Preparation method of sugarcane field herbicide containing mesotrione, triclopyr and halosulfuron-methyl

Abstract

The invention belongs to the technical field of herbicides, and particularly relates to a preparation method of a sugarcane field herbicide containing mesotrione, triclopyr and halosulfuron-methyl, and the preparation method comprises the following steps: S1, preparing mesotrione salt; s2, preparing triclopyr acetate; s3, preparation of a dosage form: adding auxiliary components which are allowed to be added in pesticide science into the mesotrione salt, the triclopyr and the halosulfuron-methyl active compound to prepare the pesticide preparation. According to the invention, the stability problem of compounding of three effective components, namely mesotrione, triclopyr and halosulfuron-methyl, is successfully solved, the compound herbicide with stable performance is prepared, and the market blank is filled; the production process is simplified, the production and packaging material cost is reduced, the production of packaging waste is reduced, and the environmental protection requirement is met; when farmers use the pesticide, independent proportioning is not needed, the operation is more convenient, and the pesticide application efficiency is improved; the product accords with national supervision policies on pesticide products, and can provide support for standard operation of production enterprises and scientific pesticide application of farmers.

Description

Technical Field

[0001] This invention belongs to the field of herbicide technology, specifically relating to a method for preparing a sugarcane field herbicide containing mesotrione, triclopyralid, and chlorpyrifos. Background Technology

[0002] Weeds compete with crops like sugarcane for crucial resources such as sunlight, water, and nutrients, seriously threatening crop safety and significantly impacting yield. Herbicides, as a core tool for weed control in modern agriculture, are both economical and highly effective; however, long-term improper use has led to increased herbicide resistance in weeds. Among existing technologies, compounding different herbicidal active ingredients is one effective and convenient way to address these problems.

[0003] Mesotrione is a benzoylcyclohexanedione herbicide, an effective competitive inhibitor of p-hydroxyphenylpyruvate dioxygenase (HPPD) enzyme. It is a selective herbicide that inhibits HPPD activity. Inhibition of HPPD in weeds disrupts the conversion of p-hydroxyphenylpyruvate to hydantoin, leading to tyrosine accumulation and plastoquinone deficiency in weed meristems. This, in turn, affects the biosynthesis of carotenoids in the target plant. After 3-5 days, bleaching symptoms appear in the meristems and new tissues of the weed, eventually spreading to the entire plant, causing the weed to bleach and die. It can control weeds such as garland chrysanthemum, cocklebur, lambsquarters, wild shepherd's purse, barnyard grass, chickweed, and crabgrass.

[0004] Triclopyralid is a pyridine carboxylic acid hormone-type herbicide developed by Dow Chemical. It is a systemic selective herbicide; after spraying, the solution is absorbed by the leaves and roots of the plant and translocated throughout the plant. It acts on the plant's nucleic acid metabolism, causing the plant to produce excessive nucleic acids. This leads to the transformation of some tissues into meristematic tissues, resulting in root, stem, and leaf malformation, depletion of stored substances, blockage or rupture of vascular bundles, and eventual plant death. It is widely used in wheat, corn, sorghum, sugarcane, and other gramineous cereal fields to control broadleaf weeds.

[0005] Pyriproxyfenozide is a selective systemic herbicide of the sulfonylurea class. It works by inhibiting the plant's ALS enzyme acetolactate synthase, preventing the biosynthesis of branched-chain amino acids such as valine, isoleucine, and leucine, ultimately disrupting protein synthesis and interfering with DNA synthesis, cell division, and growth. Pyriproxyfenozide is absorbed through the roots, stems, and leaves of the plant and is translocated within the xylem and phloem, acting on acetolactate synthase. Herbicide damage manifests as growth arrest, chlorosis, and death of the apical meristem; the plant dies after 2-3 weeks. Pyriproxyfenozide is currently the only effective pre- and post-emergence herbicide safe for sugarcane and capable of completely eradicating Cyperus rotundus in sugarcane fields.

