penetrates into the spore core through nucleoside transporters, and its ribose group is converted into 5-phosphate ribose in the pentose phosphate pathway, providing a precursor for DNA repair; at the same time, the purine ring of inosine enhances the activity of H⁺-ATPase through an allosteric effect, accelerating proton pumping to maintain the transmembrane potential difference required for germination. Fructose is converted into 5-phosphate ribose through the phosphotransferase system (P L-alanine (TS) is rapidly phosphorylated to fructose-6-phosphate. This generates ATP through glycolysis, driving sustained activation of cortical hydrolases. It also acts as an allosteric activator, upregulating pyruvate kinase activity and promoting the dissociation of the DPA-Ca²⁺ chelate in the core region. The synergistic effect of these three factors is manifested in the following: L-alanine preferentially activates germination signals, inosine simultaneously enhances energy metabolism and membrane potential remodeling, and fructose subsequently provides a carbon skeleton to support vegetative cell wall remodeling. This creates a chain reaction of "signal triggering, energy drive, and structural reconstruction," compressing germination lag time to one-third of that of traditional formulations and increasing germination synchronization to over 90%.
[0119] As a preferred technical solution of the present invention, in step (i), the mass ratio of ascorbic acid, sodium alginate and sorbitol is 1:(2-3):(1.3-1.5), for example, it can be 1:2:1.3, 1:2.1:1.32, 1:2.2:1.34, 1:2.3:1.36, 1:2.4:1.38, 1:2.5:1.4, 1:2.6:1.42, 1:2.7:1.44, 1:2.8:1.46, 1:2.9:1.48 or 1:3:1.5, but is not limited to the listed values, and other values not listed within the numerical range are also applicable.
[0120] In some optional examples, the amount of the composite protective agent added is 3-5 wt% of the mass of the Bacillus subtilis fermentation broth, for example, it can be 3.0 wt%, 3.2 wt%, 3.4 wt%, 3.6 wt%, 3.8 wt%, 4.0 wt%, 4.2 wt%, 4.4 wt%, 4.6 wt%, 4.8 wt% or 5.0 wt%, but is not limited to the listed values, and other values not listed within the numerical range are also applicable.
[0121] In some optional examples, in step (ii), the mass ratio of white carbon black, diatomaceous earth and magnesium aluminum silicate is (3-5):(4-6):1, for example, it can be 3:4:1, 3.2:4.2:1, 3.4:4.4:1, 3.6:4.6:1, 3.8:4.8:1, 4:5:1, 4.2:5.2:1, 4.4:5.4:1, 4.6:5.6:1, 4.8:5.8:1 or 5:6:1, but is not limited to the listed values, and other values not listed within the numerical range are also applicable.
[0122] In some optional examples, the mass ratio of the composite carrier to the composite fermentation broth is 1:(1.5~2.5), for example, it can be 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2.0, 1:2.1, 1:2.2, 1:2.3, 1:2.4 or 1:2.5, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
[0123] In some optional examples, the mass ratio of the potassium humate, the composite carrier and the spore germination agent is 1:(8~10):(0.3~0.5), for example, it can be 1:8:0.3, 1:8.2:0.32, 1:8.4:0.34, 1:8.6:0.36, 1:8.8:0.38, 1:9:0.4, 1:9.2:0.42, 1:9.4:0.44, 1:9.6:0.46, 1:9.8:0.48 or 1:10:0.5, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
[0124] In some optional examples, the mass ratio of L-alanine, inosine and fructose is 1:(1.5~2):(4~5), for example, it can be 1:1.5:4, 1:1.55:4.1, 1:1.6:4.2, 1:1.65:4.3, 1:1.7:4.4, 1:1.75:4.5, 1:1.8:4.6, 1:1.85:4.7, 1:1.9:4.8, 1:1.95:4.9 or 1:2:5, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
[0125] In some optional examples, the mixing and stirring time of the composite carrier, the composite fermentation liquid, the potassium humate and the spore germination agent is 30 to 40 minutes, for example, it can be 30 minutes, 31 minutes, 32 minutes, 33 minutes, 34 minutes, 35 minutes, 36 minutes, 37 minutes, 38 minutes, 39 minutes or 40 minutes, but is not limited to the listed values, and other values not listed within this numerical range are also applicable.
[0126] In some optional embodiments, in step (iii), the inlet air temperature of the spray drying is 60-70°C, for example, 60°C, 61°C, 62°C, 63°C, 64°C, 65°C, 66°C, 67°C, 68°C, 69°C or 70°C, but is not limited to the listed values, and other values not listed within this numerical range are also applicable.
[0127] In some optional embodiments, the outlet air temperature of the spray drying is 40~50°C, for example, it can be 40°C, 41°C, 42°C, 43°C, 44°C, 45°C, 46°C, 47°C, 48°C, 49°C or 50°C, but is not limited to the listed values, and other unlisted values within this numerical range are also applicable.
[0128] In some optional examples, the spray drying time is 20 to 30 seconds, for example, it can be 20 seconds, 21 seconds, 22 seconds, 23 seconds, 24 seconds, 25 seconds, 26 seconds, 27 seconds, 28 seconds, 29 seconds or 30 seconds, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
[0129] In some optional examples, the mass ratio of the aliphatic polyoxyethylene ether and polysorbate 80 is 1:(1.3~1.8), for example, it can be 1:1.3, 1:1.35, 1:1.4, 1:1.45, 1:1.5, 1:1.55, 1:1.6, 1:1.65, 1:1.7, 1:1.75 or 1:1.8, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
[0130] In some optional examples, the mass ratio of the probiotic powder to the complex surfactant is (26~28):1, for example, it can be 26:1, 26.2:1, 26.4:1, 26.6:1, 26.8:1, 27:1, 27.2:1, 27.4:1, 27.6:1, 27.8:1 or 28:1, but is not limited to the listed values, and other unlisted values within this numerical range are also applicable.
[0131] As a preferred technical solution of the present invention, in step (II), the weight of each piece of ginger seed screened out is 70-80 g, for example, it can be 70 g, 71 g, 72 g, 73 g, 74 g, 75 g, 76 g, 77 g, 78 g, 79 g or 80 g, but is not limited to the listed values, and other values not listed within the numerical range are also applicable.
[0132] In some optional embodiments, 1 to 2 strong buds are retained from each piece of seed ginger screened.
[0133] In some optional examples, the concentration of the chlorine dioxide solution is 50-100 ppm, for example, 50 ppm, 55 ppm, 60 ppm, 65 ppm, 70 ppm, 75 ppm, 80 ppm, 85 ppm, 90 ppm, 95 ppm or 100 ppm, but is not limited to the listed values, and other values not listed within the numerical range are also applicable.
[0134] In some optional examples, the soaking time of the ginger seed in the chlorine dioxide solution is 20 to 30 minutes, for example, it can be 20 minutes, 21 minutes, 22 minutes, 23 minutes, 24 minutes, 25 minutes, 26 minutes, 27 minutes, 28 minutes, 29 minutes or 30 minutes, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
[0135] In some optional examples, the drying time of the seed ginger after soaking is 1 to 2 days.
[0136] In some optional examples, the row spacing during ginger planting is 50~70cm, for example, it can be 50cm, 52cm, 54cm, 56cm, 58cm, 60cm, 62cm, 64cm, 66cm, 68cm or 70cm, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
[0137] In some optional examples, the spacing between ginger plants is 20-30 cm, for example, 20 cm, 21 cm, 22 cm, 23 cm, 24 cm, 25 cm, 26 cm, 27 cm, 28 cm, 29 cm or 30 cm, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
[0138] In some optional examples, a 50-60 cm aisle is left between every 4-6 rows of ginger plants, for example, it can be 50 cm, 51 cm, 52 cm, 53 cm, 54 cm, 55 cm, 56 cm, 57 cm, 58 cm, 59 cm or 60 cm, but is not limited to the listed values, and other values not listed within the numerical range are also applicable.
[0139] As a preferred technical solution of the present invention, in step (III), the amount of organic mature fertilizer applied is: 1000-1500 kg of decomposed feces, 40-50 kg of triple compound fertilizer, 15-25 kg of highly active humic acid, 20-30 kg of potassium calcium magnesium sulfate fertilizer, 0.8-1.2 kg of phoxim insecticide and 80-100 kg of microbial agent per mu, wherein the mass of decomposed feces can be 1000 kg, 1050 kg, 1100 kg, 1150 kg, 1200 kg, 1250 kg, 1300 kg, 1350 kg, 1400 kg, 1450 kg or 1500 kg, the mass of triple compound fertilizer can be 40 kg, 41 kg, 42 kg, 43 kg, 44 kg, 45 kg, 46 kg, 47 kg, 48 kg, 49 kg or 50 kg, the mass of highly active humic acid can be 20-30 kg. The mass of the potassium calcium magnesium fertilizer can be 15kg, 16kg, 17kg, 18kg, 19kg, 20kg, 21kg, 22kg, 23kg, 24kg or 25kg, the mass of the potassium calcium magnesium fertilizer can be 20kg, 21kg, 22kg, 23kg, 24kg, 25kg, 26kg, 27kg, 28kg, 29kg or 30kg, the mass of the phoxim insecticide can be 0.8kg, 0.85kg, 0.9kg, 0.95kg, 1kg, 1.05kg, 1.1kg, 1.15kg or 1.2kg, and the mass of the microbial agent can be 80kg, 82kg, 84kg, 86kg, 88kg, 90kg, 92kg, 94kg, 96kg, 98kg or 100kg, but is not limited to the listed values, and other values not listed within this numerical range are equally applicable.
[0140] It should be noted that the topdressing process of the organic mature fertilizer provided by the present invention is carried out in three steps, including:
[0141] (a) After the plants have all grown up and the first bifurcation occurs, the first topdressing is carried out, with 10-20 kg of urea per mu, followed by the first shallow tillage and soiling. For example, the amount of urea can be 10 kg, 11 kg, 12 kg, 13 kg, 14 kg, 15 kg, 16 kg, 17 kg, 18 kg, 19 kg or 20 kg, but is not limited to the values listed above. Other values not listed within this range are also applicable;
[0142] (b) A second topdressing shall be carried out at the three-branch stage of the plant, with 30-40 kg of triple compound fertilizer, 20 kg of potassium sulfate and 10 kg of highly active humic acid applied per mu, followed by a second shallow tillage and soiling. The mass of the triple compound fertilizer may be 30 kg, 31 kg, 32 kg, 33 kg, 34 kg, 35 kg, 36 kg, 37 kg, 38 kg, 39 kg or 40 kg, but is not limited to the values listed. Other values not listed within this range are also applicable;
[0143] (c) Before the plants are closed in the rows, the third topdressing shall be carried out during the period of underground rhizome expansion, with 20-30 kg of triple compound fertilizer, 15-20 kg of potassium sulfate and 10 kg of highly active humic acid applied per mu, followed by a third shallow tillage and soil cultivation of the soil. The mass of the triple compound fertilizer may be 20 kg, 21 kg, 22 kg, 23 kg, 24 kg, 25 kg, 26 kg, 27 kg, 28 kg, 29 kg or 30 kg, and the mass of potassium sulfate may be 15 kg, 15.5 kg, 16 kg, 16.5 kg, 17 kg, 17.5 kg, 18 kg, 18.5 kg, 19 kg, 19.5 kg or 20 kg, but are not limited to the listed values. Other values not listed within this numerical range are also applicable.
[0144] It should be noted that the present invention does not specifically limit the prevention and control of diseases, insect pests and weeds. In order to help those skilled in the art better understand the technical solutions and beneficial effects of the present invention, the present invention provides the following optional disease (root rot, anthracnose, blight), insect and weed control methods.
[0145] (1) Root rot (you can choose any of the following prevention and control options):
[0146] (1.1) Use 50-75g of root rot spirit or 30-40g of "Keshade 2000" diluted with 50-60kg of water per mu and spray three times in a row with an interval of 5-7 days;
[0147] (1.2) Use 500~600mL of Green Treasure No. 1, or 150g of Chongchaobao plus 500~800g of Dichlorobenzyl pyrophosphate, and add 150~200kg of water for root irrigation.
