Surfactitin derivative as well as preparation method and application thereof

Abstract

The invention provides a surfactin derivative, which discovers that the application activity of surfactin in the field of agricultural planting is improved in a breakthrough manner after the surfactin is esterified by C1-C8 alcohol for the first time. The derivative can significantly promote the growth and development of crops and improve the quality of agricultural products (for example, the content of sugar, protein and the like), meanwhile, the crop yield is greatly increased, the comprehensive application effect is far better than that of natural surfactin, and an efficient novel biostimulant functional product is provided for agricultural quality improvement and yield increase.

Description

Technical Field

[0001] This application relates to the fields of biochemical and agricultural technology, specifically to surfactant derivatives, their preparation methods and applications. Background Technology

[0002] Surfactin is a lipopeptide biosurfactant produced by Bacillus, known for its excellent surface activity, antibacterial, and antiviral activities. In agriculture, its application is currently mainly limited to its use as a biopesticide or antifungal agent for the control of crop diseases.

[0003] However, natural surfactants are easily and rapidly degraded in the natural environment, resulting in a short duration of effectiveness and limiting their application. More importantly, current research and applications of surfactants mainly focus on their "bactericidal" function, while there are very few reports on their direct and systematic improvement of crop intrinsic quality (such as sugar content and vitamin content) and economic yield (such as single fruit weight and yield per unit area), and the effects are not significant. Summary of the Invention

[0004] Chemical modification of natural bioactive molecules is an effective strategy to enhance their performance and discover new functions. Esterification is a common modification method, but no studies have yet systematically explored the remarkable quality and yield-enhancing effects of surfactants esterified with mono- or diols of specific chain lengths (C1-C8) in agriculture, especially the synergistic effects produced when combined with specific functional components.

[0005] The technical solution of this application is as follows: 1. A surfactant derivative, comprising at least one of the following structures: or or ; Where n=7-9, and R is a C1-C8 alkyl group or a hydroxyl-substituted C1-C8 alkyl group.

[0006] 2. The surfactant derivative according to claim 1, wherein, C1-C8 alkyl groups are selected from any one of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl.

[0007] 3. The surfactant derivative according to claim 1, wherein the surfactant derivative is formed by esterification of the carboxyl group of a surfactant with a hydroxyl group in a C1-C8 monohydric alcohol or a hydroxyl group in a C1-C8 dihydric alcohol.

[0008] 4. The surfactant derivative according to item 3, wherein, The C1-C8 monohydric alcohol is selected from any one of methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, and octanol; preferably, it is any one of methanol, ethanol, and propanol.

[0009] 5. The surfactant derivative according to item 3, characterized in that the C1-C8 diol is selected from any one of ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, dipropylene glycol, and neopentyl glycol.

[0010] 6. A method for preparing a surfactant derivative as described in any one of items 1-5, comprising esterifying a surfactant with a C1-C8 monohydric alcohol or a C1-C8 dihydric alcohol.

[0011] 7. The application of the surfactant derivatives described in any one of items 1-5 or the surfactant derivatives prepared by the method of claim 6 as biostimulants or fertilizers for grain or livestock crops, vegetable crops, fruit crops or flower crops; Preferably, the grain or livestock crop is any one of wheat, rice, upland rice, corn, oats, rye, barley, buckwheat, millet, sorghum, highland barley, wild rice, taro, Job's tears, sugarcane, sugar beet, sweet potato, oat grass, ice grass, sand grass, sheep grass, crested wheat grass, barley grass, new wheat grass, bermudagrass, three-awn grass, double flower grass, blue stem grass, bullwhit grass, alfalfa, and hollow cogon grass; The vegetable crops mentioned are any one of the following: beetroot, turnip, burdock, eggplant, potato, tomato, pepper, lettuce, bok choy, Chinese cabbage, radish, rapeseed, spinach, celery, cucumber, loofah, bitter melon, pumpkin, winter melon, watermelon, cantaloupe, honeydew melon, perilla, catnip, mint, and okra; The fruit crop is any one of the following: strawberry, blueberry, raspberry, cranberry, cherry, peach, plum, jujube, apple, pear, citrus, orange, grapefruit, bayberry, and banana; The flowering plants mentioned are any one of the following: carnation, calla lily, clivia, monstera, rose, chrysanthemum, peony, honeysuckle, magnolia, jasmine lily, and daylily.

[0012] 8. A composition comprising any of the surfactant derivatives described in items 1-5 or the surfactant derivative prepared by the method described in item 6, and at least one of the following functional components: glutamic acid, methionine, cysteine, urea, potassium dihydrogen phosphate, and dipotassium hydrogen phosphate. Preferably, the composition further comprises an agriculturally acceptable carrier and adjuvants; More preferably, the carrier is selected from one or more of liquid carriers and solid carriers; The additives are selected from one or more of the following: solvents, carriers, surfactants, adhesives, antifreeze, thickeners, buffers, defoamers, antioxidants, preservatives, fragrances, and colorants.

[0013] 9. The composition according to claim 8, wherein the composition is formulated as a wettable powder, a water-dispersible granule, an emulsifiable concentrate, or a liquid.

[0014] 10. The composition according to claim 8, wherein the composition is applied to the target crop by means of seed coating, seed soaking, drip irrigation, root irrigation or foliar spraying.

