Pesticide residue scavenger and preparation method thereof

Abstract

The invention discloses a pesticide residue scavenging agent. The feed additive is prepared from the following components in parts by weight: 90-110 parts of white hyacinth beans, 9-11 parts of papain, 90-110 parts of liquorice, 45-55 parts of folium isatidis, 25-35 parts of perilla leaves, 25-35 parts of fructus forsythiae, 25-35 parts of honeysuckle, 15-25 parts of rhizoma smilacis glabrae, 15-25 parts of ginkgo leaves, 4-6 parts of soybean protease, 9-11 parts of glutathione, 9-11 parts of amylase, 7-9 parts of walnut peptide, 1-3 parts of chitosan oligosaccharide, 0.5-1 part of sodium citrate and 1-3 parts of alkyl glycoside. The invention has the following prominent effects: the harm to crops is reduced, so that the heavy metal pollution generated after the chemical pesticide is used is solved; the problems of damage to crops and pollution to fruits caused by residues such as pesticides and harmful substances such as environment, chemical agents and biological agents can be effectively solved; the pesticide residue scavenger is a natural pesticide residue scavenger, and is simple in use method, easy to operate and low in cost.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of agricultural biochemistry, in particular to a pesticide residue removing agent and a preparation method thereof. BACKGROUND

[0002] Pesticide residues refer to the micro amount of pesticide original body, toxic metabolites, degradation products and impurities remaining in organisms, agricultural products and the environment after the use of pesticides. These residues remain in the environment for varying lengths of time and vary in residual amount. Pesticide residues not only directly affect the quality of agricultural products, but also directly relate to the health of consumers.

[0003] After the use of chemical pesticides, their residues can cause heavy metal pollution and harmful substance residues, which pollute and harm crops and fruits. The existing pesticide residue removing products are mainly used for cleaning pesticide residues on fruits, but cannot solve the problem of non-point source pollution caused by pesticide residues on leaf surfaces, such as pollution problems of tea, leafy vegetables and other crops; at the same time, it is difficult to efficiently remove heavy metal ions, or may cause damage to crops after use.

[0004] A pesticide residue removing agent and a preparation method thereof are disclosed in Chinese patent application publication No. CN119570578A, which is the technical solution invented by the applicant. The technical solution can solve the problem of pollution of harmful substances such as heavy metals and chemical pesticide residues on the leaf surface of crops. However, because amino oligosaccharide is added in the formula, and amino oligosaccharide is used as a biological pesticide preparation, the safety of the technical solution is uncertain. Although amino oligosaccharide has no obvious toxicity to the environment, crops and mammals at an appropriate dose in reality, and is safe, in order to eliminate the concerns of consumers, the above technical solution also needs to be improved. SUMMARY

[0005] The first object of the present application is to provide a pesticide residue removing agent for removing the damage of harmful substances and other residues to crops and the pollution of fruits, especially for removing heavy metal pollution and organic pollution of fruits caused by the use of chemical pesticides, in view of the deficiencies of the prior art described above.

[0006] Another object of the present application is to provide a preparation method of the pesticide residue removing agent.

[0007] To achieve the above objectives, the present invention is implemented as follows: a pesticide residue remover, comprising the following components in parts by weight: 90-110 parts white hyacinth bean, 9-11 parts papain, 90-110 parts licorice, 45-55 parts indigo leaf, 25-35 parts perilla leaf, 25-35 parts forsythia, 25-35 parts honeysuckle, 15-25 parts smilax glabra, 15-25 parts ginkgo leaf, 4-6 parts soybean protease, 9-11 parts glutathione, 9-11 parts amylase, 7-9 parts jujube peptide, 1-3 parts chitosan oligosaccharide, 0.5-1 part sodium citrate, and 1-3 parts alkyl glycoside.

[0008] Preferably, the pesticide residue remover is made from the following components in parts by weight: 100 parts white hyacinth bean, 10 parts papain, 100 parts licorice, 50 parts indigo leaf, 30 parts perilla leaf, 30 parts forsythia, 30 parts honeysuckle, 20 parts smilax glabra, 20 parts ginkgo leaf, 5 parts soybean protease, 10 parts glutathione (GSH), 10 parts amylase, 8 parts walnut peptide, 2 parts chitosan oligosaccharide, 0.8 parts sodium citrate, and 1 part alkyl glycoside (APG).