[0148] (2) Anthracnose (you can choose any of the following prevention and control options):
[0149] (2.1) Apply 100mL of Green Treasure No. 1 per mu, and topdress with 100mL of Green Treasure No. 2 every 5 days, and spray with 50-60kg of water respectively;
[0150] (2.2) Use 30-40g of "Keshade 2000" or 100mL of Xiaoyedi or 100g of 70% methyl thiophanate per mu, mixed with 50-60kg of water, and spray three times in a row with an interval of 5-7 days.
[0151] (3) Diseases (you can choose any of the following prevention and control options):
[0152] (3.1) Apply 100mL of Green Treasure No. 1 per mu, and topdress with 100mL of Green Treasure No. 2 every 5 days, and spray with 50-60kg of water respectively;
[0153] (3.2) Use 100g of Ridomil or 100g of Gel or 100g of 70% Thiophanate-methyl per mu, diluted with 50-60kg of water, and spray three times in a row with an interval of 5-7 days.
[0154] (4) Pests (you can choose any of the following control options):
[0155] (4.1) Physical control: White grubs are the larvae of scarab beetles. From mid-May to mid-June, using a high-frequency insecticidal lamp to lure and kill scarab beetles can effectively prevent and control the damage caused by white grubs to turmeric.
[0156] (4.2) At sowing time, apply 3-4 kg of 3% carbofuran, 1.5-2 kg of 10% phoxam, 5-8 kg of 1605 powder, or 5-7 kg of leafhopper powder per mu, mixed with 60-80 kg of fine soil and applied in furrows;
[0157] (4.3) Use 80-160 mL of cutworm killer or 200-300 mL of methyl parathion per mu, add 60-80 kg of water and spray on the ground.
[0158] (5) Weed damage:
[0159] (5.1) For dicotyledonous weeds before gingelly sprouts (grass without seedlings), spray 1000mL of 10% glyphosate, 250mL of 41% Roundup, 150g of 74.7% Nongminle, 200-300g of 30% Feida, or 200mL of G-Wuzong diluted with 40-60kg of water per mu;
[0160] (5.2) After sowing turmeric or weeding the old ginger field (no weeds or seedlings), spray 30-45 mL of 90% Harness or 100 mL of 72% Dole Emulsion per mu, diluted with 60 kg of water;
[0161] (5.3) After the turmeric and weeds have emerged, use 40mL of 5% quizalofop-ethyl emulsifiable concentrate, 40-50mL of 10.8% high-efficiency quizalofop-ethyl emulsifiable concentrate, 35-40mL of 8.8% quizalofop-ethyl emulsifiable concentrate, or 35-40mL of 12% quizalofop-ethyl emulsifiable concentrate per mu, and add 60kg of water for spraying.
[0162] Compared with the prior art, the present invention has the following beneficial effects:
[0163] The method for comprehensively controlling the continuous cropping disorder of small yellow ginger provided by the present invention cleverly utilizes the physical characteristics of chlorine dioxide being in a gaseous state at room temperature and having a specific gravity greater than that of air. A water-absorbing reactive chlorine dioxide slow-release granules are prepared through a scientific formula. The chlorine dioxide slow-release granules are used to disinfect and sterilize the soil before planting, which can effectively kill pathogenic microorganisms in the soil and decompose organic pesticide residues in the soil, eliminating pathogenic microorganisms and toxins. The use of probiotics can quickly restore the soil microbial environment that is conducive to the growth of small yellow ginger. Soaking and detoxifying the seedlings with a chlorine dioxide solution can kill the disease microorganisms carried by the seedlings and avoid contaminating the planting soil. During the planting period, scientific and conventional inter-field planting management techniques are used to effectively control the continuous cropping disorder of small yellow ginger. BRIEF DESCRIPTION OF THE DRAWINGS
[0164] Figure 1 This is a scanning electron microscope image of the chlorine dioxide slow-release granules prepared in Example 1 of the present invention;
[0165] Figure 2 This is a scanning electron microscope image of the surface morphology of the chlorine dioxide slow-release granules prepared in Example 1 of the present invention;
[0166] Figure 3 This is a transmission electron micrograph of the chlorine dioxide slow-release granules prepared in Example 1 of the present invention;
[0167] Figure 4 This is a partial transmission electron micrograph of the chlorine dioxide slow-release granules prepared in Example 1 of the present invention;
[0168] Figure 5 This is a scanning electron micrograph of a cross-section of the sustained-release layer of the chlorine dioxide sustained-release granules prepared in Example 1 of the present invention in a buffer solution at pH = 4.5;
[0169] Figure 6 This is a scanning electron micrograph of a cross-section of the sustained-release layer of the chlorine dioxide sustained-release granules prepared in Example 1 of the present invention in a buffer solution at pH=7.5;
[0170] Figure 7 This is a transmission electron micrograph of the chlorine dioxide slow-release particles prepared in Example 1 of the present invention in a buffer solution at pH = 7.5;
[0171] Figure 8 This is a transmission electron micrograph of the chlorine dioxide slow-release granules prepared in Example 1 of the present invention in a buffer solution at pH=5.5;
[0172] Figure 9 This is a transmission electron micrograph of the chlorine dioxide slow-release granules prepared in Example 1 of the present invention in a buffer solution at pH=4.5;
[0173] Figure 10This is a physical picture of the inhibition zone formed by the chlorine dioxide slow-release granules prepared in Example 1 of the present invention in the antibacterial test. DETAILED DESCRIPTION
[0174] The technical solutions of the present invention are described in detail below in conjunction with specific embodiments and their accompanying drawings. The embodiments described herein are specific embodiments of the present invention and are used to illustrate the concept of the present invention; these descriptions are explanatory and exemplary and should not be understood as limiting the embodiments of the present invention and the scope of protection of the present invention. In addition to the embodiments described herein, those skilled in the art can also adopt other obvious technical solutions based on the contents disclosed in the claims of this application and its specification, including technical solutions that adopt any obvious replacements and modifications to the embodiments described herein.
[0175] Example 1
[0176] This embodiment provides a method for comprehensively controlling the continuous cropping disorder of small yellow ginger by combining slow-release chlorine dioxide soil disinfection granules with probiotics, the method comprising:
[0177] (1) Soil treatment: The residual branches, leaves and roots in the soil of the planting area are treated harmlessly, and the residual plants infected by soil-borne viruses and the residual branches and leaves scattered on the ground are removed. The collected residual plants, branches and leaves are burned;
[0178] (2) Disinfection and sterilization: Level the soil and apply chlorine dioxide slow-release granules to the soil within 10 days before planting the seedlings. Apply 6 kg of chlorine dioxide slow-release granules per mu of soil. Plow the soil once within 2 hours after application to mix the soil with the chlorine dioxide slow-release granules.
[0179] Wherein, the chlorine dioxide slow-release granules are prepared by the following method:
[0180] (2.1) Sodium chlorite, citric acid, and deionized water were uniformly mixed to obtain a precursor solution, wherein the mass ratio of sodium chlorite to citric acid was 1:1, and the volume ratio of the total mass of sodium chlorite and citric acid to deionized water was 10 g:100 mL. Polyacrylic acid and chitosan were added to the precursor solution in a mass ratio of polyacrylic acid to chitosan of 3:1, and the ratio of the total mass of polyacrylic acid and chitosan to the mass of sodium chlorite in the precursor solution was 1.3:1. The mixture was stirred at 4°C and 200 rpm for 60 min to obtain a precursor gel.
[0181] The precursor gel is placed in a low-temperature environment of 3°C and allowed to stand for 3 hours. The precursor gel after standing is then subjected to a first drying stage, a second drying stage and a third drying stage in sequence. The drying temperature of the first drying stage is 48°C, the drying pressure is -0.08MPa, and the drying time is 4 hours. The drying temperature of the second drying stage is 53°C, the drying pressure is -0.1MPa, and the drying time is 3 hours. The drying temperature of the third drying stage is 38°C, the drying pressure is 0.1MPa, and the drying time is 2 hours. After drying in stages, core material particles are obtained.
[0182] (2.2) Mixing hydroxypropyl methylcellulose and deionized water at a ratio of 3 g:100 mL to obtain a hydroxypropyl methylcellulose solution, and mixing the core material particles obtained in step (2.1) with the hydroxypropyl methylcellulose solution at a mass ratio of 1:5 to obtain an intermediate solution;
[0183] The intermediate solution is dripped into a coagulation bath at 20° C. through a sharp hole device with an aperture of 0.8 mm to form gel beads, wherein the coagulation bath is a calcium chloride-ethanol aqueous solution, the volume fraction of ethanol in the ethanol aqueous solution is 70%, and the ratio of calcium chloride to ethanol aqueous solution is 10 g:100 mL. The gel beads are immersed in the coagulation bath for 5 minutes for cross-linking and curing to form a quick-release layer on the surface of the core material particles. The gel beads are removed and dried at 40° C. to obtain intermediate particles.
[0184] (2.3) Dissolve ε-polylysine in phosphate buffer at pH 6 to obtain an ε-polylysine solution, with the ratio of ε-polylysine to phosphate buffer being 2 g:100 mL. Dissolve sodium alginate in acetate buffer at pH 5.5 to obtain a sodium alginate solution, with the ratio of sodium alginate to acetate buffer being 2 g:100 mL.
[0185] The intermediate particles obtained in step (2.2) were alternately immersed in an ε-polylysine solution and a sodium alginate solution. The single immersion time in the ε-polylysine solution was 2 minutes, and the single immersion time in the sodium alginate solution was 2 minutes. After each immersion, the intermediate particles were rinsed with deionized water. After 5 alternating immersions, coated particles were obtained.
[0186] The coated particles were immersed in a genipin solution, wherein the ratio of genipin to deionized water in the genipin solution was 0.4 g:100 mL, and the mixture was stirred at a heating temperature of 45° C. and a rotation speed of 50 rpm for 55 minutes to cause a cross-linking reaction, thereby forming a sustained-release layer on the surface of the intermediate particles to obtain composite particles;
[0187] The composite particles were subjected to a first microwave intensification stage and a second microwave intensification stage in sequence, wherein the microwave power of the first microwave intensification stage was 300 W and the microwave time was 2 min, and the microwave power of the second microwave intensification stage was 400 W and the microwave time was 3 min, to obtain chlorine dioxide slow-release particles;
[0188] (3) Supplementation of probiotics: After 6 days of soil disinfection and sterilization, dilute the Bacillus subtilis wettable powder with water and spray it into the soil (1000 mL of water per gram of Bacillus subtilis wettable powder). Apply 3 kg of Bacillus subtilis wettable powder per mu of soil. Till the soil once within 2 hours after spraying to allow the Bacillus subtilis solution to penetrate deep into the soil.
[0189] Wherein, the Bacillus subtilis wettable powder is prepared by the following method:
[0190] (3.1) Centrifuge the Bacillus subtilis fermentation broth to a spore concentration of ≥1×10 11 CFU / g, a composite protective agent is added to a Bacillus subtilis fermentation broth, and the mixture is mixed uniformly to obtain a composite fermentation broth; wherein the composite protective agent is composed of ascorbic acid, sodium alginate and sorbitol, the mass ratio of ascorbic acid, sodium alginate and sorbitol is 1:2:1.3, and the amount of the composite protective agent added is 3wt% of the mass of the Bacillus subtilis fermentation broth;
[0191] (3.2) mixing white carbon black, diatomaceous earth, and magnesium aluminum silicate in a mass ratio of 3:4:1 to obtain a composite carrier, and mixing the composite carrier, the composite fermentation broth obtained in step (i), potassium humate, and a spore germination agent for 30 minutes to obtain a mixed material, wherein the mass ratio of the composite carrier to the composite fermentation broth is 1:1.5, the mass ratio of potassium humate, the composite carrier, and the spore germination agent is 1:8:0.3, and the spore germination agent comprises L-alanine, inosine, and fructose, and the mass ratio of L-alanine, inosine, and fructose is 1:1.5:4;
[0192] (3.3) Spray-dry the mixture to obtain a probiotic powder, wherein the inlet air temperature of the spray drying is 60°C, the outlet air temperature is 40°C, and the drying time is 30 seconds. The probiotic powder and a composite surfactant are uniformly mixed, sieved, and dried to obtain a Bacillus subtilis wettable powder; wherein the composite surfactant comprises an aliphatic polyoxyethylene ether and polysorbate 80 in a mass ratio of 1:1.3, and the mass ratio of the probiotic powder to the composite surfactant is 26:1.