[0015] Compared with the prior art, this application has the following technical effects. Breakthrough in activity: For the first time, it was discovered that after C1-C8 alcohol esterification, the activity of surfactants improved in quality and yield, resulting in a qualitative leap, with effects far exceeding those of natural surfactants.

[0016] The structure-activity relationship is clear: it reveals the unique advantages of C1-C8 monohydric alcohol esters in increasing yield and provides clear scientific guidance for product development.

[0017] Green and safe: It is mainly composed of biological components, has good environmental compatibility, and meets the requirements of green development in modern agriculture. Attached Figure Description

[0018] Figure 1 The mass spectrometry (MS) spectrum of the surfactant-ethyl ester prepared in Example 1 is shown.

[0019] Figure 2 The mass spectrum (MS) of the surfactant-hexyl ester prepared in Example 6 is shown. Detailed Implementation

[0020] This application provides a surfactant derivative, which has at least one of the following structures: or or ; Where n=7-9, and R is a C1-C8 alkyl group or a hydroxyl-substituted C1-C8 alkyl group.

[0021] In some embodiments of this application, n is 7, 8, or 9.

[0022] In some embodiments of this application, the C1-C8 alkyl group is selected from any one of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl.

[0023] C1-C8 alkyl groups are selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, straight-chain or branched pentyl, straight-chain or branched hexyl, straight-chain or branched heptyl, and straight-chain or branched octyl.

[0024] The term "propyl" includes 1-propyl or n-propyl ("n-Pr"), 2-propyl or isopropyl ("i-Pr").

[0025] The term “butyl” includes, but is not limited to, 1-butyl or n-butyl (“n-Bu”), 2-methyl-1-propyl or isobutyl (“i-Bu”), 1-methylpropyl or sec-butyl (“s-Bu”), and 1,1-dimethylethyl or tert-butyl (“t-Bu”).

[0026] The term "pentyl" includes, but is not limited to, 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 3-methyl-1-butyl, and 2-methyl-1-butyl.

[0027] The term "hexyl" includes, but is not limited to, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 3-methyl-3-pentyl, 2-methyl-3-pentyl, 2,3-dimethyl-2-butyl and 3,3-dimethyl-2-butyl.

[0028] The term "heptyl" includes, but is not limited to, n-heptyl, 2-methylhexyl, 5-methylhexyl, 1-ethylpentyl, 3-methylhexyl, etc.

[0029] The term "octyl" includes, but is not limited to, n-octyl, 1-methylheptyl, 1-ethylhexyl, and 1-propylpentyl.

[0030] In some embodiments of this application, the surfactant derivative is formed by esterification of the carboxyl group of surfactant with a hydroxyl group in a C1-C8 monohydric alcohol or a hydroxyl group in a C1-C8 dihydric alcohol.

[0031] In some embodiments of this application, the C1-C8 monohydric alcohol is selected from any one of methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, and octanol; preferably, it is any one of methanol, ethanol, and propanol.

[0032] In some embodiments of this application, after methanol undergoes an esterification reaction with a surfactant, the resulting R is a methyl group.

[0033] In some embodiments of this application, after ethanol undergoes an esterification reaction with a surfactant, the resulting R is an ethyl group.

[0034] In some embodiments of this application, after propanol undergoes an esterification reaction with a surfactant, the resulting R is propyl.

[0035] In some embodiments of this application, the R formed after butanol undergoes an esterification reaction with a surfactant is a butyl group.

[0036] In some embodiments of this application, after pentanol undergoes an esterification reaction with a surfactant, the resulting R is an pentyl group.

[0037] In some embodiments of this application, after hexanol undergoes an esterification reaction with a surfactant, the resulting R is a hexyl group.

[0038] In some embodiments of this application, after heptanol undergoes an esterification reaction with a surfactant, the resulting R is a heptanyl group.

[0039] In some embodiments of this application, after octanol undergoes an esterification reaction with surfactant, the resulting R is an octyl group.

[0040] In some embodiments of this application, the C1-C8 diol is selected from any one of ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, dipropylene glycol, and neopentyl glycol.

[0041] This application provides a method for preparing the above-mentioned surfactant derivative, which includes esterification of the surfactant with a C1-C8 monohydric alcohol or a C1-C8 dihydric alcohol.

[0042] In some embodiments of this application, the method for preparing the derivative includes the following steps: Surfactants are reacted with C1-C8 monohydric or dihydric alcohols in an organic solvent in the presence of a condensing agent and a catalyst. The reaction temperature is 0-50℃ and the reaction time is 1-48 hours. After the reaction is completed, the target esterified product is obtained by quenching, extraction, drying, concentration and purification.

[0043] In some embodiments of this application, the condensing agent is DCC (dicyclohexylcarbodiimide), EDC (1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride), etc.

[0044] In some embodiments of this application, the catalyst is DMAP (4-dimethylaminopyridine) or the like.

[0045] In some embodiments of this application, a surfactant, a C1-C8 monohydric alcohol, or a C1-C8 dihydric alcohol is added and dissolved in anhydrous dichloromethane. EDC·HCl and DMAP are added sequentially at room temperature. The reaction is stirred for 12 hours. After the reaction is complete as monitored by TLC, the reaction solution is washed with dilute hydrochloric acid, the organic phase is dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The residue is purified by silica gel column chromatography to obtain the surfactant derivative.