[0009] The preferred amylase is product number BF7658 from Xingtai Wanda Biotechnology Co., Ltd.

[0010] The walnut peptide mentioned is also known as walnut peptide, preferably the walnut peptide from Shenzhen Jinfuyuan Biotechnology Co., Ltd. or the product with model number HK-WNT-90 from Shaanxi Huike Biotechnology Co., Ltd.

[0011] A method for preparing a pesticide residue remover includes the following steps: (a) Preparation of enzymatic hydrolysis of white hyacinth bean solution 1. Take 90-110 parts of white hyacinth beans, add 180-200 parts of water and soak for 7-8 hours; 2. After soaking, blend the white hyacinth bean solution into a pulp, filter and discard the residue, then collect the filtered pulp. 3. Add 800-1000 parts of water to the reactor and heat it to 55-65℃. Then add the filtered slurry to the reactor and add 9-11 parts of papain. Stir for 1-3 hours. 4. Maintain the temperature at 55-65℃, and after 2 hours, raise the temperature of the reactor to 90℃ to inactivate the enzyme for 15 minutes, then lower the temperature to 40℃ to obtain the enzymatic hydrolysed white hyacinth bean solution. (II) Preparation of Chinese herbal extracts 1. Take 90-110 parts of licorice root, 45-55 parts of Isatis leaf, 25-35 parts of Perilla leaf, 25-35 parts of Forsythia, 25-35 parts of honeysuckle, 15-25 parts of Smilax glabra, and 15-25 parts of Ginkgo leaf. Crush them and pass them through a 60-100 mesh sieve to make Chinese herbal medicine powder for later use. 2. Add the above Chinese herbal powder to an ultrasonic extraction tank containing 400-600 parts of ethanol solution with a volume ratio of 50-55% for extraction. During extraction, the ultrasonic frequency is 20-50kHz, the ultrasonic power is 100-500W, the temperature is 40-60℃, and the time is 20-40min. The released extract is the Chinese herbal extract. (iii) Mix the enzymatically hydrolyzed white hyacinth bean solution with the extract of traditional Chinese medicine, stir for 0.5-2 hours to prepare a mixture; (iv) Add 4-6 parts of soybean protease, 9-11 parts of glutathione, 9-11 parts of amylase, 7-9 parts of jujube peptide, 1-3 parts of chitosan oligosaccharide, and 1-3 parts of alkyl glycoside to the mixed solution prepared in step (iii), stir for 0.5-2 hours, and prepare the final mixed solution for later use. (v) Then add 0.5-1 parts sodium citrate and 0.5-2 parts potassium sorbate to the final mixture in (iv), and continue stirring for 20-50 minutes; (vi) Packaging, warehousing, and production completed.

[0012] Preferably, in step (ii), the volume concentration of the ethanol solution is 55%, the ultrasonic frequency is 30kHz, the ultrasonic power is 300W, and the extraction temperature is 50℃.

[0013] Preferably, in step (iii), the mixture is centrifuged at 5000–6000 rpm for 3–8 min, and the supernatant is collected.

[0014] Compared with existing technologies, this invention has the following beneficial effects: it can effectively chelate heavy metal ion residues in fruits and other crops, and reduce their toxicity through bio-enzyme catalysis, thereby reducing harm to crops and solving the problem of heavy metal pollution caused by chemical pesticides; it can effectively remove the damage to crops and the pollution of fruits caused by pesticide, environmental chemical agents, biological agents and other harmful substances; it is a natural pesticide residue remover, with simple and easy-to-use method and low cost. Attached Figure Description

[0015] Fig. 1 Flowchart for preparing enzymatic hydrolysis of white hyacinth bean solution; Fig. 2 This is a flowchart of the extraction process for Chinese herbal medicine ingredients. Detailed Implementation