[0193] (4) Planting of seedlings: Select ginger seeds with good skin color, no rot and no disease. The weight of each piece of ginger seed is 70g. Each piece of ginger seed is retained with one strong bud. Soak the selected ginger seed in a 50ppm chlorine dioxide solution for 30min. After soaking, dry it naturally for 1 day and then sow it in the soil. The row spacing of ginger seed is 50cm and the plant spacing is 20cm. Leave a 50cm walkway between every 4 rows of ginger seed rows. Cover with soil after sowing.
[0194] (5) Field management: Apply organic fertilizer to the soil after planting, applying 1000kg of decomposed manure, 50kg of triple compound fertilizer, 15kg of highly active humic acid, 20kg of potassium sulfate calcium magnesium fertilizer, 0.8kg of phoxim insecticide and 100kg of microbial agent per mu;
[0195] During the plant growth period, topdressing should be carried out according to the growth situation. Topdressing should be carried out three times, including:
[0196] (5.1) After the plants have fully grown and the first bifurcation occurs, apply the first topdressing fertilizer, applying 10 kg of urea per mu, followed by the first shallow tillage of the soil;
[0197] (5.2) When the plants have three branches, apply the second topdressing fertilizer, 40kg of triple compound fertilizer, 20kg of potassium sulfate and 10kg of highly active humic acid per mu, and then carry out the second shallow tillage and soil cultivation;
[0198] (5.3) Before the plants are closed in the rows, the third topdressing should be carried out during the period of underground rhizome expansion. 20kg of triple compound fertilizer, 20kg of potassium sulfate and 10kg of highly active humic acid should be applied per mu, and then the soil should be cultivated for the third time in a shallow layer.
[0199] When diseases, insect pests and weeds occur, spray the soil with pesticides to prevent and control them.
[0200] Figure 1 and Figure 2 The overall structure and surface morphology of the chlorine dioxide slow-release particles prepared in this example are respectively shown in the scanning electron microscope images. Figure 1 It can be seen that the overall structure of the chlorine dioxide slow-release particles is a regular spherical structure with a diameter of 40~50μm. Figure 2 It can be seen that the surface of the chlorine dioxide slow-release particles is relatively dense. This is because the present invention adopts a staged microwave intensification process to construct a gradient structure of "cortical dense area-inner loose area" in the slow-release layer.
[0201] Figure 3 and Figure 4The transmission electron micrographs (TEM) of the overall structure and local structure of the chlorine dioxide slow-release granules prepared in this example are respectively. It can be seen from the figures that the chlorine dioxide slow-release granules prepared in this example have a clear double-layer core-shell structure, consisting of an internal core material, a quick-release layer coated on the surface of the core material, and a slow-release layer coated on the surface of the quick-release layer.
[0202] Figure 5 and Figure 6 The sustained-release layer of the chlorine dioxide sustained-release particles prepared in this example is respectively a cross-sectional scanning electron micrograph of the sustained-release layer in a citric acid-disodium hydrogen phosphate buffer solution at pH = 4.5 and a Tris-HCl buffer solution at pH = 7.5. As can be seen from the figure, the sustained-release layer of the chlorine dioxide sustained-release particles is a multilayer structure formed by alternating impregnation and cross-linking of ε-polylysine and sodium alginate. Figure 5 It can be seen that when in a citric acid-disodium hydrogen phosphate buffer environment with a pH of 4.5, the amino group of ε-polylysine is protonated, the electrostatic attraction with the carboxylate of sodium alginate is weakened, and the electrostatic repulsion between the molecular chains is enhanced, resulting in an expansion of the interlayer spacing of the alternately immersed layers, forming submicron pore channels. Figure 6 It can be seen that when in a Tris-HCl buffer environment with pH = 7.5, the amino group is deprotonated to restore the electrostatic attraction, the molecular chains are stacked tightly again, and the interlayer spacing of the alternately immersed layers shrinks to the nanoscale.
[0203] Figure 7 、 Figure 8 and Figure 9 The transmission electron micrographs of the chlorine dioxide slow-release particles prepared in this example in Tris-HCl buffer at pH = 7.5, acetic acid-sodium acetate buffer at pH = 5.5, and citric acid-disodium hydrogen phosphate buffer at pH = 4.5 are shown respectively. Figure 7 It can be seen that when the chlorine dioxide slow-release particles are in a Tris-HCl buffer environment with a pH of 7.5, the pores of the slow-release layer shrink, limiting the escape of chlorine dioxide gas, and the swelling degree of the quick-release layer and the core material decreases, slowing down the reaction rate of sodium chlorite and the acidic activator, and reducing the release of chlorine dioxide. Figure 8 It can be seen that when the chlorine dioxide slow-release particles are in an acetic acid-sodium acetate buffer environment with a pH of 5.5, the quick-release layer and the slow-release layer swell, H⁺ gradually penetrates into the core material, and the isolation restriction of sodium chlorite and the acid activator is released, and the two begin to react to produce chlorine dioxide. Figure 9 It can be seen that when the chlorine dioxide sustained-release particles are in a citric acid-disodium hydrogen phosphate buffer environment with a pH of 4.5, the quick-release layer, the sustained-release layer and the core material swell rapidly, and chlorine dioxide is released rapidly.
[0204] The antibacterial performance of the chlorine dioxide slow-release granules prepared in this example against Fusarium was tested, and the test steps were as follows:
[0205] First, prepare a potato dextrose agar (PDA) plate and evenly spread the Fusarium spore suspension on the plate surface to form a uniform bacterial layer; soak the chlorine dioxide slow-release granules in a citric acid-disodium hydrogen phosphate buffer solution with a pH of 4.5, and gently place them on the surface of the agar plate inoculated with Fusarium after moistening. Place the plate in an incubator at 25-28°C for 48-72 hours, and observe the inhibition zone formed around the chlorine dioxide slow-release granules, such as Figure 10 As shown by Figure 10 It can be seen that the chlorine dioxide slow-release granules prepared in this example have obvious inhibitory ability against Fusarium.
[0206] Example 2
[0207] This embodiment provides a method for comprehensively controlling the continuous cropping disorder of small yellow ginger by combining slow-release chlorine dioxide soil disinfection granules with probiotics, the method comprising:
[0208] (1) Soil treatment: The residual branches, leaves and roots in the soil of the planting area are treated harmlessly, and the residual plants infected by soil-borne viruses and the residual branches and leaves scattered on the ground are removed. The collected residual plants, branches and leaves are buried in a 1m deep pit, and the pit is filled and compacted. 8cm thick quicklime is sprinkled on the compacted soil surface, and then 10cm thick soil is covered on the quicklime.
[0209] (2) Disinfection and sterilization: Level the soil and apply chlorine dioxide slow-release granules to the soil within 11 days before planting the seedlings. Apply 6.5 kg of chlorine dioxide slow-release granules per mu of soil. Plow the soil once within 2 hours after application to mix the soil with the chlorine dioxide slow-release granules.
[0210] Wherein, the chlorine dioxide slow-release granules are prepared by the following method:
[0211] (2.1) Sodium chlorite, citric acid, and deionized water were uniformly mixed to obtain a precursor solution, wherein the mass ratio of sodium chlorite to citric acid was 1:1.05, and the volume ratio of the total mass of sodium chlorite and citric acid to deionized water was 10.5 g:100 mL. Polyacrylic acid and chitosan were added to the precursor solution in a mass ratio of polyacrylic acid to chitosan of 3.5:1, and the ratio of the total mass of polyacrylic acid and chitosan to the mass of sodium chlorite in the precursor solution was 1.35:1. The mixture was stirred at 4.5°C and 220 rpm for 58 min to obtain a precursor gel.
[0212] The precursor gel was placed in a low-temperature environment of 3.5°C and allowed to stand for 3 hours. The precursor gel after standing was then subjected to a first drying stage, a second drying stage, and a third drying stage in sequence. The drying temperature of the first drying stage was 49°C, the drying pressure was -0.085MPa, and the drying time was 3.8 hours. The drying temperature of the second drying stage was 54°C, the drying pressure was -0.105MPa, and the drying time was 2.8 hours. The drying temperature of the third drying stage was 39°C, the drying pressure was 0.1MPa, and the drying time was 1.8 hours. After drying in stages, core material particles were obtained.
[0213] (2.2) Mixing hydroxypropyl methylcellulose and deionized water at a ratio of 3.5 g:100 mL to obtain a hydroxypropyl methylcellulose solution, and mixing the core particles obtained in step (2.1) with the hydroxypropyl methylcellulose solution at a mass ratio of 1:5.5 to obtain an intermediate solution;
[0214] The intermediate solution is dripped into a coagulation bath at 22° C. through a sharp hole device with an aperture of 0.9 mm to form gel beads, wherein the coagulation bath is a calcium chloride-ethanol aqueous solution, the volume fraction of ethanol in the ethanol aqueous solution is 72%, and the ratio of calcium chloride to ethanol aqueous solution is 10.5 g:100 mL. The gel beads are immersed in the coagulation bath for 6 minutes for cross-linking and curing to form a quick-release layer on the surface of the core material particles. The gel beads are removed and dried at 41° C. to obtain intermediate particles.
[0215] (2.3) Dissolve ε-polylysine in phosphate buffer at pH 6.1 to obtain an ε-polylysine solution, with the ratio of ε-polylysine to phosphate buffer being 2.2 g:100 mL. Dissolve sodium alginate in acetate buffer at pH 5.6 to obtain a sodium alginate solution, with the ratio of sodium alginate to acetate buffer being 2.2 g:100 mL.
[0216] The intermediate particles obtained in step (2.2) were alternately immersed in an ε-polylysine solution and a sodium alginate solution. The single immersion time in the ε-polylysine solution was 2.2 minutes, and the single immersion time in the sodium alginate solution was 2.2 minutes. After each immersion, the intermediate particles were rinsed with deionized water. After four alternating immersions, coated particles were obtained.
[0217] The coated particles were immersed in a genipin solution, wherein the ratio of genipin to deionized water in the genipin solution was 0.42 g:100 mL, and the mixture was stirred at a heating temperature of 46° C. and a rotation speed of 60 rpm for 53 minutes to cause a cross-linking reaction, thereby forming a sustained-release layer on the surface of the intermediate particles to obtain composite particles;
[0218] The composite particles were subjected to a first microwave enhancement stage and a second microwave enhancement stage in sequence, wherein the microwave power of the first microwave enhancement stage was 310 W and the microwave time was 1.8 min, and the microwave power of the second microwave enhancement stage was 410 W and the microwave time was 2.8 min, to obtain chlorine dioxide slow-release particles;
[0219] (3) Supplementation of probiotics: After 7 days of soil disinfection and sterilization, dilute the Bacillus subtilis wettable powder with water and spray it into the soil (1000 mL of water per gram of Bacillus subtilis wettable powder). Apply 3.5 kg of Bacillus subtilis wettable powder per mu of soil. Till the soil once within 2 hours after spraying to allow the Bacillus subtilis solution to penetrate deep into the soil.
