Method for relieving phytotoxicity of seedling-stage rice herbicide

Abstract

The invention relates to the technical field of rice herbicide phytotoxicity prevention and control, in particular to a method for relieving rice herbicide phytotoxicity in the seedling stage. Paddy rice seeds are soaked with a pyrroloquinoline quinine solution before sowing; the concentration of pyrroloquinoline quinine in the pyrroloquinoline quinine solution is 0.3 to 0.7 [mu] mol / L; the method comprises the following steps: spraying a pyrroloquinoline quinine solution on leaf surfaces in a period from two leaves to one core to three leaves of rice, wherein the concentration of pyrroloquinoline quinine in the pyrroloquinoline quinine solution is 1-2 [mu] mol / L; within 3-7 days after the pyrroloquinoline quinone solution is sprayed on the rice leaf surfaces, cyclopropanesulfonamide and a herbicide are mixed for use. PQQ and cyclopropanesulfonamide are coordinated to effectively relieve the phytotoxicity of herbicides to rice.

Description

Technical Field

[0001] This invention relates to the field of herbicide damage control technology for rice, and in particular to a method for alleviating herbicide damage in rice seedlings. Background Technology

[0002] 1) Development and limitations of plant-derived safener technology

[0003] Plant-derived safeners are an important research direction in the field of herbicide damage mitigation, and early research mainly focused on natural plant extracts as the core technology. Chinese research teams have made pioneering explorations in this field. For example, Academician Bai Lianyang's team developed two patented technologies as early as 2005: *Asarum heterotropoides* alcohol extract (for mitigating metolachlor damage) and *Notopterygium incisum* alcohol extract (for mitigating acetochlor damage). These technologies extract active ingredients from plants using alcohol solvents, which are then sprayed onto herbicide-damaged rice or soil. The bioactivity of these extracts activates the crop's own detoxification mechanisms, thereby reducing herbicide damage to rice seedlings. The main advantage of this type of technology lies in its environmental compatibility; the extracts are easily degraded in the natural environment, causing no secondary pollution, which aligns with the development direction of green agriculture.

[0004] However, traditional plant-derived safener technologies have significant limitations in practical applications. The extraction process is complex, requiring multiple steps such as drying, pulverizing, organic solvent extraction, and concentration, resulting in high production costs. The low concentration of active ingredients leads to large application rates in the field and poor operational convenience. The mechanism of action is unclear, mostly remaining at the level of phenomenological observation, lacking in-depth analysis of the molecular mechanism. The efficacy stability is insufficient; different batches of extracts exhibit significant differences in active ingredient content due to factors such as raw material source and extraction conditions, directly affecting the reproducibility of herbicide-relieving effects. More importantly, these plant extracts are primarily designed for specific herbicides (such as acetochlor and metolachlor), offering limited protection against amide herbicides such as pretilachlor, widely used in southern rice-growing areas, and failing to meet the diverse needs of actual production.

[0005] Table 1. Technical characteristics and limitations of traditional plant-derived safeners

[0006] Technical features Specific manifestations Application limitations Source of raw materials Medicinal plants such as Asarum and Notopterygium Limited resources and high costs Extraction process Alcohol solvent reflux extraction High energy consumption and complex process Target Specific herbicides (acetochlor, metolachlor) Narrow spectrum, unable to cope with multiple herbicides Environmental characteristics Easily degradable and pollution-free Its green and environmentally friendly advantages are obvious. Effect stability Large batch differences Unstable field effects

[0007] 2) Bottlenecks in microbial remediation technology and its field application

[0008] Microbial remediation technology, which utilizes specific strains to degrade residual herbicides in soil, is another important approach to solving the problem of herbicide residue damage. This technology addresses the widespread and difficult-to-control herbicide damage in rice-growing areas of southern China by screening for highly efficient degrading strains to remediate herbicide-contaminated soil environments. The research team has successfully isolated several degrading bacteria with practical application potential, including three quinclorac acid-degrading bacteria, two butachlor-degrading bacteria, and two pyrimisulfuron-methyl-degrading bacteria. Through processes such as fermentation condition optimization, induction modification, and strain ratio optimization, they have developed highly efficient microbial remediation agents.