[0046] This application provides the use of the above-mentioned surfactant derivatives as crop biostimulants or fertilizers.

[0047] This application provides the use of the above-mentioned surfactant derivatives as biostimulants or fertilizers for grain or livestock crops, vegetable crops, fruit crops or flower crops.

[0048] In some embodiments of this application, the grain or livestock crop is any one of wheat, rice, upland rice, corn, oats, rye, barley, buckwheat, millet, sorghum, highland barley, wild rice, taro, Job's tears, sugarcane, sugar beet, sweet potato, oat grass, ice grass, sand grass, sheep grass, crested wheatgrass, barley grass, new wheatgrass, bermudagrass, three-awn grass, double flower grass, blue stem grass, bullwhip grass, alfalfa, and hollow cogon grass.

[0049] In some embodiments of this application, the vegetable crop is any one of the following: beetroot, turnip, burdock, eggplant, potato, tomato, pepper, lettuce, bok choy, Chinese cabbage, radish, rapeseed, spinach, celery, cucumber, loofah, bitter melon, pumpkin, winter melon, watermelon, cantaloupe, honeydew melon, perilla, catnip, mint, and okra.

[0050] In some embodiments of this application, the fruit crop is any one of strawberry, blueberry, raspberry, cranberry, cherry, peach, plum, jujube, apple, pear, citrus, orange, grapefruit, bayberry and banana.

[0051] In some embodiments of this application, the flowering crop is any one of carnation, calla lily, clivia, monstera, rose, chrysanthemum, peony, honeysuckle, magnolia, jasmine lily, and daylily.

[0052] This application provides a composition comprising the above-mentioned surfactant derivatives and at least one of the following functional components: glutamic acid, methionine, cysteine, urea, potassium dihydrogen phosphate, and dipotassium hydrogen phosphate.

[0053] In some embodiments of this application, a certain concentration of aqueous solution of surfactant ester derivatives is first prepared, and then mixed with 0.01-99.99% by weight of one or more functional ingredients such as cellulose, chitosan, glutamic acid, methionine, cysteine, silicon dioxide, urea, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, polyethylene glycol, xanthan gum, starch, and dodecyl sulfonate. After combination and compounding, the resulting pesticide adjuvant can be used directly as an agricultural fertilizer or pesticide. Simultaneously, the above composition can also be applied directly as a powder mixture.

[0054] In some embodiments of this application, the composition further comprises an agriculturally acceptable carrier and adjuvants; Preferably, the carrier is selected from one or more of liquid carriers and solid carriers; The additives are selected from one or more of the following: solvents, carriers, surfactants, adhesives, antifreeze, thickeners, buffers, defoamers, antioxidants, preservatives, fragrances, and colorants.

[0055] As used herein, "agriculturally acceptable carrier" refers to an agronomically acceptable solvent, suspending agent, or excipient used for the delivery of surfactant derivatives of this application to plants. The carrier may be liquid or solid. Agriculturally acceptable carriers suitable for this application are selected from the group consisting of water, buffer solutions, DMSO, surfactants such as Tween-20, or combinations thereof. Any agriculturally acceptable carrier known to those skilled in the art may be used in this application.

[0056] As used herein, “agriculturally acceptable adjuvants” refers to solvents, carriers, surfactants, adhesives, antifreeze agents, thickeners, buffers, defoamers, antioxidants, preservatives, fragrances, colorants, and combinations thereof.

[0057] In some embodiments of this application, the composition is formulated as a wettable powder, a water-dispersible granule, an emulsion, or a liquid.

[0058] In some embodiments of this application, the composition is applied to the target crop by means of seed coating, seed soaking, drip irrigation, root irrigation, or foliar spraying.

[0059] In some embodiments of this application, the above-mentioned surfactant ester derivatives are used as active ingredients and as agricultural adjuvants to improve crop quality and / or yield.

[0060] In some embodiments of this application, the aforementioned surfactant ester derivatives constitute a part of the agricultural composition as active ingredients. The agricultural composition comprises a compound system of the surfactant ester derivatives with glutamic acid and potassium dihydrogen phosphate. The agricultural composition can be supplemented with agriculturally acceptable carriers or adjuvants (such as dispersants, wetting agents, and emulsifiers) to formulate commonly used dosage forms such as wettable powders, water-dispersible granules, liquids, and emulsifiable concentrates, and applied via foliar spraying, root irrigation, drip irrigation, etc.

[0061] Obtaining surfactants The reference is Wang M, Yu H, Li X, et al. Metabolic Engineering, 2020, 62:235-248. Synthesis. Three compounds of formula (1) were prepared, where n=7~9, and the raw materials of the compounds of formula (1) were obtained from microbial fermentation metabolites.

[0062] Equation (1), where n is 7, 8, or 9.

[0063] Example 1. Formulation containing surfactant derivatives In a round-bottom flask equipped with a stir bar, surfactant (1.0 mmol) and ethanol (2 mmol) were added and dissolved in anhydrous dichloromethane (20 mL). At room temperature, EDC·HCl (1.2 mmol) and DMAP (0.1 mmol) were added sequentially. The reaction mixture was stirred at 250 rpm for 12 hours. After the reaction was complete as monitored by TLC, the reaction solution was washed with dilute hydrochloric acid, the organic phase was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography to obtain the surfactant derivative.