[0006] Currently, the market for weed control products in sugarcane fields mainly consists of combination sets of single-agent products such as 480g / L triclopyralid EC, 10% mesotrione dispersible oil suspension, and 75% chlorpyrifos water dispersible granules. However, there are stability issues when these three active ingredients are combined (e.g., the active ingredients are prone to decomposition), making it difficult to prepare stable compound formulations. Therefore, there are currently no compound products on the market that simultaneously contain all three active ingredients. In addition, such combination sets have many drawbacks in practical applications: cumbersome production processes, low efficiency of manual assembly, high packaging material costs, and a large amount of packaging waste. Farmers also need to prepare the formulations separately, which is inconvenient. Furthermore, national regulatory policies on pesticide combination sets are becoming increasingly strict. To further regulate the business practices of manufacturers and promote scientific pesticide use by farmers, some regions have explicitly banned the sale of pesticide combination sets. Summary of the Invention

[0007] The purpose of this invention is to provide a method for preparing a sugarcane field herbicide containing nicosulfuron, triclopyralid, and chlorpyrifos, in order to solve the problems existing in the prior art.

[0008] To achieve the above objectives, the present invention provides the following technical solution: A method for preparing a sugarcane herbicide includes the following steps: S1. Preparation of nicosulfuron salt An alkaline solution was added dropwise to a nicosulfuron suspension, and the reaction was stirred until complete to obtain nicosulfuron salt. S2. Preparation of triclopyroxyacetic acid salt An alkaline solution was added dropwise to a suspension of triclopyroxyacetic acid, and the reaction was allowed to proceed until complete with stirring to obtain triclopyroxyacetic acid salt. S3. Preparation of pesticide formulations Pesticide formulations are prepared by adding pesticide-permitted auxiliary ingredients to nicotinamide technical grade pesticides such as nicotinamide salt, triclopyralid, and chlorpyrifos.

[0009] Further, step S1 specifically involves: preparing a 20-60% nicosulfuron suspension using deionized water; then adding a 20-30% sodium hydroxide aqueous solution dropwise to the nicosulfuron suspension, stirring at 50-80°C until the reaction is complete, thereby obtaining the sodium nicosulfuron salt.

[0010] Furthermore, after the reaction is complete, the pH value of the reaction system is 6.0-9.5; the molar ratio of nicosulfuron to sodium hydroxide is 1:0.95-1.05.

[0011] Further, step S2 specifically involves: preparing a 10-40% triclopyroxyacetic acid suspension using deionized water, then adding a 20-30% potassium hydroxide aqueous solution dropwise to the triclopyroxyacetic acid suspension, stirring at 50-80°C until the reaction is complete, thereby obtaining the potassium triclopyroxyacetic acid salt.

[0012] Furthermore, after the reaction is complete, the pH value of the reaction system is 6.0-9.5; the molar ratio of nicosulfuron to sodium hydroxide is 1:0.95-1.05.

[0013] Furthermore, in step S3, the pesticide-permitted auxiliary ingredients are selected from at least one of sodium lignosulfonate, NNO, alkyl sulfonates, alkylphenol polyoxyethyl ether sulfonates, pull-apart powder BX, K12, and Morwet EFW.

[0014] Furthermore, in step S3, the active ingredient and pesticide-permitted auxiliary ingredients are prepared into pesticide formulations using appropriate equipment and processes. The formulations include, but are not limited to, wettable powders, aqueous suspensions, dispersible oil suspensions, water-dispersible granules, dry suspensions, and soluble concentrates.

[0015] Furthermore, in step S3, the technical grades of nicosulfuron, triclopyralid, and chlorpyrifos account for 2-40%, 5-45%, and 1-20% of the total mass of the pesticide formulation, respectively. Furthermore, in step S3, the total effective content of the pesticide formulation is 10-90%.

[0016] Compared with the prior art, the present invention has the following beneficial effects: (1) This invention successfully solved the stability problem of the compound of three active ingredients, mesotrione, triclopyralid and chlorpyrifos, and prepared a stable compound herbicide. After heat storage, the decomposition rate of each pesticide active ingredient was less than 5%, and all other indicators met the control standards.

[0017] (2) The sodium salt of nicosulfuron and potassium salt of triclopyralid of the present invention can be completely dissolved in water and exist in ionic form, which makes them easier to be absorbed and transported by weeds, and their control effect is better than that of traditional combination products.