[0009] Field trials have shown that microbial remediation technology can effectively repair herbicide damage to rice under ideal conditions, increasing rice yield by 8.3%–12.4%. The application of butachlor-degrading microbial agents has shown significant remediation effects on dichloroquinoline herbicide damage in solanaceous crops; pyrimisulfuron-methyl-degrading microbial agents have demonstrated excellent effects in the remediation of herbicide damage in rice. These microbial agents, combined with cultivation methods such as crop rotation in southern rice-growing areas, have formed an environmentally friendly herbicide damage remediation technology system.

[0010] However, microbial remediation technology faces three major challenges in practical applications:

[0011] Poor field adaptability of strains: The degrading bacteria screened in the laboratory face survival competition pressure in complex field environments. Their degradation activity is significantly affected by environmental factors such as soil temperature, pH value, and organic matter content, resulting in large fluctuations in performance.

[0012] Long time to take effect: Microbial reproduction and metabolism take a certain amount of time, which cannot meet the need for rapid relief of sudden pesticide damage in seedlings, and may miss the best rescue period.

[0013] The technology for preserving microbial agents is not mature: microbial preparations are easily deactivated during storage and transportation, resulting in short product shelf life and affecting the actual application effect.

[0014] While microbial-phytoremediation technology theoretically possesses a synergistic effect, numerous technical bottlenecks remain in its practical application. Microbial remediation needs to be complementary and combined with other technologies to realize its full value in the rapid treatment of pesticide damage in rice seedlings.

[0015] 3) Technological breakthroughs in nanocarriers and intelligent delivery systems

[0016] Innovation in supramolecular nano-formulation

[0017] The development of nanotechnology has brought revolutionary breakthroughs to the field of herbicide safeners. The MNS@HBPCD supramolecular nanoformulation successfully developed by Academician Bai Lianyang's team in 2025 represents the current cutting-edge technology. This technology encapsulates the previously developed MNS organic ionic salt within a hydroxypropyl-β-cyclodextrin (HBPCD) supramolecular carrier, forming a nanoscale delivery system. This innovative design overcomes several technical bottlenecks inherent in traditional safeners:

[0018] Improved solubility and stability: The special cavity structure of cyclodextrin effectively encapsulates the active ingredient of MNS, significantly improving its solubility and chemical stability in aqueous environments;

[0019] Enhanced cellular absorption efficiency: Nanoscale particles significantly improve the absorption efficiency of active ingredients by rice cells;

[0020] Reduced environmental toxicity: The formulation showed significantly lower toxicity to zebrafish embryos, HepG2 cells, and HaCaT cells than the commercially available safer herbicides.

[0021] Field trials have confirmed that MNS@HBPCD performs exceptionally well in protecting rice from pretilachlor damage. Compared to chlorpyrifos, it significantly increases seedling quantity, plant height, root length, fresh weight, and final yield without affecting the herbicidal efficacy of pretilachlor. This technology opens up new avenues for safener development, but its large-scale production costs and process stability still require further verification.

[0022] Table 2. Performance comparison of novel nano-formulation MNS@HBPCD with traditional safety agents

[0023] Performance indicators MNS@HBPCD Nanoformulation Traditional safener (glyphosate) Improvement range solubility Significantly improved Low >50％ Cell penetration Significantly enhanced weak >60％ Detoxification efficiency Precisely activate the GST pathway Mechanism of action unclear Increase by more than 30% Crop growth indicators Plant height, root length, and fresh weight increased significantly. Limited effect Increase by 20-35% Environmental toxicity Significantly reduced toxicity to aquatic organisms higher Reduce by 40-60% Final output Significant improvement generally Increase by 15-25%

[0024] 4) Intelligent response release system

[0025] The intelligent co-delivery system of herbicides and safeners represents another significant technological innovation in recent years. The "vaccine-encapsulated herbicide" technology (2023) developed earlier by Bai Lianyang's team employs a strategy of first encapsulation followed by self-assembly. Using a special material as a carrier, the safener AD-67 is adsorbed onto the carrier surface, while the herbicide pretilachlor is encapsulated within the material. This design creatively solves the critical issue of the timing of action between the safener and herbicide.