[0016] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below in conjunction with specific embodiments. Obviously, the described embodiments are only a part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0017] The mechanism of action of this invention is as follows: Heavy metals denature proteins primarily by binding to specific groups within the protein, thereby disrupting its spatial conformation. These heavy metal ions include common ones such as Hg²⁺, Cd²⁺, Pb²⁺, Cu²⁺, and Ag⁺, which can interact with proteins. Proteins are composed of amino acids, and their sulfhydryl, carboxyl, amino, and imidazole groups are binding sites for heavy metal ions. For example, Hg²⁺ readily binds to sulfhydryl groups, forming stable complexes that alter the protein's structure. When heavy metal ions bind to protein groups, the existing non-covalent interactions within the protein molecule, such as hydrogen bonds, disulfide bonds, and van der Waals forces, are disrupted. Simultaneously, new chemical bonds may be formed, leading to a change in the protein's spatial conformation, transforming it from an ordered, compact structure to a disordered, loose structure, ultimately resulting in denaturation. Conversely, the same principle applies to the enzymatic hydrolysis of white hyacinth bean solution, which involves the complexation of heavy metals.

[0018] This invention uses natural plant protein as raw material and enzymatically hydrolyzes white hyacinth bean solution to obtain white hyacinth bean protein peptides. On the one hand, the peptide chains of white hyacinth bean protein peptides contain amino and carboxyl groups, and some peptide chains also contain functional groups such as imidazole groups of histidine. These functional groups are affinity binding sites for heavy metal ions, providing a structural basis for complexation reactions. On the other hand, the spatial structure of white hyacinth bean protein peptides can adsorb heavy metal ions through hydrophobic interactions, further promoting binding and causing heavy metal ions to form stable chelates with peptide chains. Since peptides, as one of the raw materials for chelates, are derived from natural plant protein, there are almost no safety issues. Affected by environmental factors such as pH and ionic strength, the chelates lose their solubility and form precipitates. These precipitates cannot be actively absorbed by the roots of crops, nor can they be easily transported to fruits within the plant, thereby reducing the accumulation of heavy metals in crops.

[0019] This invention utilizes the catalytic action of biological enzymes to reduce the toxicity of heavy metals. Soybean protease can catalyze the hydrolysis of soybean protein to generate small-molecule soybean bioactive peptides, achieving indirect detoxification. On one hand, soybean protease can cleave the peptide bonds of soybean 7S and 11S proteins, generating peptides containing functional groups such as amino and carboxyl groups, which can chelate with heavy metal ions such as lead and cadmium, reducing the concentration of free heavy metals in plant cells and minimizing their damage to cytoplasmic enzyme systems and metabolic processes. On the other hand, the hydrolysate, soybean antioxidant peptides, can enhance the activity of the plant's antioxidant system, reduce the reactive oxygen species induced by heavy metals, alleviate the damage of lipid peroxidation to plant cell membranes, and maintain normal plant physiological functions.

[0020] Glutathione (GSH) serves as a raw material for the synthesis of phytochelates (PCs) and an antioxidant. When heavy metal ions enter cells, they activate the synthesis of phytochelate synthase. This enzyme uses GSH as a substrate to synthesize PCs. The sulfhydryl groups of PCs bind with heavy metal ions to form a complex. This complex is recognized by ATP-driven transport proteins and pumped into the vacuole, achieving effective binding and isolation of heavy metals.

[0021] Amylase can catalyze the hydrolysis of starch to produce glucose, providing energy for plant growth under heavy metal stress, maintaining key physiological processes such as root vitality and photosynthesis, and enhancing the plant's resistance to stress.

[0022] Jugland peptides contain phenolic hydroxyl groups and carboxyl groups, which can combine with heavy metal ions to form stable complexes, reducing their bioavailability and decreasing the absorption of heavy metals by plants. At the same time, after being absorbed by plants, jugland peptides can act as signaling molecules or antioxidants, indirectly enhancing the overall stress resistance of plants and thus indirectly reducing the toxic effects of heavy metals.

[0023] The herbal extract of this invention has excellent detoxification and neutralization effects. The complex active substances in each component, together with other components of the formula such as various enzymes, can effectively remove harmful substances such as heavy metals, chemical pesticide residues, and environmental pollution from crops.