[0220] Wherein, the Bacillus subtilis wettable powder is prepared by the following method:
[0221] (3.1) Centrifuge the Bacillus subtilis fermentation broth to a spore concentration of ≥1×10 11 CFU / g, adding a composite protective agent to a Bacillus subtilis fermentation broth and mixing them uniformly to obtain a composite fermentation broth; wherein the composite protective agent is composed of ascorbic acid, sodium alginate and sorbitol, the mass ratio of ascorbic acid, sodium alginate and sorbitol is 1:2.2:1.35, and the amount of the composite protective agent added is 3.5wt% of the mass of the Bacillus subtilis fermentation broth;
[0222] (3.2) mixing white carbon black, diatomaceous earth, and magnesium aluminum silicate in a mass ratio of 3.5:4.5:1 to obtain a composite carrier, and mixing the composite carrier, the composite fermentation liquid obtained in step (i), potassium humate, and a spore germination agent for 32 minutes to obtain a mixed material, wherein the mass ratio of the composite carrier to the composite fermentation liquid is 1:1.8, the mass ratio of potassium humate, the composite carrier, and the spore germination agent is 1:8.5:0.35, and the spore germination agent comprises L-alanine, inosine, and fructose, and the mass ratio of L-alanine, inosine, and fructose is 1:1.6:4.2;
[0223] (3.3) Spray-dry the mixture to obtain a probiotic powder, wherein the inlet air temperature of the spray drying is 62°C, the outlet air temperature is 42°C, and the drying time is 28 seconds. The probiotic powder and a composite surfactant are uniformly mixed, sieved, and dried to obtain a Bacillus subtilis wettable powder; wherein the composite surfactant comprises an aliphatic polyoxyethylene ether and polysorbate 80 in a mass ratio of 1:1.4, and the mass ratio of the probiotic powder to the composite surfactant is 26.5:1.
[0224] (4) Planting of seedlings: Select ginger seeds with good skin color, no rot and no disease. The weight of each piece of ginger seed is 72g. Each piece of ginger seed is retained with one strong bud. Soak the selected ginger seed in a 60ppm chlorine dioxide solution for 28min. After soaking, dry it naturally for 1 day and then sow it in the soil. The row spacing of ginger seed is 55cm and the plant spacing is 22cm. Leave a 52cm walkway between every 4 rows of ginger seed rows. Cover with soil after sowing.
[0225] (5) Field management: Apply organic fertilizer to the soil after planting, applying 1100kg of decomposed manure, 48kg of triple compound fertilizer, 18kg of highly active humic acid, 22kg of potassium sulfate calcium magnesium fertilizer, 0.9kg of phoxim insecticide and 95kg of microbial agent per mu;
[0226] During the plant growth period, topdressing should be carried out according to the growth situation. Topdressing should be carried out three times, including:
[0227] (5.1) After the plants have fully grown and the first bifurcation occurs, apply the first topdressing fertilizer, applying 12 kg of urea per mu, followed by the first shallow tillage of the soil;
[0228] (5.2) When the plants have three branches, apply the second topdressing fertilizer, 38kg of triple compound fertilizer, 20kg of potassium sulfate and 10kg of highly active humic acid per mu, and then carry out the second shallow tillage and soil cultivation;
[0229] (5.3) Before the plants are closed in the rows, the third topdressing should be carried out during the period of underground rhizome expansion. 22kg of triple compound fertilizer, 18kg of potassium sulfate and 10kg of highly active humic acid should be applied per mu, followed by the third shallow tillage and soil cultivation.
[0230] When diseases, insect pests and weeds occur, spray the soil with pesticides to prevent and control them.
[0231] Example 3
[0232] This embodiment provides a method for comprehensively controlling the continuous cropping disorder of small yellow ginger by combining slow-release chlorine dioxide soil disinfection granules with probiotics, the method comprising:
[0233] (1) Soil treatment: The residual branches, leaves and roots in the soil of the planting area are treated harmlessly, and the residual plants infected by soil-borne viruses and the residual branches and leaves scattered on the ground are removed. The collected residual plants, branches and leaves are burned;
[0234] (2) Disinfection and sterilization: Level the soil and apply chlorine dioxide slow-release granules to the soil within 12 days before planting the seedlings. Apply 7 kg of chlorine dioxide slow-release granules per mu of soil. After application, plow the soil once within 2 hours to mix the soil with the chlorine dioxide slow-release granules.
[0235] Wherein, the chlorine dioxide slow-release granules are prepared by the following method:
[0236] (2.1) Sodium chlorite, tartaric acid, and deionized water were uniformly mixed to obtain a precursor solution, wherein the mass ratio of sodium chlorite to tartaric acid was 1:1.1, and the volume ratio of the total mass of sodium chlorite and tartaric acid to deionized water was 11 g:100 mL. Polyacrylic acid and chitosan were added to the precursor solution in a mass ratio of polyacrylic acid to chitosan of 4:1, and the ratio of the total mass of polyacrylic acid and chitosan to the mass of sodium chlorite in the precursor solution was 1.4:1. The mixture was stirred at 5°C and 250 rpm for 55 min to obtain a precursor gel.
[0237] The precursor gel is placed in a low-temperature environment of 4°C and allowed to stand for 2 hours. The precursor gel after standing is then subjected to a first drying stage, a second drying stage, and a third drying stage in sequence. The drying temperature of the first drying stage is 50°C, the drying pressure is -0.09 MPa, and the drying time is 3.5 hours. The drying temperature of the second drying stage is 55°C, the drying pressure is -0.11 MPa, and the drying time is 2.5 hours. The drying temperature of the third drying stage is 40°C, the drying pressure is 0.1 MPa, and the drying time is 1.5 hours. After drying in stages, core material particles are obtained;
[0238] (2.2) Mixing hydroxypropyl methylcellulose and deionized water at a ratio of 4 g:100 mL to obtain a hydroxypropyl methylcellulose solution, and mixing the core material particles obtained in step (2.1) with the hydroxypropyl methylcellulose solution at a mass ratio of 1:6 to obtain an intermediate solution;
[0239] The intermediate solution is dripped into a coagulation bath at 25°C through a sharp hole device with an aperture of 1 mm to form gel beads, wherein the coagulation bath is a calcium chloride-ethanol aqueous solution, the volume fraction of ethanol in the ethanol aqueous solution is 75%, and the ratio of calcium chloride to ethanol aqueous solution is 11 g:100 mL. The gel beads are immersed in the coagulation bath for 7 minutes for cross-linking and curing to form a quick-release layer on the surface of the core material particles. The gel beads are removed and dried at 42°C to obtain intermediate particles.
[0240] (2.3) Dissolve ε-polylysine in phosphate buffer at pH 6.2 to obtain an ε-polylysine solution, with the ratio of ε-polylysine to phosphate buffer being 2.5 g:100 mL. Dissolve sodium alginate in acetate buffer at pH 5.8 to obtain a sodium alginate solution, with the ratio of sodium alginate to acetate buffer being 2.5 g:100 mL.
[0241] The intermediate particles obtained in step (2.2) were alternately immersed in an ε-polylysine solution and a sodium alginate solution. The single immersion time in the ε-polylysine solution was 2.5 minutes, and the single immersion time in the sodium alginate solution was 2.5 minutes. After each immersion, the intermediate particles were rinsed with deionized water. After four alternating immersions, coated particles were obtained.
[0242] The coated particles were immersed in a genipin solution, wherein the ratio of genipin to deionized water in the genipin solution was 0.45 g:100 mL, and the mixture was stirred at a heating temperature of 47° C. and a rotation speed of 70 rpm for 52 minutes to cause a cross-linking reaction, thereby forming a sustained-release layer on the surface of the intermediate particles to obtain composite particles;
[0243] The composite particles were subjected to a first microwave enhancement stage and a second microwave enhancement stage in sequence, wherein the microwave power of the first microwave enhancement stage was 320 W and the microwave time was 1.5 min, and the microwave power of the second microwave enhancement stage was 420 W and the microwave time was 2.5 min, to obtain chlorine dioxide slow-release particles;
[0244] (3) Supplementation of probiotics: After 8 days of soil disinfection and sterilization, dilute the Bacillus subtilis wettable powder with water and spray it into the soil (1000 mL of water per gram of Bacillus subtilis wettable powder). Apply 4 kg of Bacillus subtilis wettable powder per mu of soil. Till the soil once within 3 hours after spraying to allow the Bacillus subtilis solution to penetrate deep into the soil.
[0245] Wherein, the Bacillus subtilis wettable powder is prepared by the following method:
[0246] (3.1) Centrifuge the Bacillus subtilis fermentation broth to a spore concentration of ≥1×10 11 CFU / g, a composite protective agent was added to a Bacillus subtilis fermentation broth, and the mixture was uniformly mixed to obtain a composite fermentation broth; wherein the composite protective agent consisted of ascorbic acid, sodium alginate, and sorbitol, the mass ratio of ascorbic acid, sodium alginate, and sorbitol being 1:2.5:1.4, and the amount of the composite protective agent added was 4 wt % of the mass of the Bacillus subtilis fermentation broth;
[0247] (3.2) mixing white carbon black, diatomaceous earth, and magnesium aluminum silicate in a mass ratio of 4:5:1 to obtain a composite carrier, and mixing the composite carrier, the composite fermentation broth obtained in step (i), potassium humate, and a spore germination agent for 35 minutes to obtain a mixed material, wherein the mass ratio of the composite carrier to the composite fermentation broth is 1:2, the mass ratio of potassium humate, the composite carrier, and the spore germination agent is 1:9:0.4, and the spore germination agent comprises L-alanine, inosine, and fructose, and the mass ratio of L-alanine, inosine, and fructose is 1:1.7:4.5;
[0248] (3.3) Spray-dry the mixture to obtain a probiotic powder, wherein the inlet air temperature of the spray drying is 65°C, the outlet air temperature is 45°C, and the drying time is 25 seconds. The probiotic powder and a composite surfactant are uniformly mixed, sieved, and dried to obtain a Bacillus subtilis wettable powder; wherein the composite surfactant comprises an aliphatic polyoxyethylene ether and polysorbate 80 in a mass ratio of 1:1.5, and the mass ratio of the probiotic powder to the composite surfactant is 27:1.
[0249] (4) Planting of seedlings: Select ginger seeds with good skin color, no rot and no disease. The weight of each piece of ginger seed is 75g. Two strong buds are retained in each piece of ginger seed. The selected ginger seed is soaked in a 70ppm chlorine dioxide solution for 25min. After soaking, it is naturally dried for 2 days and then sown in the soil. The row spacing of ginger seed is 60cm and the plant spacing is 25cm. A 55cm walkway is left between every 5 rows of ginger seed rows. Cover with soil after sowing.
[0250] (5) Field management: Apply organic fertilizer to the soil after planting, applying 1200kg of decomposed manure, 45kg of triple compound fertilizer, 20kg of highly active humic acid, 25kg of potassium calcium magnesium sulfate fertilizer, 1kg of phoxim insecticide and 90kg of microbial agent per mu;
[0251] During the plant growth period, topdressing should be carried out according to the growth situation. Topdressing should be carried out three times, including:
[0252] (5.1) After the plants have fully grown and the first bifurcation occurs, apply the first topdressing fertilizer, applying 15 kg of urea per mu, followed by the first shallow tillage of the soil;
[0253] (5.2) When the plants have three branches, apply the second topdressing fertilizer, 35kg of triple compound fertilizer, 20kg of potassium sulfate and 10kg of highly active humic acid per mu, and then carry out the second shallow tillage and soil cultivation;
[0254] (5.3) Before the plants are closed in the rows, the third topdressing should be carried out during the period of underground rhizome expansion. 25kg of triple compound fertilizer, 17kg of potassium sulfate and 10kg of highly active humic acid should be applied per mu, followed by the third shallow tillage and soil cultivation.
[0255] When diseases, insect pests and weeds occur, spray the soil with pesticides to prevent and control them.
[0256] Example 4
[0257] This embodiment provides a method for comprehensively controlling the continuous cropping disorder of small yellow ginger by combining slow-release chlorine dioxide soil disinfection granules with probiotics, the method comprising:
[0258] (1) Soil treatment: The residual branches, leaves and roots in the soil of the planting area are treated harmlessly, and the residual plants infected by soil-borne viruses and the residual branches and leaves scattered on the ground are removed. The collected residual plants, branches and leaves are buried in a 1.8m deep pit, which is then filled and compacted. A 9.5cm thick layer of quicklime is sprinkled on the compacted soil surface, and then a 13cm thick layer of soil is covered on the quicklime.