[0026] Optimized timing of action: The safener on the carrier surface can be released rapidly, activating the rice detoxification system in advance;

[0027] Herbicide slow-release: The internal pretilachlor is slowly released based on a pH slow-release system, prolonging the effective period;

[0028] Reduced dosage and increased efficiency: Greenhouse trials show that this system improves weed control by more than 30% compared to commercially available pretilachlor emulsifiable concentrate formulations.

[0029] The newly developed Pre@ZIF-67@AD-67 system (2025) further upgrades this concept. This system uses a ZIF-67 metal-organic framework (MOF) as a carrier to load the herbicide pretilachlor, with the surface-assembled safener AD-67, forming a smart drug delivery system with pH-responsive release capabilities. Under slightly acidic rhizosphere conditions, the system can intelligently trigger the release of pretilachlor; simultaneously, AD-67 can alleviate the toxic side effects of pretilachlor on rice. This dual-function design not only improves pesticide utilization but also significantly reduces acute toxicity to soil and aquatic organisms, reflecting the development direction of precision agriculture and green pesticides.

[0030] However, the industrialization of intelligent delivery systems still faces many challenges. The synthesis cost of carrier materials such as MOFs is high, and large-scale production processes are not yet mature; their environmental fate is unclear, and research on the migration and transformation patterns and long-term safety of nanomaterials in soil ecosystems is insufficient; application technology requirements are high, necessitating precise adjustments to application rates based on factors such as soil pH and organic matter content, placing higher demands on farmers' technical skills. These issues restrict the large-scale application of nano-intelligent pesticides in the field.

[0031] 5) Integrated application of comprehensive governance technology system

[0032] To address the challenge of single-technology solutions being insufficient to comprehensively resolve herbicide damage, integrated pest management (IPM) systems have emerged. This system combines multiple technologies to form a complete solution encompassing herbicide damage prevention, rapid assessment, and efficient control.

[0033] Artificial intelligence decision support system: Based on big data and machine learning algorithms, it guides farmers to use herbicides scientifically and rationally, reducing the risk of herbicide damage from the source;

[0034] Rapid herbicide damage assessment technology: Using ultrafiltration centrifugation to extract herbicides from in-situ soil pore water, eliminating interference from soil physicochemical properties, and accurately and rapidly assessing the degree of herbicide damage to crops in different soils;

[0035] Integrated herbicide damage control technology: Scientifically combining plant-derived safe agents with microbial degradation agents to synergistically control existing herbicide damage.

[0036] This system has established technical solutions adapted to cultivation methods such as continuous cropping and water-dryland rotation in rice-growing areas of southern China. Between 2004 and 2013, it was promoted on a cumulative scale of 95.26 million mu (approximately 6.3 million hectares) in multiple southern provinces, saving farmers 2.02 billion yuan in economic losses and generating 420 million yuan in new output value for enterprises, demonstrating significant economic and social benefits.

[0037] However, this integrated system still faces challenges in its widespread application. Its high technical complexity tests the technical acceptance capabilities of grassroots agricultural technicians and farmers; its strong equipment dependence, requiring specialized instruments such as centrifuges for rapid evaluation, makes it difficult to implement in remote rural areas; and its high cost, with IoT sensing devices and molecularly imprinted materials being prohibitively expensive for small-scale growers. These factors limit the system's widespread application in resource-scarce regions. Summary of the Invention

[0038] To address the aforementioned problems, this invention provides a method for mitigating herbicide damage in rice seedlings.

[0039] To achieve the above objectives, the present invention provides the following technical solution:

[0040] This invention provides a method for mitigating herbicide damage in rice seedlings, comprising the following steps:

[0041] 1) Rice seeds were soaked in a pyrroloquinoline quinone solution before sowing; the concentration of pyrroloquinoline quinone in the pyrroloquinoline quinone solution was 0.3–0.7 μmol / L;

[0042] 2) Spray pyrroloquinoline quinone solution on the leaves of rice at the 2-leaf-1-heart to 3-leaf stage, wherein the concentration of pyrroloquinoline quinone in the pyrroloquinoline quinone solution is 1-2 μmol / L;

[0043] 3) Within 3 to 7 days after foliar spraying of pyrroloquinoline quinone solution on rice, mix cyclopropanesulfonamide and herbicide before use.

[0044] Preferably, the concentration of pyrroloquinoline quinone in the pyrroloquinoline quinone solution in step 1) is 0.5 μmol / L.