[0018] In summary, this invention successfully solves the stability problem of compounding three active ingredients—mesosulfuron, triclopyralid, and chlorpyrifos—and produces a stable compound herbicide, filling a market gap. It simplifies the production process, reduces production and packaging material costs, minimizes packaging waste, and meets environmental protection requirements. Farmers do not need to mix the herbicides separately, making operation more convenient and improving application efficiency. The product complies with national regulations on pesticide products, helping manufacturers operate in a standardized manner and farmers use pesticides scientifically. Detailed Implementation

[0019] The technical solution of this invention patent will be clearly and completely described below. Obviously, the described embodiments are some embodiments of this invention, but not all embodiments.

[0020] Example 1: 28.5% Triclopyralid·Nicosulfuron·Clopyrimisulfuron Wettable Powder A method for preparing a 28.5% triclopyralid·nicosulfuron·clopyralid wettable powder, comprising, by mass percentage, the following components: triclopyralid 14.5%, nicosulfuron 10%, clopyralid 4%, sodium lignosulfonate 5%, NNO 3%, K12 2%, silica 10%, and kaolin balance. The specific steps are as follows: S1. Preparation of sodium nicosulfuron-methyl The technical grade mesotrione was mixed with water to form a mesotrione suspension, and then an aqueous solution of sodium hydroxide was added dropwise. The sodium hydroxide solution contained 25% sodium hydroxide by mass. The mixture was then stirred at 80°C until the reaction was complete. When the reaction was complete, the pH of the reaction system was 8.0-9.5, and the sodium salt of mesotrione was obtained. S2. Preparation of potassium triclopyroxyacetate Triclopyroxyacetic acid technical was mixed with water to form a triclopyroxyacetic acid suspension, and then a 25% (w / w) potassium hydroxide aqueous solution was added dropwise. The mixture was then stirred at 80°C until the reaction was complete. When the reaction was complete, the pH of the reaction system was 8.0-9.5, and potassium triclopyroxyacetic acid was obtained. S3. Preparation of formulations Sodium nicosulfuron, potassium triclopyralid, and chlorpyrifos technical grade were mixed together, and sodium lignosulfonate, NNO, K12, silica, and kaolin were added and mixed evenly. The mixture was then pulverized by air jet milling to prepare a 28.5% triclopyralid·nicosulfuron·chlorpyrifos wettable powder.

[0021] Example 2: 75% Triclopyralid·Nicosulfuron·Clopyrimisulfuron Water Dispersible Granules A method for preparing 75% triclopyralid·nicosulfuron·clopyralid-sulfuron water-dispersible granules, comprising, by mass percentage: 38% triclopyralid, 25% nicosulfuron, 12% clopyralid, 5% polycarboxylate, 3% Morwet EFW, 5% silica, and the balance kaolin. The specific steps are as follows: S1. Preparation of sodium nicosulfuron-methyl The technical grade mesotrione was mixed with water to form a mesotrione suspension, and then an aqueous solution of sodium hydroxide was added dropwise. The sodium hydroxide solution contained 30% sodium hydroxide by mass. The mixture was then stirred at 60°C until the reaction was complete. When the reaction was complete, the pH of the reaction system was 8.0-9.5, and the sodium salt of mesotrione was obtained. S2. Preparation of potassium triclopyroxyacetate Triclopyroxyacetic acid technical was mixed with water to form a triclopyroxyacetic acid suspension, and then an aqueous solution of potassium hydroxide was added dropwise. The potassium hydroxide solution contained 30% potassium hydroxide by mass. The mixture was then stirred at 60°C until the reaction was complete. When the reaction was complete, the pH of the reaction system was 8.0-9.5, and potassium triclopyroxyacetic acid was obtained. S3. Preparation of formulations Sodium nicosulfuron, potassium triclopyralid, and chlorpyrifos technical grade were mixed together, and polycarboxylate, Morwet EFW, kaolin, and silica were added and mixed evenly. The composition was then subjected to air jet milling, water mixing and granulation, and drying to prepare 80% nicosulfuron·triclopyralid·chlorpyrifos water-dispersible granules.