[0259] (2) Disinfection and sterilization: Level the soil and apply chlorine dioxide slow-release granules to the soil within 13 days before planting the seedlings. Apply 7.5 kg of chlorine dioxide slow-release granules per mu of soil. After application, plow the soil once within 2 hours to mix the soil with the chlorine dioxide slow-release granules.
[0260] Wherein, the chlorine dioxide slow-release granules are prepared by the following method:
[0261] (2.1) Sodium chlorite, tartaric acid, and deionized water were uniformly mixed to obtain a precursor solution, wherein the mass ratio of sodium chlorite to tartaric acid was 1:1.15, and the volume ratio of the total mass of sodium chlorite and tartaric acid to deionized water was 11.5 g:100 mL. Polyacrylic acid and chitosan were added to the precursor solution in a mass ratio of polyacrylic acid to chitosan of 4.5:1, and the ratio of the total mass of polyacrylic acid and chitosan to the mass of sodium chlorite in the precursor solution was 1.45:1. The mixture was stirred at 5.5°C and 280 rpm for 52 min to obtain a precursor gel.
[0262] The precursor gel was placed in a low-temperature environment of 4.5°C and allowed to stand for 2 hours. The precursor gel after standing was then subjected to a first drying stage, a second drying stage, and a third drying stage in sequence. The drying temperature of the first drying stage was 51°C, the drying pressure was -0.095MPa, and the drying time was 3.2 hours. The drying temperature of the second drying stage was 56°C, the drying pressure was -0.115MPa, and the drying time was 2.2 hours. The drying temperature of the third drying stage was 41°C, the drying pressure was 0.1MPa, and the drying time was 1.2 hours. After drying in stages, core material particles were obtained.
[0263] (2.2) Mix hydroxypropyl methylcellulose and deionized water in a ratio of 4.5 g:100 mL to obtain a hydroxypropyl methylcellulose solution, and mix the core material particles obtained in step (2.1) with the hydroxypropyl methylcellulose solution in a mass ratio of 1:6.5 to obtain an intermediate solution;
[0264] The intermediate solution is dripped into a coagulation bath at 28°C through a sharp hole device with an aperture of 1.1 mm to form gel beads, wherein the coagulation bath is a calcium chloride-ethanol aqueous solution, the volume fraction of ethanol in the ethanol aqueous solution is 78%, and the ratio of calcium chloride to ethanol aqueous solution is 11.5 g:100 mL. The gel beads are immersed in the coagulation bath for 8 minutes for cross-linking and curing to form a quick-release layer on the surface of the core material particles. The gel beads are removed and dried at 43°C to obtain intermediate particles.
[0265] (2.3) Dissolve ε-polylysine in phosphate buffer at pH 6.3 to obtain an ε-polylysine solution, with the ratio of ε-polylysine to phosphate buffer being 2.8 g:100 mL. Dissolve sodium alginate in acetate buffer at pH 5.9 to obtain a sodium alginate solution, with the ratio of sodium alginate to acetate buffer being 2.8 g:100 mL.
[0266] The intermediate particles obtained in step (2.2) were alternately immersed in an ε-polylysine solution and a sodium alginate solution. The single immersion time in the ε-polylysine solution was 2.8 min, and the single immersion time in the sodium alginate solution was 2.8 min. After each immersion, the intermediate particles were rinsed with deionized water. After three alternating immersions, coated particles were obtained.
[0267] The coated particles were immersed in a genipin solution, wherein the ratio of genipin to deionized water in the genipin solution was 0.48 g:100 mL, and the mixture was stirred at a heating temperature of 48° C. and a rotation speed of 80 rpm for 51 minutes to cause a cross-linking reaction, thereby forming a sustained-release layer on the surface of the intermediate particles to obtain composite particles;
[0268] The composite particles were subjected to a first microwave enhancement stage and a second microwave enhancement stage in sequence, wherein the microwave power of the first microwave enhancement stage was 330 W and the microwave time was 1.2 min, and the microwave power of the second microwave enhancement stage was 430 W and the microwave time was 2.2 min, to obtain chlorine dioxide slow-release particles;
[0269] (3) Supplementation of probiotics: After 9 days of soil disinfection and sterilization, dilute the Bacillus subtilis wettable powder with water and spray it into the soil (1000 mL of water per gram of Bacillus subtilis wettable powder). Apply 4.5 kg of Bacillus subtilis wettable powder per mu of soil. Till the soil once within 3 hours after spraying to allow the Bacillus subtilis solution to penetrate deep into the soil.
[0270] Wherein, the Bacillus subtilis wettable powder is prepared by the following method:
[0271] (3.1) Centrifuge the Bacillus subtilis fermentation broth to a spore concentration of ≥1×10 11CFU / g, adding a composite protective agent to a Bacillus subtilis fermentation broth and mixing them uniformly to obtain a composite fermentation broth; wherein the composite protective agent is composed of ascorbic acid, sodium alginate and sorbitol, the mass ratio of ascorbic acid, sodium alginate and sorbitol is 1:2.8:1.45, and the amount of the composite protective agent added is 4.5wt% of the mass of the Bacillus subtilis fermentation broth;
[0272] (3.2) mixing white carbon black, diatomaceous earth, and magnesium aluminum silicate in a mass ratio of 4.5:5.5:1 to obtain a composite carrier, and mixing the composite carrier, the composite fermentation broth obtained in step (i), potassium humate, and a spore germination agent for 38 minutes to obtain a mixed material, wherein the mass ratio of the composite carrier to the composite fermentation broth is 1:2.2, the mass ratio of potassium humate, the composite carrier, and the spore germination agent is 1:9.5:0.45, and the spore germination agent comprises L-alanine, inosine, and fructose, and the mass ratio of L-alanine, inosine, and fructose is 1:1.8:4.8;
[0273] (3.3) Spray-dry the mixture to obtain a probiotic powder, wherein the inlet air temperature of the spray drying is 68°C, the outlet air temperature is 48°C, and the drying time is 22 seconds. The probiotic powder and a composite surfactant are uniformly mixed, sieved, and dried to obtain a Bacillus subtilis wettable powder; wherein the composite surfactant comprises an aliphatic polyoxyethylene ether and polysorbate 80 in a mass ratio of 1:1.6, and the mass ratio of the probiotic powder to the composite surfactant is 27.5:1.
[0274] (4) Planting of seedlings: Select ginger seeds with good skin color, no rot and no disease. The weight of each piece of ginger seed is 78g. Two strong buds are retained in each piece of ginger seed. The selected ginger seed is soaked in 80ppm chlorine dioxide solution for 22 minutes. After soaking, it is naturally dried for 2 days and then sown in the soil. The row spacing of ginger seed is 65cm and the plant spacing is 28cm. A 58cm walkway is left between every 5 rows of ginger seed rows. Cover with soil after sowing.
[0275] (5) Field management: Apply organic fertilizer to the soil after planting, applying 1300kg of decomposed manure, 42kg of triple compound fertilizer, 22kg of high-activity humic acid, 28kg of potassium calcium magnesium sulfate fertilizer, 1.1kg of phoxim insecticide and 85kg of microbial agent per mu;
[0276] During the plant growth period, topdressing should be carried out according to the growth situation. Topdressing should be carried out three times, including:
[0277] (5.1) After the plants have fully grown and the first bifurcation occurs, apply the first topdressing fertilizer, applying 18 kg of urea per mu, followed by the first shallow tillage of the soil;
[0278] (5.2) When the plants have three branches, apply the second topdressing fertilizer, 32kg of triple compound fertilizer, 20kg of potassium sulfate and 10kg of highly active humic acid per mu, and then carry out the second shallow tillage and soil cultivation;
[0279] (5.3) Before the plants are closed in the rows, the third topdressing should be carried out during the period of underground rhizome expansion. 28kg of triple compound fertilizer, 16kg of potassium sulfate and 10kg of highly active humic acid should be applied per mu, followed by the third shallow tillage of the soil.
[0280] When diseases, insect pests and weeds occur, spray the soil with pesticides to prevent and control them.
[0281] Example 5
[0282] This embodiment provides a method for comprehensively controlling the continuous cropping disorder of small yellow ginger by combining slow-release chlorine dioxide soil disinfection granules with probiotics, the method comprising:
[0283] (1) Soil treatment: The residual branches, leaves and roots in the soil of the planting area are treated harmlessly, and the residual plants infected by soil-borne viruses and the residual branches and leaves scattered on the ground are removed. The collected residual plants, branches and leaves are buried in a 2m deep pit, and the pit is filled and compacted. A 10cm thick layer of quicklime is sprinkled on the compacted soil surface, and then a 15cm thick layer of soil is covered on the quicklime.
[0284] (2) Disinfection and sterilization: Level the soil and apply chlorine dioxide slow-release granules to the soil within 15 days before planting the seedlings. Apply 8 kg of chlorine dioxide slow-release granules per mu of soil. Plow the soil once within 2 hours after application to mix the soil with the chlorine dioxide slow-release granules.
[0285] Wherein, the chlorine dioxide slow-release granules are prepared by the following method:
[0286] (2.1) Sodium chlorite, tartaric acid, and deionized water were uniformly mixed to obtain a precursor solution, wherein the mass ratio of sodium chlorite to tartaric acid was 1:1.2, and the volume ratio of the total mass of sodium chlorite and tartaric acid to deionized water was 12 g:100 mL. Polyacrylic acid and chitosan were added to the precursor solution in a mass ratio of polyacrylic acid to chitosan of 5:1, and the ratio of the total mass of polyacrylic acid and chitosan to the mass of sodium chlorite in the precursor solution was 1.5:1. The mixture was stirred at 6°C and 300 rpm for 50 min to obtain a precursor gel.
[0287] The precursor gel is placed in a low-temperature environment of 5°C and allowed to stand for 2 hours. The precursor gel after standing is then subjected to a first drying stage, a second drying stage, and a third drying stage in sequence. The drying temperature of the first drying stage is 52°C, the drying pressure is -0.1MPa, and the drying time is 3 hours. The drying temperature of the second drying stage is 57°C, the drying pressure is -0.12MPa, and the drying time is 2 hours. The drying temperature of the third drying stage is 42°C, the drying pressure is 0.1MPa, and the drying time is 1 hour. After drying in stages, core material particles are obtained.
[0288] (2.2) Mixing hydroxypropyl methylcellulose and deionized water at a ratio of 5 g:100 mL to obtain a hydroxypropyl methylcellulose solution, and mixing the core material particles obtained in step (2.1) with the hydroxypropyl methylcellulose solution at a mass ratio of 1:7 to obtain an intermediate solution;
[0289] The intermediate solution is dripped into a coagulation bath at 30°C through a sharp hole device with an aperture of 1.2 mm to form gel beads, wherein the coagulation bath is a calcium chloride-ethanol aqueous solution, the volume fraction of ethanol in the ethanol aqueous solution is 80%, and the ratio of calcium chloride to ethanol aqueous solution is 12 g:100 mL. The gel beads are immersed in the coagulation bath for 10 minutes for cross-linking and curing to form a quick-release layer on the surface of the core material particles. The gel beads are removed and dried at 45°C to obtain intermediate particles.
[0290] (2.3) Dissolve ε-polylysine in phosphate buffer at pH 6.5 to obtain an ε-polylysine solution, with the ratio of ε-polylysine to phosphate buffer being 3 g:100 mL. Dissolve sodium alginate in acetate buffer at pH 6 to obtain a sodium alginate solution, with the ratio of sodium alginate to acetate buffer being 3 g:100 mL.
[0291] The intermediate particles obtained in step (2.2) were alternately immersed in an ε-polylysine solution and a sodium alginate solution. The single immersion time in the ε-polylysine solution was 3 minutes, and the single immersion time in the sodium alginate solution was 3 minutes. After each immersion, the intermediate particles were rinsed with deionized water. After alternating immersion for 3 times, coated particles were obtained.