[0045] Preferably, the soaking time in step 1) is 20-28 hours, and the soaking temperature is 28-37°C.

[0046] Preferably, the soaking time in step 1) is 24 hours, and the soaking temperature is 30-35°C.

[0047] Preferably, in step 3), the cyclopropanesulfonamide and herbicide are mixed and used 5 days after the pyrroloquinoline quinone solution is sprayed on the rice leaves.

[0048] Preferably, the amount of cyclopropanesulfonamide used in step 3) is 50-80 g / ha.

[0049] Preferably, the herbicide in step 3) includes one or more of butachlor, acetochlor, pyrimisulfuron, cyprosulfuron, quinclorac, methoxyfenozide, and nicotine.

[0050] Preferably, when the rice planting site has sandy soil, the dosage of the herbicide is reduced by 15-25%.

[0051] Preferably, when the rice leaf margins turn yellow, a mixture of 0.1-0.2% brassinolide and 0.2-0.4% potassium dihydrogen phosphate is sprayed.

[0052] Synergistic mechanism:

[0053] PQQ (pyrroloquinoline quinone) pretreatment: Through a dual approach of seed soaking and seedling spraying, the content of membrane lipid peroxidation product MDA is reduced by ≥30%, thus mitigating oxidative stress induced by herbicides;

[0054] Immediate intervention with cyclopropanesulfonamide: competitively inhibits herbicide target enzymes (such as ALS) and induces cytochrome P450 enzymes to accelerate herbicide metabolism, shortening the period of herbicide damage by 10-15 days;

[0055] Dual protective effect: PQQ enhances endogenous repair capacity (preventative) + cyclopropanesulfonamide directly detoxifies (therapeutic), achieving a herbicide damage inhibition rate increase of over 40%. Pretreatment with PQQ promotes robust rice growth and vigorous metabolism, enhances basic stress resistance, and induces the activity of antioxidant-related enzymes in rice, clearing ROS from the rice body. Cyclopropanesulfonamide induces the activity of cytochrome P450 monooxygenase and glutathione S-transferase in rice, converting herbicides into non-toxic forms for isolation or excretion, reducing the content of herbicides binding to target sites, and the induced GST itself also participates in ROS scavenging. In this invention, the fresh weight inhibition rate of herbicides on rice after PQQ treatment was 30.89%, after cyclopropanesulfonamide treatment it was 28.63%, and the fresh weight inhibition rate of herbicides on rice after the combined use of PQQ and cyclopropanesulfonamide was 21.37%. The synergistic effect of PQQ and cyclopropanesulfonamide can effectively alleviate herbicide damage to rice.

[0056] I. Technological Innovation: Breaking Through the Limitations of a Single Mechanism

[0057] 1. A dual synergistic mechanism of "prevention + treatment"

[0058] Current shortcomings: Existing technologies mostly rely on a single action pathway (such as plant-derived safeners that only activate detoxification enzymes, and microbial remediation that only degrades residues), and cannot simultaneously address the suddenness and complexity of pesticide damage.

[0059] Invention and Innovation:

[0060] PQQ pretreatment (seed soaking + seedling spraying) systematically enhances the endogenous resistance of rice (reduces MDA by ≥30%), strengthens antioxidant capacity from the source, which is equivalent to building an "immune barrier";

[0061] Immediate intervention with cyclopropanesulfonamide accelerates herbicide metabolism by competitively inhibiting target enzymes (such as ALS) and inducing P450 enzymes, thus achieving rapid detoxification.

[0062] Synergistic effect: Dual protection increases the pesticide damage inhibition rate by more than 40% and shortens the pesticide damage period by 10-15 days, solving the pain points of "slow effect" of microbial remediation and "unstable effect" of plant-derived safe agents.

[0063] 2. Broad-spectrum compatibility covering mainstream herbicides

[0064] Current shortcomings: Traditional plant-derived safeners (such as Ligusticum chuanxiong extract) are only effective against acetochlor / metolachlor, while the nanocarrier MNS@HBPCD is mainly compatible with metolachlor, resulting in a narrow protective spectrum.

[0065] Invention and Innovation:

[0066] Cyclopropanesulfonamide is compatible with 7 types of herbicides in 4 categories (including amides, sulfonylureas, quinoline carboxylic acids, imidazolinones, etc.), covering more than 90% of commonly used herbicides in rice-growing areas of southern China;

[0067] PQQ enhances the basic resistance mechanism of cell membrane stability and is effective against oxidative stress induced by various herbicides.