[0064] Mass spectra (MS) of surfactant derivatives are shown below. Figure 1 .

[0065] Weigh 1.0 g of the above-mentioned surfactant derivative, 3 g of glutamic acid, and 5 g of potassium dihydrogen phosphate, dissolve them in 84 g of deionized water, and stir until completely dissolved to obtain a compound preparation containing 1% ester, 3% glutamic acid, and 5% phosphorus and potassium fertilizer.

[0066] Example 2. Formulation containing surfactant derivatives In a round-bottom flask equipped with a stir bar, surfactant (1.0 mmol) and methanol (2 mmol) were added and dissolved in anhydrous dichloromethane (20 mL). At room temperature, EDC·HCl (1.2 mmol) and DMAP (0.1 mmol) were added sequentially. The reaction mixture was stirred at 250 rpm for 12 hours. After the reaction was complete as monitored by TLC, the reaction solution was washed with dilute hydrochloric acid, the organic phase was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography to obtain the surfactant derivative.

[0067] Weigh 1.0 g of the above-mentioned surfactant derivative, 3 g of glutamic acid, and 5 g of potassium dihydrogen phosphate, dissolve them in 84 g of deionized water, and stir until completely dissolved to obtain a compound preparation containing 1% ester, 3% glutamic acid, and 5% phosphorus and potassium fertilizer.

[0068] Example 3. Formulation containing surfactant derivatives In a round-bottom flask equipped with a stir bar, surfactant (1.0 mmol) and n-propanol (2 mmol) were added and dissolved in anhydrous dichloromethane (20 mL). At room temperature, EDC·HCl (1.2 mmol) and DMAP (0.1 mmol) were added sequentially. The reaction mixture was stirred at 250 rpm for 12 hours. After the reaction was complete as monitored by TLC, the reaction solution was washed with dilute hydrochloric acid, the organic phase was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography to obtain the surfactant derivative.

[0069] Weigh 1.0 g of the above-mentioned surfactant derivative, 3 g of glutamic acid, and 5 g of potassium dihydrogen phosphate, dissolve them in 84 g of deionized water, and stir until completely dissolved to obtain a compound preparation containing 1% ester, 3% glutamic acid, and 5% phosphorus and potassium fertilizer.

[0070] Example 4. Formulation containing surfactant derivatives In a round-bottom flask equipped with a stir bar, surfactant (1.0 mmol) and n-butanol (2 mmol) were added and dissolved in anhydrous dichloromethane (20 mL). At room temperature, EDC·HCl (1.2 mmol) and DMAP (0.1 mmol) were added sequentially. The reaction mixture was stirred at 250 rpm for 12 hours. After the reaction was complete as monitored by TLC, the reaction solution was washed with dilute hydrochloric acid, the organic phase was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography to obtain the surfactant derivative.

[0071] Weigh 1.0 g of the above-mentioned surfactant derivative, 3 g of glutamic acid, and 5 g of potassium dihydrogen phosphate, dissolve them in 84 g of deionized water, and stir until completely dissolved to obtain a compound preparation containing 1% ester, 3% glutamic acid, and 5% phosphorus and potassium fertilizer.

[0072] Example 5. Formulation containing surfactant derivatives In a round-bottom flask equipped with a stir bar, surfactant (1.0 mmol) and n-pentanol (2 mmol) were added and dissolved in anhydrous dichloromethane (20 mL). At room temperature, EDC·HCl (1.2 mmol) and DMAP (0.1 mmol) were added sequentially. The reaction mixture was stirred at 250 rpm for 12 hours. After the reaction was complete as monitored by TLC, the reaction solution was washed with dilute hydrochloric acid, the organic phase was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography to obtain the surfactant derivative.

[0073] Weigh 1.0 g of the above-mentioned surfactant derivative, 3 g of glutamic acid, and 5 g of potassium dihydrogen phosphate, dissolve them in 84 g of deionized water, and stir until completely dissolved to obtain a compound preparation containing 1% ester, 3% glutamic acid, and 5% phosphorus and potassium fertilizer.

[0074] Example 6. Formulation containing surfactant derivatives In a round-bottom flask equipped with a stir bar, surfactant (1.0 mmol) and n-hexanol (2 mmol) were added and dissolved in anhydrous dichloromethane (20 mL). At room temperature, EDC·HCl (1.2 mmol) and DMAP (0.1 mmol) were added sequentially. The reaction mixture was stirred at 250 rpm for 12 hours. After the reaction was complete as monitored by TLC, the reaction solution was washed with dilute hydrochloric acid, the organic phase was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography to obtain the surfactant derivative.

[0075] Mass spectra (MS) of surfactant derivatives are shown below. Figure 2 .

[0076] Weigh 1.0 g of the above-mentioned surfactant derivative, 3 g of glutamic acid, and 5 g of potassium dihydrogen phosphate, dissolve them in 84 g of deionized water, and stir until completely dissolved to obtain a compound preparation containing 1% ester, 3% glutamic acid, and 5% phosphorus and potassium fertilizer.