[0292] The coated particles were immersed in a genipin solution, wherein the ratio of genipin to deionized water in the genipin solution was 0.5 g:100 mL, and the mixture was stirred at a heating temperature of 50° C. and a rotation speed of 100 rpm for 50 minutes to cause a cross-linking reaction, thereby forming a sustained-release layer on the surface of the intermediate particles to obtain composite particles;
[0293] The composite particles were subjected to a first microwave enhancement stage and a second microwave enhancement stage in sequence, wherein the microwave power of the first microwave enhancement stage was 350 W and the microwave time was 1 min, and the microwave power of the second microwave enhancement stage was 450 W and the microwave time was 2 min, to obtain chlorine dioxide slow-release particles;
[0294] (3) Supplementation of probiotics: After 10 days of soil disinfection and sterilization, dilute the Bacillus subtilis wettable powder with water and spray it into the soil (1000 mL of water per gram of Bacillus subtilis wettable powder). Apply 5 kg of Bacillus subtilis wettable powder per mu of soil. Till the soil once within 3 hours after spraying to allow the Bacillus subtilis solution to penetrate deep into the soil.
[0295] Wherein, the Bacillus subtilis wettable powder is prepared by the following method:
[0296] (3.1) Centrifuge the Bacillus subtilis fermentation broth to a spore concentration of ≥1×10 11 CFU / g, a composite protective agent is added to a Bacillus subtilis fermentation broth, and the mixture is mixed uniformly to obtain a composite fermentation broth; wherein the composite protective agent is composed of ascorbic acid, sodium alginate and sorbitol, the mass ratio of ascorbic acid, sodium alginate and sorbitol is 1:3:1.5, and the amount of the composite protective agent added is 5wt% of the mass of the Bacillus subtilis fermentation broth;
[0297] (3.2) mixing white carbon black, diatomaceous earth, and magnesium aluminum silicate in a mass ratio of 5:6:1 to obtain a composite carrier, and mixing the composite carrier, the composite fermentation broth obtained in step (i), potassium humate, and a spore germination agent for 40 minutes to obtain a mixed material, wherein the mass ratio of the composite carrier to the composite fermentation broth is 1:2.5, the mass ratio of potassium humate, the composite carrier, and the spore germination agent is 1:10:0.5, and the spore germination agent comprises L-alanine, inosine, and fructose, and the mass ratio of L-alanine, inosine, and fructose is 1:2:5;
[0298] (3.3) Spray-dry the mixture to obtain a probiotic powder, wherein the air inlet temperature of the spray drying is 70°C, the air outlet temperature is 50°C, and the drying time is 20 seconds. The probiotic powder and a composite surfactant are uniformly mixed, sieved, and dried to obtain a Bacillus subtilis wettable powder; wherein the composite surfactant comprises an aliphatic polyoxyethylene ether and polysorbate 80 in a mass ratio of 1:1.8, and the mass ratio of the probiotic powder to the composite surfactant is 28:1.
[0299] (4) Planting of seedlings: Select ginger seeds with good skin color, no rot and no disease. The weight of each piece of ginger seed is 80g. Two strong buds are retained in each piece of ginger seed. The selected ginger seed is soaked in a 100ppm chlorine dioxide solution for 20 minutes. After soaking, it is naturally dried for 2 days and then sown in the soil. The row spacing of ginger seed is 70cm and the plant spacing is 30cm. A 60cm walkway is left between every 6 rows of ginger seed rows. Cover with soil after sowing.
[0300] (5) Field management: Apply organic fertilizer to the soil after planting, applying 1500kg of decomposed manure, 40kg of triple compound fertilizer, 25kg of highly active humic acid, 30kg of potassium calcium magnesium sulfate fertilizer, 1.2kg of phoxim insecticide and 80kg of microbial agent per mu;
[0301] During the plant growth period, topdressing should be carried out according to the growth situation. Topdressing should be carried out three times, including:
[0302] (5.1) After the plants have fully grown and the first bifurcation occurs, apply the first topdressing fertilizer, 20 kg of urea per mu, and then carry out the first shallow tillage and soil cultivation;
[0303] (5.2) When the plants have three branches, apply the second topdressing fertilizer, 30kg of triple compound fertilizer, 20kg of potassium sulfate and 10kg of highly active humic acid per mu, and then carry out the second shallow tillage and soil cultivation;
[0304] (5.3) Before the plants are closed in the rows, the third topdressing should be carried out during the period of underground rhizome expansion. 30kg of triple compound fertilizer, 15kg of potassium sulfate and 10kg of highly active humic acid should be applied per mu, followed by the third shallow tillage of the soil.
[0305] When diseases, insect pests and weeds occur, spray the soil with pesticides to prevent and control them.
[0306] Example 6
[0307] This example provides a method for comprehensively controlling the continuous cropping problem of small yellow ginger by combining slow-release chlorine dioxide soil disinfection granules with probiotics. The method differs from Example 1 in that, in step (2.1), the mass ratio of polyacrylic acid to chitosan is adjusted to 2:1, and the other process parameters and operating conditions are exactly the same as those in Example 1.
[0308] Example 7
[0309] This example provides a method for comprehensively controlling the continuous cropping problem of small yellow ginger by combining slow-release chlorine dioxide soil disinfection granules with probiotics. The method differs from Example 1 in that, in step (2.1), the mass ratio of polyacrylic acid to chitosan is adjusted to 6:1, and the other process parameters and operating conditions are exactly the same as those in Example 1.
[0310] Example 8
[0311] This example provides a method for comprehensively controlling the continuous cropping problem of small yellow ginger by combining slow-release chlorine dioxide soil disinfection granules with probiotics. The method differs from Example 1 in that, in step (2.1), only the second drying stage is retained, and the first and third drying stages are omitted. The other process parameters and operating conditions are exactly the same as those in Example 1.
[0312] Example 9
[0313] This example provides a method for comprehensively controlling the continuous cropping problem of small yellow ginger by combining slow-release chlorine dioxide soil disinfection granules with probiotics. The method differs from Example 1 in that, in step (2.2), the mass ratio of the core material granules to the hydroxypropyl methylcellulose solution is adjusted to 1:4, and the other process parameters and operating conditions are exactly the same as those in Example 1.
[0314] Example 10
[0315] This example provides a method for comprehensively controlling the continuous cropping problem of small yellow ginger by combining slow-release chlorine dioxide soil disinfection granules with probiotics. The method differs from Example 1 in that, in step (2.2), the mass ratio of the core material granules to the hydroxypropyl methylcellulose solution is adjusted to 1:8, and the other process parameters and operating conditions are exactly the same as those in Example 1.
[0316] Example 11
[0317] This example provides a method for comprehensively controlling the continuous cropping problem of small yellow ginger by combining slow-release chlorine dioxide soil disinfection granules with probiotics. The method differs from Example 1 in that, in step (2.2), the immersion time of the gel granules in the coagulation bath is adjusted to 3 minutes. The other process parameters and operating conditions are exactly the same as those in Example 1.
[0318] Example 12
[0319] This example provides a method for comprehensively controlling the continuous cropping problem of small yellow ginger by combining slow-release chlorine dioxide soil disinfection granules with probiotics. The method differs from Example 1 in that, in step (2.2), the immersion time of the gel granules in the coagulation bath is adjusted to 12 minutes. The other process parameters and operating conditions are exactly the same as those in Example 1.
[0320] Example 13
[0321] This example provides a method for comprehensively controlling the continuous cropping problem of small yellow ginger by combining slow-release chlorine dioxide soil disinfection granules with probiotics. The method differs from Example 1 in that, in step (2.3), only the second microwave intensification stage is retained, and the first microwave intensification stage is omitted. The other process parameters and operating conditions are exactly the same as those in Example 1.
[0322] The sustained-release properties of the chlorine dioxide slow-release granules prepared in Examples 1-13 were tested. The specific testing steps are as follows:
[0323] (1) 1 g of the chlorine dioxide slow-release particles prepared in Example 1-13 was spread evenly in a reaction kettle, and 200 mL of acetic acid-sodium acetate buffer solution with a pH of 5.5 was added to the reaction kettle. The liquid surface of the acetic acid-sodium acetate buffer solution was completely immersed in the chlorine dioxide slow-release particles. Magnetic stirring was turned on and stirred at 25±0.5°C and 300 rpm in a dark environment;
[0324] (2) Two absorption bottles were connected in series at the gas outlet of the reactor. Each absorption bottle was filled with 50 mL of absorption liquid containing 5 g / L malonic acid and 5 g / L potassium iodide. Nitrogen was introduced into the reactor at a flow rate of 0.5 L / min to bring the released chlorine dioxide gas into the absorption bottle. A new set of absorption bottles was replaced every 2 hours. When the test was completed at the 24th, 48th, 72nd, 96th and 120th hours, all the absorption liquids in the previous absorption bottles were collected, 1 mL of starch indicator (1 wt% starch aqueous solution) was added, and the solution was titrated with 0.01 mol / L Na2S2O3 solution until the blue color disappeared. The volume V (mL) of the consumed Na2S2O3 solution was recorded.
[0325] The following formula is used to calculate the cumulative release of chlorine dioxide from chlorine dioxide slow-release particles within 24h, 48h, 72h, 96h and 120h (m i , mg / g):
[0326]
[0327] Where C is the concentration of Na2S2O3 solution (mol / L), m is the sampling mass of chlorine dioxide slow-release particles (g);
[0328] (3) Calculate the maximum release of chlorine dioxide from chlorine dioxide slow-release granules:
[0329] Place the chlorine dioxide slow-release granules in a strong acid solution (1 mol / L sulfuric acid solution) with a pH of ≤ 2, heat it to 60°C to accelerate the release of chlorine dioxide, and absorb the generated chlorine dioxide through an absorption bottle. Collect the absorption liquid in the absorption bottle every 2 hours and titrate it using the above method until the difference in the results of three consecutive sampling titration tests is less than 1%, indicating that the chlorine dioxide in the chlorine dioxide slow-release granules is completely released. Calculate the maximum chlorine dioxide release m max (mg / g);
[0330] (4) The following formula is used to calculate the cumulative release rate (%) of chlorine dioxide released by chlorine dioxide slow-release granules within 24 hours, 48 hours, 72 hours, 96 hours and 120 hours:
[0331]
[0332] The test results are shown in Table 1.
[0333] Table 1 Cumulative release rate of chlorine dioxide from chlorine dioxide slow-release granules in different time periods (pH = 5.5)
[0334]
[0335] The test data from Examples 1, 6, and 7 show that when the amount of polyacrylic acid deviates from the optimal value, the stability of the sustained-release system is severely compromised. In Example 6, due to the insufficient amount of polyacrylic acid used, the core material's polymer network crosslinking density is insufficient, resulting in a loose core material structure and increased porosity. This defect causes the initial 24-hour release rate to soar to 45.2% (a 39% increase from 32.5% in Example 1). However, after 72 hours, the release rate plummets due to the collapse of the carrier structure, resulting in a final cumulative release rate of only 78.4% over 120 hours. In contrast, in Example 7, the excessive amount of polyacrylic acid leads to excessive crosslinking, and the dense network severely hinders the diffusion of chlorine dioxide molecules, resulting in a 24-hour release rate of only 18.6%. Furthermore, the later release is continuously limited, with a cumulative release rate of 73.9% over 120 hours, exposing the dual defects of "release hysteresis" and "incomplete release."
[0336] The test data of Examples 1 and 8 show that the defects of the single drying process directly affect the microstructural integrity of the core material. Since staged drying was not adopted in Example 8, the moisture gradient inside the core material suddenly changed, causing microcracks. These cracks became rapid release channels in the initial period (24-48 hours), causing the cumulative release rate of chlorine dioxide to rise to 59.2% in 48 hours (close to the level of Example 1). However, as the medium penetrates, the cracks close due to swelling pressure after 72 hours, resulting in almost stagnant release from 96 to 120 hours, and a final cumulative release rate of 67.3%, exposing the key influence of the drying process on the sustainability of sustained release.