[0068] II. Breakthrough in Application Performance: Balancing Stability and Ease of Use

[0069] 1. Standardized formulations resolve batch variation issues.

[0070] Current shortcomings: The active ingredients in plant-derived safeners fluctuate due to differences in raw material sources and extraction processes; the survival rate of microbial agents is limited by storage conditions.

[0071] Patent Innovation:

[0072] The chemical standards PQQ and cyclopropanesulfonamide are used directly, with precise and controllable concentrations (μmol / L level) and no batch-to-batch differences.

[0073] No complex extraction or microbial fermentation process is required; it can be implemented through conventional "seed soaking + leaf spraying" operations.

[0074] 2. Rapid response capability meets the needs of seedling treatment.

[0075] Current shortcomings: Microbial remediation takes 3-5 days to take effect, missing the golden rescue period for seedlings; intelligent delivery systems (such as MOF vectors) are expensive and have complex processes.

[0076] Patent Innovation:

[0077] Cyclopropanesulfonamide should be mixed and used immediately, and it takes effect immediately after spraying.

[0078] The basic resistance established by PQQ pretreatment can delay the occurrence of phytotoxicity and buy time for chemical detoxification.

[0079] III. Advantages of Application and Promotion: Low Cost and Easy Operation

[0080] 1. Simplify the technology chain and lower the barrier to entry.

[0081] Current shortcomings: The comprehensive management system requires IoT devices to support pesticide damage assessment, and nanocarriers rely on specialized production processes, making it difficult to promote to farmers.

[0082] Invention and Innovation:

[0083] Only standard agricultural equipment (seed soaking tank, sprayer) is required;

[0084] Farmers can easily master the "two-stage dilution method" for mixing herbicides and antidotes.

[0085] 2. Dynamic adjustment mechanism adapts to complex environments

[0086] Current shortcomings: Microbial remediation is greatly affected by soil pH / temperature; intelligent delivery systems are sensitive to soil organic matter content.

[0087] Patent Innovation:

[0088] Provide guidelines for adapting to environmental parameters (e.g., 20% reduction for sandy soils, spraying temperature ≤30℃);

[0089] A remedial plan for pesticide damage (brassinolide + potassium dihydrogen phosphate) is prepared to form a closed-loop management system.

[0090] IV. Benefit Comparison: Significant Overall Advantages

[0091] Table 3. Comparison of Benefits

[0092] Evaluation Dimensions Existing technology representative Invention Solution Patent advantages Protection spectrum Only 1-2 types of herbicides (plant-derived) 4 categories and 7 types of herbicides Covering mainstream pesticide damage types speed of action Microbial repair takes 3-5 days Instant detoxification + pretreatment resistance Meeting the needs of seedling rescue Effect stability Plant-derived batch variation >30% Chemical standards, error <5% High repeatability Cost-effectiveness Nanocarriers have high synthesis costs Conventional formulations reduce cost per acre by 40%. Applicable to small farmers Environmental friendliness Risk of plant-derived solvent contamination PQQ is a biological agent with low toxicity and rapid degradation. In line with the direction of green agriculture

[0093] V. Conclusion

[0094] This patent achieves a technological breakthrough at three levels through the synergistic mechanism of PQQ-induced endogenous resistance and cyclopropanesulfonamide-targeted detoxification:

[0095] 1. Scientific level: It pioneers a dual-pathway model of "prevention-treatment", from basic antioxidant defense to precise intervention at the enzyme level;

[0096] 2. Application level: Standardization, broad application scope, and lightweight design address the pain points of existing technologies, such as narrow applicability, unstable performance, and high cost;

[0097] 3. Promotion level: The operation process is tailored to farmers' habits.

[0098] The core value lies in transforming the complex mechanisms in the laboratory into a simple operation of "seed soaking + spraying", while taking into account both high efficiency and universality, providing a scalable and practical solution for the management of herbicide damage in rice.

[0099] I. Key Points of Core Technologies

[0100] 1. "Dual-time sequence - dual-mechanism" collaborative system

[0101] Synergistic timing: PQQ pretreatment (seed soaking + seedling spraying) establishes basic resistance → pre-application window (3-5 days) for herbicide → immediate detoxification by mixing cyclopropanesulfonamide and herbicide.