[0077] Example 7. Formulation containing surfactant derivatives In a round-bottom flask equipped with a stir bar, surfactant (1.0 mmol) and n-heptanol (2 mmol) were added and dissolved in anhydrous dichloromethane (20 mL). At room temperature, EDC·HCl (1.2 mmol) and DMAP (0.1 mmol) were added sequentially. The reaction mixture was stirred at 250 rpm for 12 hours. After the reaction was complete as monitored by TLC, the reaction solution was washed with dilute hydrochloric acid, the organic phase was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography to obtain the surfactant derivative.

[0078] Weigh 1.0 g of the above-mentioned surfactant derivative, 3 g of glutamic acid, and 5 g of potassium dihydrogen phosphate, dissolve them in 84 g of deionized water, and stir until completely dissolved to obtain a compound preparation containing 1% ester, 3% glutamic acid, and 5% phosphorus and potassium fertilizer.

[0079] Example 8. Formulation containing surfactant derivatives In a round-bottom flask equipped with a stir bar, surfactant (1.0 mmol) and n-octanol (2 mmol) were added and dissolved in anhydrous dichloromethane (20 mL). At room temperature, EDC·HCl (1.2 mmol) and DMAP (0.1 mmol) were added sequentially. The reaction mixture was stirred at 250 rpm for 12 hours. After the reaction was complete as monitored by TLC, the reaction solution was washed with dilute hydrochloric acid, the organic phase was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography to obtain the surfactant derivative.

[0080] Weigh 1.0 g of the above-mentioned surfactant derivative, 3 g of glutamic acid, and 5 g of potassium dihydrogen phosphate, dissolve them in 84 g of deionized water, and stir until completely dissolved to obtain a compound preparation containing 1% ester, 3% glutamic acid, and 5% phosphorus and potassium fertilizer.

[0081] Example 9. Formulation containing surfactant derivatives In a round-bottom flask equipped with a stir bar, surfactant (1.0 mmol) and ethylene glycol (2 mmol) were added and dissolved in anhydrous dichloromethane (20 mL). At room temperature, EDC·HCl (1.2 mmol) and DMAP (0.1 mmol) were added sequentially. The reaction mixture was stirred at 250 rpm for 12 hours. After the reaction was complete as monitored by TLC, the reaction solution was washed with dilute hydrochloric acid, the organic phase was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography to obtain the surfactant derivative.

[0082] Weigh 1.0 g of the above-mentioned surfactant derivative, 3 g of glutamic acid, and 5 g of potassium dihydrogen phosphate, dissolve them in 84 g of deionized water, and stir until completely dissolved to obtain a compound preparation containing 1% ester, 3% glutamic acid, and 5% phosphorus and potassium fertilizer.

[0083] Example 10. Formulation containing surfactant derivatives In a round-bottom flask equipped with a stir bar, surfactant (1.0 mmol) and 1,2-propanediol (2 mmol) were added and dissolved in anhydrous dichloromethane (20 mL). At room temperature, EDC·HCl (1.2 mmol) and DMAP (0.1 mmol) were added sequentially. The reaction mixture was stirred at 250 rpm for 12 hours. After the reaction was complete as monitored by TLC, the reaction solution was washed with dilute hydrochloric acid, the organic phase was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography to obtain the surfactant derivative.

[0084] Weigh 1.0 g of the above-mentioned surfactant derivative, 3 g of glutamic acid, and 5 g of potassium dihydrogen phosphate, dissolve them in 84 g of deionized water, and stir until completely dissolved to obtain a compound preparation containing 1% ester, 3% glutamic acid, and 5% phosphorus and potassium fertilizer.

[0085] Example 11. Formulation containing surfactant derivatives In a round-bottom flask equipped with a stir bar, surfactant (1.0 mmol) and 1,3-propanediol (2 mmol) were added and dissolved in anhydrous dichloromethane (20 mL). At room temperature, EDC·HCl (1.2 mmol) and DMAP (0.1 mmol) were added sequentially. The reaction mixture was stirred at 250 rpm for 12 hours. After the reaction was complete as monitored by TLC, the reaction solution was washed with dilute hydrochloric acid, the organic phase was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography to obtain the surfactant derivative.

[0086] Weigh 1.0 g of the above-mentioned surfactant derivative, 3 g of glutamic acid, and 5 g of potassium dihydrogen phosphate, dissolve them in 84 g of deionized water, and stir until completely dissolved to obtain a compound preparation containing 1% ester, 3% glutamic acid, and 5% phosphorus and potassium fertilizer.

[0087] Comparative Example 1. Formulations containing iturobrine derivatives In a round-bottom flask equipped with a stir bar, 1.0 mmol of iturobrine and 1 mmol of methanol were added and dissolved in 20 mL of anhydrous dichloromethane. At room temperature, 1.2 mmol of EDC·HCl and 0.1 mmol of DMAP were added sequentially. The reaction mixture was stirred at 250 rpm for 12 hours. After the reaction was complete as monitored by TLC, the reaction solution was washed with dilute hydrochloric acid, the organic phase was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography to obtain the iturobrine derivative.