[0022] Example 3: 20% Triclopyralid·Nicosulfuron·Clopyrimisulfuron Dispersible Oil Suspension A method for preparing a 20% triclopyralid·nicosulfuron·clopyralid-sulfuron dispersible oil suspension, comprising, by mass percentage: 8% triclopyralid, 10% nicosulfuron, 2% clopyralid, 1.5% organobentonite, 2% silica, 20% methyl oleate emulsifier, and the balance being methyl oleate. The specific steps are as follows: S1. Preparation of sodium nicosulfuron-methyl The technical grade mesotrione was mixed with water to form a mesotrione suspension, and then an aqueous solution of sodium hydroxide was added dropwise. The sodium hydroxide solution contained 25% sodium hydroxide by mass. The mixture was then stirred at 50°C until the reaction was complete. When the reaction was complete, the pH of the reaction system was 8.0-9.5, and the sodium salt of mesotrione was obtained. S2. Preparation of potassium triclopyroxyacetate Triclopyroxyacetic acid technical was mixed with water to form a triclopyroxyacetic acid suspension, and then an aqueous solution of potassium hydroxide was added dropwise. The potassium hydroxide solution contained 30% potassium hydroxide by mass. The mixture was then stirred at 50°C until the reaction was complete. When the reaction was complete, the pH of the reaction system was 8.0-9.5, and potassium triclopyroxyacetic acid was obtained. S3. Preparation of formulations Methyl oleate was added to the preparation vessel, followed by methyl oleate emulsifier, silica, and organobentonite. Then, sodium nicosulfuron, potassium triclopyralid, and chlorpyrifos technical grade were added and stirred until homogeneous. Subsequently, the composition was sand-milled to prepare a 20% nicosulfuron·triclopyralid·chlorpyrifos dispersible oil suspension.

[0023] Example 4: 50% Triclopyralid·Nicosulfuron·Clopyrimazole Wettable Powder A method for preparing a 50% triclopyralid·nicosulfuron·clopyralid wettable powder, comprising, by mass percentage, the following components: 30% triclopyralid, 12% nicosulfuron, 8% clopyralid, 5% alkyl sulfonate, 3% alkylphenol polyoxyethyl ether sulfonate, 3% separating agent BX, 5% silica, and the balance being light calcium carbonate. The specific steps are as follows: S1. Preparation of sodium nicosulfuron-methyl The technical grade mesotrione was mixed with water to form a mesotrione suspension, and then an aqueous solution of sodium hydroxide was added dropwise. The sodium hydroxide solution contained 25% sodium hydroxide by mass. The mixture was then stirred at 55°C until the reaction was complete. When the reaction was complete, the pH of the reaction system was 8.0-9.5, and the sodium salt of mesotrione was obtained. S2. Preparation of potassium triclopyroxyacetate Triclopyroxyacetic acid technical was mixed with water to form a triclopyroxyacetic acid suspension, and then potassium hydroxide aqueous solution was added dropwise. The potassium hydroxide solution contained 25% potassium hydroxide by mass. The mixture was then stirred at 55°C until the reaction was complete. When the reaction was complete, the pH of the reaction system was 8.0-9.5, and potassium triclopyroxyacetic acid salt was obtained. S3. Preparation of formulations Sodium nicosulfuron, potassium triclopyralid, and chlorpyrifos technical grade were mixed together, and alkyl sulfonates, alkylphenol polyoxyethyl ether sulfonates, BX splitting powder, light calcium carbonate, and fumed silica were added and mixed evenly. The composition was then air-jet pulverized to prepare a 50% nicosulfuron·triclopyralid·chlorpyrifos wettable powder.

[0024] Example 5 Herbicide Performance Test The basic performance tests of the 28.5% triclopyralid·nicosulfuron·chlorpyrifos wettable powder prepared in Example 1 were carried out, including appearance, wetting time, heat storage stability, persistent foaming (after 1 min), fineness, and content and suspension rate of each active ingredient under normal temperature and heat storage conditions. The results are shown in Table 1. Table 1 also includes standard indicators as a control.

[0025] The following methods were used to determine the following properties: suspension rate, pH value, moisture content, wetting time, sustained foaming ability, and thermal storage stability: 1. The determination of suspension rate shall be in accordance with GB / T 14825-2023; 2. pH value determination shall be performed in accordance with GB / T 1601-2023; 3. Moisture determination shall be performed according to the Karl Fischer method in GB / T 1600-2021; 4. Wetting time should refer to GB / T 5451-2001; 5. The determination of persistent foaming properties shall be performed in accordance with GB / T 28137-2011; 6. Fineness conforms to GB / T 16150-2025; 7. Thermal storage stability was determined according to the method for "Liquid Preparations, Powder Preparations and Granular Preparations" in GB / T 19136-2003: The sample was placed in a sealed glass bottle and stored in a constant temperature incubator at 54±2℃ for 14 days. Afterward, it was removed, placed in a desiccator, and cooled to room temperature. The mass fraction of the active ingredient and other test indicators were determined within 24 hours. The results are shown in Table 1.