[0102] Mechanism coordination:

[0103] PQQ induces endogenous resistance: activates antioxidant enzymes (SOD / POD) and reduces membrane lipid peroxidation (MDA ↓ ≥ 30%).

[0104] Cyclopropanesulfonamide targeted detoxification: competitively inhibits herbicide target enzymes (ALS, etc.) + induces P450 enzymes to accelerate metabolism.

[0105] 2. Precise parameter control

[0106] Table 4 Precise Parameter Control

[0107] Processing stage Core parameters Functional Objectives PQQ soaking 0.5 μmol / L, 24 h, 30-35 ℃ Activate seed stress resistance genes PQQ seedling spraying 2 μmol / L (2-3 leaf stage) Enhance cell membrane stability Antidote dosage Cyclopropanesulfonamide 50-80 g / ha Blocks toxicity and shortens the phytotoxicity period by 10-15 days. Collaboration window period Apply PQQ 3-5 days after spraying. Maximizing the dual protection effect

[0108] 3. Broad-spectrum adaptation design

[0109] Compatible herbicide types: Simultaneously covers amides (butachlor / acetochlor), sulfonylureas (pyrimisulfuron / cyprosulfuron), quinoline carboxylic acids (dichloroquinoline acid), and imidazolinones (methoxymethylene / metazidine).

[0110] Dynamic remedial mechanism: For sudden pesticide damage (yellowing of leaf margins), apply an additional spray of 0.15% brassinolide + 0.3% potassium dihydrogen phosphate. Attached Figure Description

[0111] Figure 1 The phenotypes of rice after treatment with different concentrations of PQQ combined with methoxyfenozide are shown. A is the control (CK), B is the control without PQQ, and C, D, E, F and G are the treatments with 1, 2, 4, 8 and 16 μmol / L PQQ, respectively.

[0112] Figure 2 The rice phenotypes are those of rice treated with methoxyfenozide. A represents the control (CK), B represents the treatment with PQQ and cyclopropanesulfonamide, and C represents the treatment without PQQ and cyclopropanesulfonamide.

[0113] Figure 3The rice phenotypes are represented by methyl nicotinic acid treatment. A represents the control (CK), B represents the treatment with PQQ and cyclopropanesulfonamide, and C represents the treatment without PQQ and cyclopropanesulfonamide. Detailed Implementation

[0114] This invention provides a method for mitigating herbicide damage in rice seedlings, comprising the following steps:

[0115] 1) Rice seeds were soaked in a pyrroloquinoline quinone solution before sowing; the concentration of pyrroloquinoline quinone in the pyrroloquinoline quinone solution was 0.3–0.7 μmol / L;

[0116] 2) Spray pyrroloquinoline quinone solution on the leaves of rice at the 2-leaf-1-heart to 3-leaf stage, wherein the concentration of pyrroloquinoline quinone in the pyrroloquinoline quinone solution is 1-2 μmol / L;

[0117] 3) Within 3 to 7 days after foliar spraying of pyrroloquinoline quinone solution on rice, mix cyclopropanesulfonamide and herbicide before use.

[0118] In this invention, rice seeds are soaked in a pyrroloquinoline quinone solution before sowing; the concentration of pyrroloquinoline quinone in the solution is 0.3–0.7 μmol / L.

[0119] There are no specific limitations on the rice variety. In this invention, the mass ratio of rice seeds to the volume ratio of pyrrolquinoline quinone solution is 1:3. The concentration of pyrrolquinoline quinone in the solution is preferably 0.5 μmol / L. The soaking time is preferably 20–28 h, and the soaking temperature is preferably 28–37 °C. More preferably, the soaking time is 24 h, and the soaking temperature is preferably 30–35 °C. In this invention, soaking rice seeds with pyrrolquinoline quinone activates seed stress-resistance genes. If the soaking concentration is too low or the soaking time is too short, PQQ will not effectively activate the expression of related stress-resistance genes; if the concentration is too high or the soaking time is too long, it will inhibit seed germination and significantly reduce the induction ability of PQQ.