[0337] The test data from Examples 1, 9, and 10 show that varying the amount of hydroxypropyl methylcellulose disrupts the synergistic effect between the immediate-release layer and the sustained-release layer. In Example 9, the insufficient amount of hydroxypropyl methylcellulose resulted in an insufficient thickness of the immediate-release layer, which was unable to effectively buffer the initial release. The cumulative chlorine dioxide release rate over 24 hours was as high as 41.5%. Furthermore, due to incomplete coating, the sustained-release layer was prematurely exposed after 72 hours, triggering uncontrolled release (the slope of the 96-120 hour release curve increased sharply from a baseline of 0.18% / h to 0.32% / h). In Example 10, the excessive amount of hydroxypropyl methylcellulose resulted in an excessively thick immediate-release layer, significantly delaying the onset of release. The cumulative chlorine dioxide release rate over 24 hours was only 26.4%. Furthermore, the dense coating hindered contact between the core material and the medium (extending the medium penetration time to 18 hours compared to a baseline of 6 hours). Ultimately, the cumulative chlorine dioxide release rate over 120 hours was only 79.2%.
[0338] The test data from Examples 1, 11, and 12 show that the immersion time in Example 11 was too short, resulting in insufficient penetration of the crosslinking agent genipin and insufficient surface crosslinking, leading to an initial burst release (the cumulative chlorine dioxide release rate over 24 hours was as high as 48.9%). However, after 72 hours, the uncrosslinked core material rapidly disintegrated, leading to a stagnation of release in the later stages (the cumulative chlorine dioxide release rate over 96-120 hours increased by only 0.4%). In contrast, the immersion time in Example 12 was too long, resulting in excessive crosslinking, which in turn caused a loss of the carrier's swelling capacity and made it difficult for the medium to penetrate the core material, resulting in suppressed release throughout the entire process (the cumulative chlorine dioxide release rate over 120 hours was only 66.4%).
[0339] The test data from Examples 1 and 13 show that, because Example 13 did not employ a two-stage microwave intensification process, its cross-linked structure exhibited significant defects. A single high-power microwave exposure resulted in excessive cross-linking of the outer sodium alginate-ε polylysine composite layer, forming a dense barrier that impeded medium penetration (the cumulative chlorine dioxide release rate over 24 hours was only 28.7%, an 11.7% decrease from 32.5% in Example 1). Furthermore, uneven energy distribution in the inner layer led to a sudden drop in cross-linking. After 72 hours, swelling pressure triggered local rupture of the coating, manifesting as abnormal fluctuations in release rate after 48 hours (a sudden 12.3% increase in release from 48 hours to 72 hours). However, later, due to collapse of the carrier structure, the cumulative chlorine dioxide release rate over 120 hours was only 82.1%.
[0340] The pH response performance of the chlorine dioxide slow-release granules prepared in Examples 1-13 was tested. The specific test steps are as follows:
[0341] (1) Take 1 g of each of 4 portions of the chlorine dioxide slow-release granules prepared in Examples 1-13 and spread them in 4 reactors of the same volume. Add 200 mL of pH = 4.5 buffer, pH = 5.5 buffer, pH = 6.5 buffer, and pH = 7.5 buffer to each of the 4 reactors. The formulas of the four buffers are as follows:
[0342] The buffer solution for pH 4.5 is citric acid-disodium hydrogen phosphate buffer. Weigh 21.01 g of C6H8O7·H2O and dissolve it in 1 L of ultrapure water to obtain a 0.1 M citric acid solution. Weigh 35.61 g of Na2HPO4·2H2O and dissolve it in 1 L of ultrapure water to obtain a 0.2 M disodium hydrogen phosphate solution. Take 20.5 mL of citric acid solution and 29.5 mL of disodium hydrogen phosphate solution, mix them evenly, and calibrate the pH to 4.50 ± 0.05 using a pH meter. If necessary, fine-tune the solution with citric acid solution (to lower the pH) or disodium hydrogen phosphate solution (to raise the pH).
[0343] The pH value of 5.5 is acetic acid-sodium acetate buffer. Weigh 11.55 mL of glacial acetic acid (CH3COOH, 99%) and dilute it to 1 L to obtain acetic acid solution. Weigh 27.22 g of CH3COONa·3H2O and dissolve it in 1 L of ultrapure water to obtain sodium acetate solution. Take 4.8 mL of acetic acid solution and 45.2 mL of sodium acetate solution, mix them evenly, and adjust the pH to 5.50±0.05 using a pH meter (you can add acetic acid solution or sodium acetate solution dropwise). Make up to 100 mL and filter sterilize.
[0344] The pH of 6.5 is phosphate buffer. Weigh 27.6 g of NaH2PO4·H2O and dissolve it in 1 L of ultrapure water to obtain Solution A. Weigh 53.65 g of Na2HPO4·7H2O and dissolve it in 1 L of ultrapure water to obtain Solution B. Take 31.0 mL of Solution A and 69.0 mL of Solution B, mix them evenly, and adjust the pH to 6.50 ± 0.05 using a pH meter. If necessary, adjust with Solution A (to lower the pH) or Solution B (to raise the pH). Make up to 200 mL and store at 4°C after sterilization.
[0345] The pH = 7.5 buffer is Tris-HCl buffer. Weigh 24.23g of Tris (trishydroxymethylaminomethane) and dissolve it in 800mL of ultrapure water to obtain a Tris solution. Measure 16.8mL of concentrated hydrochloric acid (36-38%) and dilute to 1L to obtain a hydrochloric acid solution. Take 50mL of the Tris solution and slowly add the hydrochloric acid solution dropwise until the pH is 7.50±0.05. Add ultrapure water to 200mL and filter through a 0.22μm filter membrane.
[0346] The buffer solutions of different pH values were added to the four reactors until the chlorine dioxide slow-release particles were completely submerged. Magnetic stirring was turned on and the mixture was stirred at 25±0.5°C and 300 rpm in a dark environment.
[0347] (2) The gas outlet of each reactor is connected in series with two absorption bottles, each of which is filled with 50 mL of absorption liquid containing 5 g / L malonic acid and 5 g / L potassium iodide. Nitrogen is introduced into the reactor at a flow rate of 0.5 L / min to bring the released chlorine dioxide gas into the absorption bottle. A new set of absorption bottles is replaced every 2 hours. When the test reaches the 72nd hour, all the absorption liquids in the previous absorption bottles are collected, 1 mL of starch indicator (1 wt% starch aqueous solution) is added, and the solution is titrated with 0.01 mol / L Na2S2O3 solution until the blue color disappears. The volume V (mL) of the consumed Na2S2O3 solution is recorded.
[0348] The following formula is used to calculate the cumulative release of chlorine dioxide from chlorine dioxide slow-release particles within 72 hours (m i , mg / g):
[0349]
[0350] Where C is the concentration of Na2S2O3 solution (mol / L), m is the sampling mass of chlorine dioxide slow-release particles (g);
[0351] (3) The following formula is used to calculate the cumulative release rate (%) of chlorine dioxide released by chlorine dioxide slow-release particles within 72 hours under buffer conditions of pH = 4.5, 5.5, 6.5 and 7.5:
[0352] .
[0353] in, is the maximum release of chlorine dioxide.
[0354] The test results are shown in Table 2.
[0355] Table 2 Cumulative release rate of chlorine dioxide from chlorine dioxide slow-release granules at different pH values (72h)
[0356]
[0357] The test data from Examples 1, 6, and 7 show that insufficient polyacrylic acid in Example 6 results in a loose core material cross-linked network, resulting in a burst release rate of 92.4% at pH 4.5. However, acidic media accelerate carrier disintegration, causing a sharp drop in the cumulative release rate at pH 5.5 and above (only 12.3% at pH 7.5), revealing the supporting role of core material structural strength in long-term sustained release. When the amount of polyacrylic acid is too low, excessive swelling and loss of mechanical strength in an acidic environment lead to irreversible damage. Excessive polyacrylic acid in Example 7 results in an overly dense cross-linked network. At pH 4.5, due to impeded medium penetration, the cumulative release rate is only 81.7%, but it abnormally increases to 82.6% at pH 5.5. This is due to the delayed swelling effect of the highly cross-linked network in moderately acidic conditions. The medium requires more than 24 hours to break through the dense surface layer, triggering delayed release. This nonlinear response leads to pH-dependent disorder and loss of controllability.
[0358] It can be seen from the test data of Example 1 and Example 8 that staged drying was not adopted in Example 8, resulting in uneven distribution of the pores in the core material and the formation of through-hole channels. The cumulative release rate at pH = 4.5 was as high as 95.2%, and the cumulative release rate at pH = 7.5 was still as high as 32.8%, proving that defects in the drying process caused the coating layer to lose pH selectivity, the porous structure allowed the neutral medium to directly contact the core material, and the sustained-release mechanism failed.
[0359] It can be seen from the test data of Examples 1, 9 and 10 that in Example 9, insufficient hydroxypropyl methylcellulose resulted in the quick-release layer being too thin, and the core material could not be effectively activated at pH = 4.5, resulting in an overall low cumulative release rate of chlorine dioxide (only 72.3% at pH = 4.5); while in Example 10, excessive hydroxypropyl methylcellulose resulted in the quick-release layer being too thick, and the sustained-release layer cracked due to concentrated swelling stress at pH = 7.5, resulting in an excessively high cumulative release rate at pH = 7.5.
[0360] It can be seen from the test data of Examples 1, 11 and 12 that the immersion time in Example 11 is too short, the cross-linked layer is too thin, and it cannot resist the erosion of the neutral medium, resulting in a cumulative release rate of 60.1% at pH = 6.5; while the immersion time in Example 12 is too long, and excessive cross-linking causes swelling to be hindered at pH = 4.5, and the cumulative release rate plummets to 67.5%.
[0361] It can be seen from the test data of Example 1 and Example 13 that Example 13 did not adopt the gradient microwave process, resulting in an inverted cross-linking density distribution. The cumulative release rate at pH = 7.5 was abnormal, as high as 41.5%. This was because the highly cross-linked surface layer shrank and cracked under a neutral environment, exposing the low-cross-linked core for rapid release; and the cumulative release rate at pH = 4.5 was 91.3%, which seemed normal, but was actually due to premature rupture of the surface layer, leading to uncontrolled release in the later stage.
[0362] Comparative Example 1
[0363] This embodiment provides a method for comprehensively controlling the continuous cropping disorder of small yellow ginger by combining slow-release chlorine dioxide soil disinfection granules with probiotics. The difference from Example 1 is that step (2) is omitted, the soil is not disinfected and sterilized, and probiotics are supplemented to the soil within 12 days after the soil treatment. The other process parameters and operating conditions are exactly the same as those in Example 1.
[0364] Comparative Example 2
[0365] This embodiment provides a method for comprehensively controlling the continuous cropping disorder of small yellow ginger by combining slow-release chlorine dioxide soil disinfection granules with probiotics. The difference from Example 1 is that step (3) is omitted, probiotics are not added to the soil, and seedlings are planted on the fourth day after the soil is disinfected and sterilized. Other process parameters and operating conditions are exactly the same as those in Example 1.
[0366] Other process parameters and operating conditions are exactly the same as those in Example 1.
[0367] Comparative Example 3
[0368] This embodiment provides a method for comprehensively controlling the continuous cropping disorder of small yellow ginger by combining slow-release chlorine dioxide soil disinfection granules with probiotics. The difference from Example 1 is that steps (2) and (3) are omitted, the soil is not disinfected and sterilized, and probiotics are not added to the soil. The seedlings are planted on the fourth day after the residual branches, leaves and roots in the soil are harmlessly treated. The other process parameters and operating conditions are exactly the same as those in Example 1.
[0369] The killing rate of Fusarium in the soil by the methods provided in Examples 1-13 and Comparative Examples 1-3 was tested, and the specific testing steps were as follows:
[0370] Soil (pH = 5.8, organic matter content 2.1%) was harmlessly treated according to the harmless treatment method provided by the present invention. The soil was then divided into two equal parts, namely a control group and an experimental group. Equal amounts of Fusarium spores (ATCC 48112) were artificially inoculated in the control group and the experimental group, and the soil moisture content of the control group and the experimental group was adjusted to 25wt%. Chlorine dioxide slow-release granules and Bacillus subtilis wettable powder were applied to the soil of the experimental group at a rate of 8 kg / mu. The operating steps were carried out according to Example 1 provided by the present invention.