[0026]

[0027] As shown in Table 1, after 14 days of heat storage at room temperature and 54±2℃, the content of the active ingredients of nicosulfuron, triclopyralid, and chlorpyrifos showed no significant fluctuations, indicating that the active ingredients of the formulation of this invention have good stability and have solved the technical problem of easy decomposition of the three components when combined. The suspension rates of the three active ingredients at both room temperature and after heat storage far exceeded the control standard of ≥70%. The suspension rates of mesotrione and triclopyralid both reached 99%, while clopyralid still reached 80% after heat storage. This indicates that the formulation of this invention has good dispersibility in water, can evenly cover the surface of weeds, and ensures weed control efficacy. The wetting time at room temperature is 36 seconds and after heat storage is 35 seconds, indicating that the formulation of this invention can dissolve quickly when it comes into contact with water, making it convenient for field dilution and use without the need for long-term stirring.

[0028] The moisture content at room temperature is 1.0%, and the moisture content during heat storage is 0.8%, indicating that the preparation of the present invention is dry and loose, does not easily absorb moisture and clump, and is conducive to long-term storage.

[0029] The sustained foaming properties (after 1 minute) are 25 mL at room temperature and 24 mL at heat storage, which is lower than the standard of 60 mL. This indicates that the formulation of the present invention does not cause excessive foam interference when sprayed, and can ensure the uniformity of spraying.

[0030] The proportion of particles passing through a 75μm sieve reaches 98%, which meets the standard requirements and the particles are fine; at room temperature and after heat storage, they are uniform and loose powders without lumps and have stable physical state.

[0031] In summary, the 28.5% nicosulfuron-triclopyralid-chlorpyrifos wettable powder of the present invention exhibits excellent stability of active ingredients, dispersion and wetting properties, physical state, and storage stability. It solves the problems of poor stability and inconvenience of use in existing compound formulations and has good application prospects.

[0032] Example 6 Field efficacy trial 6.1 Test reagents The pharmaceutical preparations in Examples 1, 2, and 3 Control agent 1: 45% triclopyralid EC (Sichuan Lier Crop Science) + 10% nicosulfuron-methyl SC (Shandong Binnong Technology) + 75% chlorpyrifos WP (Anhui Fengle Agricultural Chemicals) Control 2: 81% Atrazine wettable powder (Jinan Tianbang Chemical) 6.2 Test Crops The sugarcane is growing well and is free from other diseases and pests.

[0033] 6.3 Target of Prevention and Control Crabapple, Bermuda grass, Five-clawed golden dragon, Cyperus rotundus 5.4 Test Methods The small-area random sampling method was used, with each treatment agent tested over an area of ​​100m². 2 Five random sampling points (1 square meter each) were selected from each plot to observe the growth of weeds and sugarcane. All herbicides were accurately weighed, diluted with water, and then sprayed evenly using a backpack sprayer with a fan-shaped nozzle specifically designed for herbicides. A control group was established by spraying with water. Weed mortality was observed at 10 and 20 days post-application to compare the herbicidal activity of each herbicide; the results are shown in Tables 2 and 3. Crop growth was also observed for 1-20 days to assess any potential phytotoxicity; the results are shown in Table 4.

[0034] Fresh weight control efficacy (%) = (fresh weight of weeds in blank control area - fresh weight of weeds in treatment area) ÷ fresh weight of weeds in blank control area; Plant height inhibition rate (%) = (plant height of sugarcane after manual weeding - plant height of sugarcane in the treatment area) ÷ plant height of sugarcane after manual weeding; As shown in Tables 2 and 3, the herbicide compositions of Examples 1-3 are effective in controlling grassy and broadleaf weeds. In addition, due to the synergistic effect of different components, the overall control effect can be improved. The efficacy is faster and the difference in efficacy is not significant after 10 days and 20 days of application. The weed control effect is significantly better than that of control agent 1 and control agent 2. Example 1 is preferred.