[0120] This invention involves foliar spraying of pyrroloquinoline quinone solution on rice plants during the 2-leaf to 3-leaf stage. The concentration of pyrroloquinoline quinone in the solution is 1–2 μmol / L. In this invention, spraying pyrroloquinoline quinone enhances the rice's tolerance to the herbicide methoxyfenozide. When PQQ was sprayed at concentrations of 0, 1, 2, 4, 8, and 16 μmol / L during the seedling stage, the rice treated with 0 μmol / L pyrroloquinoline quinone showed that most of the leaves turned yellow and withered, while the rice treated with PQQ showed significantly reduced methoxyfenozide damage, with only some leaves showing chlorosis and withering. When PQQ was used at concentrations of 0, 1, 2, 4, 8 and 16 μmol / L, the inhibition rates of methoxyfenozide on rice were 64.46%, 49.02%, 31.68%, 51.22%, 52.73% and 49.81%, respectively. Among them, 2 μmol / L PQQ induced the best rice tolerance to methoxyfenozide, which was significantly different from the 0 μmol / L pyrroloquinoline quinone treatment.

[0121] Table 5. Inhibition rate of methoxyimidazolium on rice at different PQQ concentrations

[0122] PQQ concentration (μmol / L) Inhibition rate (%) 0 <![CDATA[64.46 a ]]> 1 <![CDATA[49.02 b ]]> 2 <![CDATA[31.68 c ]]> 4 <![CDATA[51.22 b ]]> 8 <![CDATA[52.73 ab ]]> 16 <![CDATA[49.81 b ]]>

[0123] This invention involves mixing cyclopropanesulfonamide and a herbicide for application within 3-7 days after foliar spraying of pyrroloquinoline quinone solution on rice plants. Preferably, the mixture is applied 5 days after foliar spraying. The preferred dosage of cyclopropanesulfonamide is 50 g / ha. The herbicide preferably includes one or more of butachlor, acetochlor, pyrimisulfuron, cyclopropanesulfuron, quinclorac, methoxyfenozide, and methylphenidate. No specific dosage is required; conventional methods are sufficient for those skilled in the art. The effect of spraying cyclopropanesulfonamide is to block herbicide toxicity and accelerate metabolism.

[0124] In this invention, when the rice planting site is preferably sandy soil, the dosage of the herbicide is preferably reduced by 15-25%. In this invention, when the rice leaf margins turn yellow, a mixture of 0.1-0.2% brassinolide and 0.2-0.4% potassium dihydrogen phosphate by mass is preferably sprayed.

[0125] To further illustrate the present invention, the following detailed description is provided in conjunction with embodiments, but these should not be construed as limiting the scope of protection of the present invention.

[0126] Example 1

[0127] A method for mitigating herbicide damage in rice seedlings includes the following steps:

[0128] 1) Huang Huazhan soaked rice seeds in a pyrroloquinoline quinone solution before sowing; wherein the concentration of pyrroloquinoline quinone in the pyrroloquinoline quinone solution was 0.5 μmol / L, the soaking time was 24 h, and the soaking temperature was 30-35℃;

[0129] 2) Spray pyrroloquinoline quinone solution on the leaves of rice at the 2-leaf-1-heart to 3-leaf stage, wherein the concentration of pyrroloquinoline quinone in the pyrroloquinoline quinone solution is 2 μmol / L;

[0130] 3) Five days after foliar spraying of pyrroloquinoline quinone solution on rice, cyclopropanesulfonamide and herbicide are mixed and used. The dosage of cyclopropanesulfonamide is 50 g / ha. The herbicide types are 60% butachlor EC (Nantong Jiangshan Pesticide Chemical Co., Ltd., Jiangsu Province), 20% acetochlor WP (Dalian Jiuxin Crop Science Co., Ltd.), 10% pyrimisulfuron WP (Jiangxi Jiatiansen Biotechnology Co., Ltd.), 10% cyclopropanesulfonamide WP (BASF AG), 50% quinclorac WP (Jiangsu Kuida Agrochemical Co., Ltd.), 4% methoxyfenozide WP (Weifang Xianda Chemical Co., Ltd.), and 240 g / L methoxyfenozide WP (Shandong Xianda Agrochemical Co., Ltd.), with dosages of 100 mL / mu, 30 g / mu, 20 g / mu, 20 g / mu, 40 g / mu, 75 mL / mu, and 20 mL / mu, respectively.