[0371] After 5 days of incubation, the soil samples of the control group and the experimental group were sampled and the plate count method was used to test the number of Fusarium colonies in the soil of the experimental group and the control group. The sterilization rate (%) was calculated according to the following formula:
[0372]
[0373] The incidence of ginger blight in small yellow ginger planted using the methods provided in Examples 1-13 and Comparative Examples 1-3 was calculated, and the specific steps were as follows:
[0374] A five-point sampling method was used for field surveys. Five 1m² plots were selected in the ginger field. The number of diseased plants with wilting leaves, stem base rot, or browning of ginger pieces was counted. The total number of plants surveyed must be ≥ 200. The incidence of ginger blight was calculated using the following formula:
[0375]
[0376] The per-acre yield of small yellow ginger planted using the methods provided in Examples 1-13 and Comparative Examples 1-3 was calculated, and the specific steps were as follows:
[0377] The sampling was carried out during the maturity period of ginger (usually 8 to 10 months after planting, when the stems and leaves begin to turn yellow), and within 3 days after rainfall (to avoid interference with water content), the ginger field was divided into 5 sampling points, including the intersection of diagonals and the four corners, with each point marked with a 1m 2 Dig up all ginger plants within the sampling area (approximately 15 to 20 plants). Shake off the soil and keep the whole ginger pieces (including the main ginger, sub-ginger, and grandchild ginger) to avoid mechanical damage.
[0378] The fresh weight per unit area of ginger field was calculated using the following formula:
[0379]
[0380] The following formula is used to calculate the per mu yield of ginger field:
[0381]
[0382] The test data is shown in Table 3.
[0383] Table 3
[0384]
[0385] The test data of Examples 1, 6, and 7 show that the amount of polyacrylic acid used in Example 6 was too little, resulting in an increase in the porosity of the composite gel network and an accelerated initial release rate of chlorine dioxide, but insufficient structural strength, resulting in failure of sustained release in the soil in the middle and late stages. The killing rate of Fusarium was only 85.4%, and the incidence of ginger blight caused by residual bacteria that were not eliminated climbed to 12.7%. In Example 7, the amount of polyacrylic acid used was too high, resulting in a decrease in the porosity of the composite gel network, an increase in the medium's permeability resistance, and a shortened effective release period of chlorine dioxide. Although the incidence of ginger blight was slightly lower than that of Example 6, the per-acre yield was lower.
[0386] It can be seen from the test data of Examples 1 and 8 that staged drying was not adopted in Example 8, which caused stress concentration inside the core material and formed a network of microcracks. These cracks became channels for rapid release of chlorine dioxide, resulting in excessively high local concentrations in the soil, which could temporarily inhibit Fusarium. However, in the later stage, due to the collapse of the carrier structure, the sustained release of chlorine dioxide was interrupted, causing the incidence of ginger plague to increase to 10.2% and the yield per mu to drop to 2901 kg.
[0387] The test data from Examples 1, 9, and 10 show that in Example 9, the dosage of hydroxypropyl methylcellulose was too low, resulting in a thinner immediate-release layer, a reduced swelling rate, delayed core material activation, and delayed effective disinfecting, leading to a ginger blight incidence rate of 15.3%. In Example 10, however, the dosage of hydroxypropyl methylcellulose was too high, forming an excessively thick immediate-release layer. Swelling stress caused cracks in the sustained-release layer, and the chlorine dioxide release exceeded the standard within 24 hours. Although the initial Fusarium kill rate was as high as 83.9%, the sustained-release ability of chlorine dioxide was lost in the later stages, causing the ginger blight incidence rate to increase to 14.8% and the yield per mu to drop to 2752 kg.
[0388] From the test data of Examples 1, 11, and 12, it can be seen that in Example 11, the immersion time was too short, resulting in a thin cross-linked layer and insufficient surface cross-linking. After soil moisture penetration, the sustained-release layer swelled and ruptured, resulting in a sudden release of chlorine dioxide. Although the initial Fusarium kill rate was as high as 87.2%, the sustained-release ability of chlorine dioxide was lost in the later stage, causing the incidence of ginger blight to increase to 11.4% and the yield per mu to drop to 2856 kg. In Example 12, the immersion time was too long, the cross-linking was too high, the surface swelling rate was reduced, the medium penetration was blocked, the sustained-release period was extended to 60 days, and the peak chlorine demand during the ginger expansion period was missed, resulting in a yield of only 2654 kg per mu.
[0389] It can be seen from the test data of Example 1 and Example 13 that Example 13 uses a single high-power microwave, which leads to an imbalance in the cross-linking density distribution. Excessive cross-linking of the surface inhibits the initial release, insufficient cross-linking of the core causes swelling and rupture, and the late sudden release damages the probiotic community. Although the incidence of ginger plague is lower, the per mu yield is still lower than that of Example 1.
[0390] It can be seen from the test data of Example 1, Comparative Example 1, Comparative Example 2 and Comparative Example 3 that the incidence rates of ginger blight in Comparative Example 1 and Comparative Example 3, which were not disinfected and sterilized, were as high as 65.8% and 82.6% respectively due to the rampant pathogens, and the yield was less than 50% of that in Example 1; in Comparative Example 2, which was only disinfected and sterilized but not supplemented with probiotics, although the killing rate of Fusarium was as high as 96.0%, due to the lack of probiotics, the incidence rate of ginger blight was still as high as 25.4%, and the yield per mu was only 2307 kg, which confirmed the necessity of the "disinfection and sterilization-probiotic synergy" mechanism.
[0391] The applicant declares that the above is only a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention fall within the scope of protection and disclosure of the present invention.
Claims
1. A method for comprehensively controlling the continuous cropping disorder of small yellow ginger by combining slow-release chlorine dioxide soil disinfection granules with probiotics, characterized in that: The method comprises: Chlorine dioxide slow-release granules are applied to the soil to disinfect and sterilize the soil, and then Bacillus subtilis wettable powder is diluted and sprayed on the soil to supplement the soil with probiotics; The chlorine dioxide slow-release granules are prepared by drying a sodium chlorite precursor gel in stages to obtain a core material, which is then coated with hydroxypropyl methylcellulose to form a quick-release layer, and finally a slow-release layer is constructed by alternately soaking and cross-linking ε-polylysine / sodium alginate, which is then microwave-enhanced. The chlorine dioxide slow-release granules are prepared by the following method: Sodium chlorite, an acidic activator, and deionized water are mixed, and polyacrylic acid and chitosan are added in a mass ratio of (3-5):1, mixed and stirred to obtain a precursor gel, and the precursor gel is allowed to stand and dried to obtain core material particles; the mass ratio of the sodium chlorite and the acidic activator is 1:(1-1.2), the volume ratio of the total mass of the sodium chlorite and the acidic activator to the deionized water is (10-12) g:100 mL, the acidic activator includes citric acid or tartaric acid, and the mass ratio of the total mass of the polyacrylic acid and chitosan to the sodium chlorite is (1.3-1.5):1; The core material particles and the hydroxypropyl methylcellulose solution are mixed in a mass ratio of 1:(5-7) and then dripped into a coagulation bath to form gel beads, which are then allowed to stand in the coagulation bath for crosslinking and dried to obtain intermediate particles. The coagulation bath is a calcium chloride ethanol aqueous solution, the ratio of calcium chloride to ethanol aqueous solution in the coagulation bath is (10-12) g:100 mL, and the gel beads are immersed in the coagulation bath for 5-10 minutes. The intermediate particles are alternately soaked in ε-polylysine solution and sodium alginate solution multiple times to obtain coated particles; then, they are soaked in genipin solution, heated for cross-linking, and microwave-enhanced to obtain the coated particles; The Bacillus subtilis wettable powder is prepared by the following method: First, the Bacillus subtilis fermentation liquid is centrifuged and concentrated, and then a composite protective agent consisting of ascorbic acid, sodium alginate and sorbitol is added; then, it is mixed with a composite carrier consisting of white carbon black, diatomaceous earth and magnesium aluminum silicate, potassium humate and a spore germination agent, and then spray-dried and mixed with a composite surfactant and sieved.
2. The method for comprehensively controlling the continuous cropping disorder of small yellow ginger by combining the slow-release chlorine dioxide soil disinfection granules and probiotics according to claim 1, characterized in that: The intermediate particles are immersed in the ε-polylysine solution for 3 to 5 times; The intermediate particles are immersed in the sodium alginate solution for 3 to 5 times.
3. The method for comprehensively controlling the continuous cropping disorder of small yellow ginger by combining the slow-release chlorine dioxide soil disinfection granules and probiotics according to claim 1, characterized in that: The heating temperature when the coated particles are immersed in the genipin solution is 45-50° C.; The soaking time of the coated particles in the genipin solution is 50 to 55 minutes.
4. The method for comprehensively controlling the continuous cropping disorder of small yellow ginger by combining the slow-release chlorine dioxide soil disinfection granules and probiotics according to claim 1, characterized in that: The Bacillus subtilis wettable powder is prepared by the following method: (i) centrifuging and concentrating the Bacillus subtilis fermentation broth to a spore concentration of ≥1×10¹¹ CFU / g, adding a composite protective agent, wherein the composite protective agent comprises ascorbic acid, sodium alginate, and sorbitol, and mixing to obtain a composite fermentation broth; (ii) mixing white carbon black, diatomaceous earth and magnesium aluminum silicate to form a composite carrier, and mixing the composite fermentation liquid, potassium humate and a spore germination agent to obtain a mixed material, wherein the spore germination agent comprises L-alanine, inosine and fructose; (iii) spray drying the mixture to obtain probiotic powder, mixing the probiotic powder with a composite surfactant, and then sieving and drying the mixture. The composite surfactant is composed of aliphatic polyoxyethylene ether and polysorbate 80.
5. The method for comprehensively controlling the continuous cropping disorder of small yellow ginger by combining the slow-release chlorine dioxide soil disinfection granules and probiotics according to claim 4, characterized in that: In step (i), the mass ratio of ascorbic acid, sodium alginate and sorbitol is 1:(2-3):(1.3-1.5); The added amount of the composite protective agent is 3-5 wt% of the mass of the Bacillus subtilis fermentation broth.
6. The method for comprehensively controlling the continuous cropping disorder of small yellow ginger by combining the slow-release chlorine dioxide soil disinfection granules and probiotics according to claim 4, characterized in that: In step (ii), the mass ratio of white carbon black, diatomaceous earth and magnesium aluminum silicate is (3-5):(4-6):1; The mass ratio of the composite carrier to the composite fermentation liquid is 1:(1.5-2.5); The mass ratio of the potassium humate, the composite carrier and the spore germination agent is 1:(8-10):(0.3-0.5); The mass ratio of L-alanine, inosine and fructose is 1:(1.5-2):(4-5).
7. The method for comprehensively controlling the continuous cropping disorder of small yellow ginger by combining the slow-release chlorine dioxide soil disinfection granules and probiotics according to claim 4, characterized in that: In step (iii), the inlet air temperature of the spray drying is 60-70°C; The outlet air temperature of the spray drying is 40-50°C; The spray drying time is 20 to 30 seconds; The mass ratio of the aliphatic polyoxyethylene ether to polysorbate 80 is 1:(1.3-1.8); The mass ratio of the probiotic powder to the complex surfactant is (26-28):1.
Citation Information
Patent Citations
Bacillus subtillis GB519 wettable powder and aqueous solution as well as preparation method and application of bacillus subtillis GB519 wettable powder and aqueous solution
CN115581228A
Method for comprehensively controlling root rot and dry rot of pecan plants through cooperation of chlorine dioxide and probiotics
CN118786857A
Controlled release mucoadhesive matrix formulation containing tolterodine and a process for its preparation
WO2005105036A1