[0035] As shown in Tables 2 and 3, the herbicide compositions of Examples 1-3 are effective in controlling grassy and broadleaf weeds. In addition, due to the synergistic effect of different components, the overall control effect can be improved. The efficacy is faster and the difference in efficacy is not significant after 10 days and 20 days of application. The weed control effect is significantly better than that of control agent 1 and control agent 2. Example 1 is preferred.

[0036]

[0037] As shown in Table 4, the sugarcane in each plot of Examples 1-3 grew well and no pesticide spots were observed, indicating that each pesticide is safe for sugarcane.

[0038] The foregoing description of specific exemplary embodiments of the invention is for illustrative and explanatory purposes. These descriptions are not intended to limit the invention to the precise forms disclosed, and it will be apparent that many changes and variations can be made in accordance with the foregoing teachings. The exemplary embodiments were chosen and described in order to explain the specific principles of the invention and its practical application, thereby enabling those skilled in the art to implement and utilize various different exemplary embodiments of the invention, as well as various different choices and variations. The scope of the invention is intended to be defined by the claims and their equivalents.

Claims

1. A method for preparing a sugarcane herbicide, characterized in that, Includes the following steps: S1. Preparation of nicosulfuron salt An alkaline solution was added dropwise to a nicosulfuron suspension, and the reaction was stirred until complete to obtain nicosulfuron salt. S2. Preparation of triclopyroxyacetic acid salt An alkaline solution was added dropwise to a suspension of triclopyroxyacetic acid, and the reaction was allowed to proceed until complete with stirring to obtain triclopyroxyacetic acid salt. S3. Preparation of pesticide formulations Pesticide formulations are prepared by adding pesticide-permitted auxiliary ingredients to nicotinamide salt, triclopyralid, and chlorpyrifos technical grade pesticides, and then using appropriate equipment and processes.

2. The method for preparing the sugarcane herbicide according to claim 1, characterized in that, Step S1 specifically involves preparing a 20-60% nicosulfuron suspension using deionized water; then adding a 20-30% sodium hydroxide aqueous solution dropwise to the nicosulfuron suspension, stirring at 50-80°C until the reaction is complete, thereby obtaining the sodium nicosulfuron salt.

3. The method for preparing the sugarcane herbicide according to claim 2, characterized in that, After the reaction is complete, the pH value of the reaction system is 6.0-9.5; the molar ratio of nicosulfuron to sodium hydroxide is 1:0.95-1.

05.

4. The method for preparing the sugarcane herbicide according to claim 1, characterized in that, Step S2 specifically involves preparing a 10-40% triclopyroxyacetic acid suspension using deionized water, then adding a 20-30% potassium hydroxide aqueous solution dropwise to the triclopyroxyacetic acid suspension, stirring at 50-80°C until the reaction is complete, thereby obtaining the potassium triclopyroxyacetic acid salt.

5. The method for preparing the sugarcane herbicide according to claim 4, characterized in that, After the reaction is complete, the pH value of the reaction system is 6.0-9.5; the molar ratio of trichloropyroxyacetic acid to potassium hydroxide is 1:0.95-1.

05.

6. The method for preparing the sugarcane herbicide according to claim 1, characterized in that, In step S3, the pesticide-permitted auxiliary ingredients are selected from at least one of sodium lignosulfonate, NNO, alkyl sulfonates, alkylphenol polyoxyethyl ether sulfonates, pull-apart powder BX, K12, and Morwet EFW.

7. The method for preparing the sugarcane herbicide according to claim 1, characterized in that, In step S1, nicosulfuron salts include, but are not limited to, nicosulfuron sodium and potassium salts; in step S2, triclopyroxyacetic acid salts include, but are not limited to, triclopyroxyacetic acid potassium and sodium salts.

8. The method for preparing the sugarcane herbicide according to claim 1, characterized in that, In step S3, the technical grade pesticides of nicosulfuron, triclopyralid, and chlorpyrifos account for 2-40%, 5-45%, and 1-20% of the total mass of the pesticide formulation, respectively, with preferred proportions of 5-30%, 10-45%, and 2-12%.

9. The method for preparing the sugarcane herbicide according to claim 1, characterized in that, In step S3, the pesticide formulation includes, but is not limited to, wettable powders, aqueous suspensions, dispersible oil suspensions, water-dispersible granules, dry suspensions, and soluble concentrates.

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