[0131] 4) Rice seeds were sterilized by soaking in a 0.13% effective concentration of strong chlorine solution at a temperature maintained between 25 and 30°C. Residual strong chlorine was then rinsed off with clean water. The treatment group was then soaked in 0.5 μmol / L PQQ solution for 24 hours, while the control group was soaked in clean water for 24 hours. The germination temperature in the incubator was set at 30°C. After 24 hours of germination, the seeds were removed, and the emerging rice seeds were sown into 96-well PCR plates using tweezers. Yoshida rice nutrient solution was used at a concentration of 0.46085 g / L, and the seeds were cultured until the 3-4 leaf stage before treatment. After treatment with PQQ and cyclopropanesulfonamide, the fresh weight inhibition rate of butachlor was 8.26%, while that of rice without PQQ and cyclopropanesulfonamide treatment was 13.62%. The fresh weight inhibition rate of acetochlor was 9.03%, while that of rice without PQQ and cyclopropanesulfonamide treatment was 14.98%. The fresh weight inhibition rate of pyrimisulfuron was 11.21%, while that of rice without PQQ and cyclopropanesulfonamide treatment was 19.93%. The fresh weight inhibition rate of cyclopropanesulfonamide was 13.04%, while that of rice without PQQ and cyclopropanesulfonamide treatment was [not specified in the original text]. The fresh weight inhibition rates of rice treated with PQQ and cyclopropanesulfonamide were 26.73%, while those of dichloroquinoline were 13.77%, compared to 29.63% for rice not treated with PQQ and cyclopropanesulfonamide. Methoxyfenozide inhibited fresh weight by 21.37%, while the inhibition rate for rice not treated with PQQ and cyclopropanesulfonamide was 65.29%, showing a significant difference. Imidazole nicotinic acid inhibited fresh weight by 25.66%, while the inhibition rate for rice not treated with PQQ and cyclopropanesulfonamide was 68.23%. These results indicate that treatment with PQQ and cyclopropanesulfonamide can alleviate herbicide damage in rice.

[0132] Although the above embodiments have provided a detailed description of the present invention, they are only some embodiments of the present invention, and not all embodiments. People can obtain other embodiments based on these embodiments without creative effort, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A method for mitigating herbicide damage in rice seedlings, characterized in that, Includes the following steps: 1) Rice seeds were soaked in a pyrroloquinoline quinone solution before sowing; the concentration of pyrroloquinoline quinone in the pyrroloquinoline quinone solution was 0.3–0.7 μmol / L; 2) Spray pyrroloquinoline quinone solution on the leaves of rice at the 2-leaf-1-heart to 3-leaf stage, wherein the concentration of pyrroloquinoline quinone in the pyrroloquinoline quinone solution is 1-2 μmol / L; 3) Within 3 to 7 days after foliar spraying of pyrroloquinoline quinone solution on rice, mix cyclopropanesulfonamide and herbicide before use.

2. The method according to claim 1, characterized in that, In step 1), the concentration of pyrroloquinoline quinone in the pyrroloquinoline quinone solution is 0.5 μmol / L.

3. The method according to claim 1, characterized in that, Step 1) The soaking time is 20-28 hours, and the soaking temperature is 28-37°C.

4. The method according to claim 1, characterized in that, Step 1) The soaking time is 24 hours, and the soaking temperature is 30-35℃.

5. The method according to claim 1, characterized in that, Step 3) Five days after applying pyrroloquinoline quinone solution to the rice leaves, mix cyclopropanesulfonamide and the herbicide together before use.

6. The method according to claim 1 or 5, characterized in that, Step 3) The amount of cyclopropanesulfonamide used is 50-80 g / ha.

7. The method according to claim 1, characterized in that, Step 3) The herbicide includes one or more of butachlor, acetochlor, pyrimisulfuron, cyprosulfuron, quinclorac, methoxyfenozide, and nicotine.

8. The method according to claim 1, characterized in that, When the rice-growing area has sandy soil, the dosage of the herbicide should be reduced by 15-25%.

9. The method according to claim 1, characterized in that, When the edges of rice leaves turn yellow, spray a mixture of 0.1-0.2% brassinolide and 0.2-0.4% potassium dihydrogen phosphate.

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