[0088] Weigh out 1.0 g of the above-mentioned iturobrine derivative, 3 g of glutamic acid, and 5 g of potassium dihydrogen phosphate, dissolve them in 84 g of deionized water, and stir until completely dissolved to obtain a compound preparation containing 1% ester, 3% glutamic acid, and 5% phosphorus and potassium fertilizer.

[0089] Comparative Example 2. Formulations containing sophorolipid derivatives In a round-bottom flask equipped with a stir bar, sophorolipid (1.0 mmol) and methanol (1 mmol) were added and dissolved in anhydrous dichloromethane (20 mL). At room temperature, EDC·HCl (1.2 mmol) and DMAP (0.1 mmol) were added sequentially. The reaction mixture was stirred at 250 rpm for 12 hours. After the reaction was complete as monitored by TLC, the reaction solution was washed with dilute hydrochloric acid, the organic phase was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography to obtain the sophorolipid derivative.

[0090] Weigh 1.0 g of the above-mentioned sophorolipid derivative, 3 g of glutamic acid, and 5 g of potassium dihydrogen phosphate, dissolve them in 84 g of deionized water, and stir until completely dissolved to obtain a compound preparation containing 1% ester, 3% glutamic acid, and 5% phosphorus and potassium fertilizer.

[0091] Comparative Example 3. Formulations containing carboxylated lignin sulfonate derivatives In a round-bottom flask equipped with a stir bar, carboxylated lignin sulfonate (1.0 mmol) and methanol (1 mmol) were added and dissolved in anhydrous dichloromethane (20 mL). At room temperature, EDC·HCl (1.2 mmol) and DMAP (0.1 mmol) were added sequentially. The reaction mixture was stirred at 250 rpm for 12 hours. After the reaction was complete as monitored by TLC, the reaction solution was washed with dilute hydrochloric acid, the organic phase was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography to obtain the carboxylated lignin sulfonate derivative.

[0092] Weigh 1.0 g of the above carboxylated lignin sulfonate derivative, 3 g of glutamic acid, and 5 g of potassium dihydrogen phosphate, dissolve them in 84 g of deionized water, and stir until completely dissolved to obtain a compound preparation containing 1% ester, 3% glutamic acid, and 5% phosphorus and potassium fertilizer.

[0093] Table 1

[0094] Experiment 1: Used to improve the internal quality of strawberries and promote growth In a typical greenhouse strawberry growing environment, a 10 m... 2 In one planting plot, the surfactant derivative compound agents described in Examples 1-11 and Comparative Examples 1-4 were applied to strawberry plants via foliar spraying. The application was specifically timed during the strawberry flower bud differentiation and full bloom stages to ensure even coverage of the entire plant. The results are shown in Table 2. After practical application, significant effects were observed in both strawberry quality improvement and growth promotion. The surfactant derivative compound agents effectively optimized strawberry quality. Regarding fruit appearance, the number of deformed fruits treated with the compound agents was significantly reduced, with an average decrease of 30%–80% per planting plot. Tests showed that, compared to the control group, the internal quality of the strawberry fruit, such as soluble sugar content (a key indicator of sweetness), increased by 7%–20%; protein content (an important indicator of nutrition), increased by 12%–50%; and pectin content (affecting fruit crispness and shelf life), increased by up to 30% or more.

[0095] The test method for soluble sugar content in Table 2 is the same as that in standard NY / T 2637-2014 "Determination of soluble solids content in fruits and vegetables by refractometer method"; The protein content in Table 2 was tested using the BCA method (diquinoline carboxylic acid method). The test method for pectin content in Table 2 is NY / T 2331-2013 "Determination of Pectin in Fruits and Fruit Products - Carbazole Colorimetric Method"; In addition, deformed fruits are often characterized by overall asymmetry in shape, residual flower parts or multiple petals, and incomplete fruit development.

[0096] Table 2 Comparison of the effects of each treatment group on strawberry quality

[0097] Note: The control group consisted of drugs formulated without the use of surfactant derivatives.

[0098] As shown in Table 2, compared with the control group, the application of the agents in Examples 1-11 significantly reduced the rate of deformed fruit, increased the number of normal fruit, and improved the content of soluble sugar, protein, and pectin in the fruit. Among them, Example 2 (methanol derivative) showed the best effect. With the increase of alcohol chain length (Examples 3 to 8), the effect gradually decreased, but it was still better than the unmodified surfactant (corresponding to Example 4). The effect of diol derivatives on strawberry quality (corresponding to Examples 9 to 11) was also better than the control group, but slightly lower than that of short-chain monohydric alcohol derivatives. In contrast, the application of the agents in Examples 1 to 3 had limited effect.

[0099] Experiment 2 was used to improve pumpkin quality and promote growth. The tested pumpkin varieties were selected from locally grown high-quality varieties. After seedling cultivation, robust seedlings with uniform growth (15-20cm in height and 3-4 true leaves) were selected and transplanted to the field at a row spacing of 2.5 m and a plant spacing of 1.2 m. Conventional field management was implemented (deep plowing, sufficient basal fertilizer application, and basic pest, disease, and weed control). The experiment included 15 treatments (Examples 1-11 and Comparative Examples 1-4), with 3 replicates per group and 30 plants per replicate, arranged in a randomized block design. The control group was irrigated with the same amount of water.

[0100] After transplanting, pumpkin seedlings were allowed to recover naturally for one week (ensuring root recovery and no wilting). The target agent was then applied via root drenching: 200 mL of the surfactant derivative compound from Examples 1-11 and Comparative Examples 1-4 (concentration prepared according to the established formula for each example) was slowly poured into the soil around the plant roots (5-8 cm from the stem base, avoiding direct contact with the stem). The control group was irrigated with 200 mL of water. All treatments were applied simultaneously. The effects of the agent on pumpkin flowering, fruiting, and quality were examined; the results are shown in Tables 3 and 4.

[0101] The calculation method for the earlier appearance of the first female flower in Table 3 is as follows: the number of days earlier the first female flower appears = the time taken for the first female flower to appear in the control group - the time taken for the first female flower to appear in the treatment group. The results are in days, and all are based on the planting date.

[0102] The calculation method for the earlier first fruit time in Table 3 is as follows: the number of days earlier the first fruit time = the time taken for the first fruit in the control group - the time taken for the first fruit in the treatment group. The results are in days, and all are based on the planting date.

[0103] The calculation method for shortening the fruit enlargement cycle in Table 3 is as follows: Number of days the enlargement cycle is shortened = Fruit enlargement cycle of control group - Fruit enlargement cycle of treatment group. The result is in days, and the starting point is the fruit setting day.

[0104] Table 3 Comparison of the effects of each treatment group on pumpkin quality

[0105] Note: The control group consisted of drugs formulated without the use of surfactant derivatives.

[0106] Table 3 shows that all treatment groups in Examples 1-11 significantly promoted the reproductive growth process of pumpkin. Compared with the control group, the first appearance of female flowers was advanced by 2 to 6 days, the first fruit ripening was advanced by 8 to 14 days, and the fruit enlargement period was shortened by 5 to 8 days. This indicates that the derivative described in this application can effectively shorten the growth cycle of pumpkin, enabling earlier market entry. After ripening, quality testing was conducted.

[0107] The test method for soluble sugar content in Table 4 is the same as that in standard NY / T 2637-2014 "Determination of soluble solids content in fruits and vegetables by refractometer method"; The test methods for carotenoid content in Table 4 are as described in GH / T 1386—2022 "Determination of Lutein, Zeaxanthin, Cryptoxanthin and Carotene in Fruits and Vegetables". The test methods for the amino acid content in Table 4 are as described in GB / T 30987-2020 "Determination of Free Amino Acids in Plants".

[0108] Table 4. Results of quality testing of mature pumpkin fruits in each group

[0109] Note: The control group consisted of drugs formulated without the use of surfactant derivatives.

[0110] Table 4 shows that the single fruit weight, soluble sugar, carotenoid and amino acid content of fruits treated with the preparations of Examples 1-11 were significantly increased.

[0111] Experiment 3 was used to improve sorghum quality and promote growth. A randomized block design was adopted, with treatment and control groups set up. The plants were medium-stemmed varieties, planted at a density of 6,000 plants / mu, and other field management (fertilization, irrigation, weeding) were the same.

[0112] Treatment group: When sorghum embryos emerge from the soil (7 days after sowing, seedling height 3-5cm), the roots are irrigated with a diluted solution of surfactant derivative compound from Examples 1-11 and Comparative Examples 1-4 (500 times concentration), at a rate of 20 L per acre, applied only once. Control group: The roots are irrigated with the same amount of water at the same time, and other conditions are completely consistent with the treatment group. At 32 days and 55 days after treatment, the differentiation of young sorghum panicles in both groups is observed and recorded (the differentiation is judged by whether a trumpet-shaped morphology appears). After maturity, 5 quadrats are randomly selected from each plot, and 4 plants are selected from each quadrat, for a total of 20 plants. Plant height (height from ground surface to panicle top), stem diameter (diameter of the middle stem of the third segment above ground, measured with vernier calipers), and panicle length (length from panicle base to panicle tip) are measured, and the average values ​​are calculated.

[0113] The results observed 32 days after the treatment showed that in the control group, about 88% of the young spikelets were undifferentiated and had no trumpet-shaped morphology, and were still in the vegetative growth stage; in Examples 1-11, about 86% of the young spikelets of the plants completed differentiation, and the trumpet-shaped structure could be clearly observed with the naked eye, indicating that the surfactant derivative stimulant can significantly accelerate the initiation of reproductive growth of sorghum and advance the time of young spikelet differentiation. 2. Effects on agronomic traits of sorghum The data on agronomic traits measured at harvest are shown in Table 5 below: Table 5. Effects of surfactant derivatives on agronomic morphology of sorghum.

[0114] Note: The control group consisted of drugs formulated without the use of surfactant derivatives.

[0115] Table 5 shows that, compared with the control group, the treatment groups treated with the formulations from Examples 1-11 all showed significant improvements in three key agronomic traits: plant height, stem diameter, and ear length. This demonstrates that the formulations of this application can effectively optimize sorghum plant morphology, enhance stem support capacity, and provide more ample ear space for grain development, thus laying the foundation for yield improvement.

[0116] Meanwhile, after the sorghum harvest, sorghum grains from each plot were collected, dried (at 60℃ for 48 hours), and pulverized (through an 80-mesh sieve). The quality of the sorghum grains in each group was then measured, as shown in Table 6. The test method for anthocyanin content in Table 6 is NY / T 2640-2014 "Determination of anthocyanins in plant-derived foods by high performance liquid chromatography". The test methods for vitamin B3 content in Table 6 are as specified in GB 5009.89-2023 "National Food Safety Standard - Determination of Niacin and Nicotinamide in Food"; The protein content in Table 6 is tested using the BCA method (diquinoline carboxylic acid method).

[0117] Table 6 Results of sorghum grain quality testing for each group

[0118] Note: The control group consisted of drugs formulated without the use of surfactant derivatives.

[0119] After harvest, the quality of sorghum grains in each group was tested. Table 6 shows that the anthocyanin, vitamin B3, and protein content in the grains of the treatment groups treated with the formulations from Examples 1-11 were significantly higher than those in the control group. This indicates that the adjuvant can effectively improve the nutritional quality and commercial value of sorghum while promoting growth.

[0120] In summary, the surfactant derivatives provided by this invention, as pesticide adjuvants, exhibit excellent growth-promoting and quality-enhancing effects on a variety of crops. Their effects are significantly superior to unmodified surfactants and several other commonly used surfactants. Data shows that by modifying surfactants with short-chain alcohol esterification (especially ethanol and methanol), their bioactivity can be maximized, which is of great significance for the development of novel, highly efficient, and green pesticide adjuvants.

[0121] Although this case has been disclosed above with examples and comparative examples, it is not intended to limit the scope of this case. Anyone skilled in the art can make some modifications and refinements without departing from the spirit and scope of this case. The scope of protection of this patent is not limited to the core technical solution, but also includes the technical solutions corresponding to the comparative examples disclosed herein. All implementation methods (including comparative examples) based on the technical concept of this invention are included in the protection scope. The final scope of protection shall be determined by the scope of the appended patent application.

Claims

1. A surfactant derivative, comprising at least one of the following structures: or or ; in, n=7-9, R is a C1-C8 alkyl group or a hydroxyl-substituted C1-C8 alkyl group.

2. The surfactant derivative according to claim 1, wherein, C1-C8 alkyl groups are selected from any one of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl.

3. The surfactant derivative according to claim 1, wherein, The surfactant derivative is formed by esterification of the carboxyl group of surfactant with the hydroxyl group in a C1-C8 monohydric alcohol or a C1-C8 dihydric alcohol.

4. The surfactant derivative according to claim 3, wherein, The C1-C8 monohydric alcohol is selected from any one of methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, and octanol; preferably, it is selected from any one of methanol, ethanol, and propanol.

5. The surfactant derivative according to claim 3, characterized in that, The C1-C8 diols are selected from any one of ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, dipropylene glycol, and neopentyl glycol.

6. A method for preparing a surfactant derivative as described in any one of claims 1-5, comprising esterifying a surfactant with a C1-C8 monohydric alcohol or a C1-C8 dihydric alcohol.

7. The application of the surfactant derivative as described in any one of claims 1-5 or the surfactant derivative prepared by the method described in claim 6 as a biostimulant or fertilizer for grain or livestock crops, vegetable crops, fruit crops or flower crops; Preferably, the grain or livestock crop is any one of wheat, rice, upland rice, corn, oats, rye, barley, buckwheat, millet, sorghum, highland barley, wild rice, taro, Job's tears, sugarcane, sugar beet, sweet potato, oat grass, ice grass, sand grass, sheep grass, crested wheat grass, barley grass, new wheat grass, bermudagrass, three-awn grass, double flower grass, blue stem grass, bullwhit grass, alfalfa, and hollow cogon grass; The vegetable crops mentioned are any one of the following: beetroot, turnip, burdock, eggplant, potato, tomato, pepper, lettuce, bok choy, Chinese cabbage, radish, rapeseed, spinach, celery, cucumber, loofah, bitter melon, pumpkin, winter melon, watermelon, cantaloupe, honeydew melon, perilla, catnip, mint, and okra; The fruit crop is any one of the following: strawberry, blueberry, raspberry, cranberry, cherry, peach, plum, jujube, apple, pear, citrus, orange, grapefruit, bayberry, and banana; The flowering plants mentioned are any one of the following: carnation, calla lily, clivia, monstera, rose, chrysanthemum, peony, honeysuckle, magnolia, jasmine lily, and daylily.

8. A composition comprising a surfactant derivative according to any one of claims 1-5 or a surfactant derivative prepared by the method of claim 6, and at least one of the following functional components: glutamic acid, methionine, cysteine, urea, potassium dihydrogen phosphate, and dipotassium hydrogen phosphate. Preferably, the composition further comprises an agriculturally acceptable carrier and adjuvants; More preferably, the carrier is selected from one or more of liquid carriers and solid carriers; The additives are selected from one or more of the following: solvents, carriers, surfactants, adhesives, antifreeze, thickeners, buffers, defoamers, antioxidants, preservatives, fragrances, and colorants.

9. The composition according to claim 8, wherein, The composition is formulated as a wettable powder, a water-dispersible granule, an emulsifiable concentrate, or a liquid.

10. The composition according to claim 8, wherein, The composition is applied to the target crop by means of seed coating, seed soaking, drip irrigation, root irrigation or foliar spraying.

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