[0024] In the formulation of herbal extracts, licorice, Smilax glabra, ginkgo leaves, and honeysuckle are rich in flavonoids, organic acids, and polyphenols. Their molecular structures contain a large number of phenolic hydroxyl and carboxyl groups. These groups together form a heavy metal chelating network, which can bind with heavy metal ions to form stable metal complexes. The stability is higher than that of using a single herbal ingredient, and it can quickly reduce the concentration of free heavy metal ions in the environment. At the same time, the flavonoids, phenylethanol glycosides, and phenolic acids in ginkgo leaves, forsythia, honeysuckle, and Isatis indigotica are natural antioxidants. They can remove reactive oxygen species (ROS) produced in plants or enhance the activity of the plant's own antioxidant enzymes, reduce oxidative stress caused by heavy metals, and protect the integrity of cell membranes and organelles. The aromatic rings and ester groups in phenylpropanoids from ginkgo leaves, forsythia, and honeysuckle, indole alkaloids from Isatis indigotica leaves, and volatile oils from perilla leaves can bind to hydrophobic groups of organophosphorus and organochlorine pesticide molecules through van der Waals forces and hydrophobic interactions. Glycyrrhizic acid and ginkgolides can be recognized by plants as exogenous signaling molecules, inducing the expression of detoxification enzyme genes such as glutathione S-transferase (GST) and peroxidase (POD) in plants, thus increasing the activity of these enzymes and accelerating the metabolism and degradation of pesticides. Simultaneously, the volatile oils and surfactants (such as saponins) in perilla leaves and honeysuckle can improve the wettability and permeability of herbal extracts. These components help the extracts penetrate better into the surface of crops, separating lipid-soluble pesticides attached to the waxy layer, making them easier to degrade or wash away. They also assist other active ingredients in the extracts to enter the plant body smoothly, exerting an endogenous detoxification effect. The active ingredients in the extract can provide nutrients for beneficial microorganisms (such as Bacillus and Actinomycetes). During their growth and metabolism, these microorganisms produce a variety of organic acids, extracellular polysaccharides and other substances, which further chelate heavy metals, degrade pesticides, enhance their own purification capabilities, and achieve long-term maintenance of detoxification effects.

[0025] Furthermore, this invention replaces amino oligosaccharides with chitosan oligosaccharides, eliminating potential safety hazards of raw materials. It is supplemented with sodium citrate and alkyl glycosides, which synergistically enhance the effects of other components in this invention, thereby improving the removal efficiency of heavy metals and pesticide residues.

[0026] The pesticide residue removers of Examples 1-5 are respectively prepared from the weight proportions shown in Table 1 below.

[0027]

[0028] The preparation method of the above-mentioned pesticide residue remover is as follows: Figs. 1-2 As shown, the steps involved are as follows: (a) Preparation of enzymatic hydrolysis of white hyacinth bean solution 1. Take white hyacinth beans and soak them in 200 parts water for 8 hours; 2. After soaking, blend the white hyacinth bean solution into a pulp, filter and discard the residue, then collect the filtered pulp. 3. Add 1000 parts of water to the reactor and heat it to 60°C. Then add the filtered slurry to the reactor and add papain at the same time. Stir for 2 hours. 4. After maintaining the temperature at 60℃ for 2 hours, raise the temperature of the reactor to 90℃ to inactivate the enzyme for 15 minutes, and then lower the temperature to 40℃ to obtain the enzymatic hydrolysed white hyacinth bean solution. (II) Preparation of Chinese herbal extracts 1. Take licorice root, indigo leaf, perilla leaf, forsythia, honeysuckle, smilax glabra, and ginkgo leaf, crush them and pass them through a 100-mesh sieve to make Chinese herbal powder for later use; 2. Add the above Chinese herbal powder to an ultrasonic extraction vessel containing 500 parts by volume of 55% ethanol solution for extraction. During extraction, the ultrasonic frequency is 30kHz, the ultrasonic power is 300W, the temperature is 50℃, and the time is 30min. The released extract is the Chinese herbal extract. (iii) Mix the enzymatic hydrolysed white hyacinth bean solution with the herbal extract, stir for 1 hour, then centrifuge at 5000 rpm for 5 minutes, and collect the supernatant as the mixture. (iv) Soybean protease, glutathione, amylase, jujube peptide, chitosan oligosaccharide and alkyl glycoside are respectively placed into the mixed solution prepared in step (iii), and stirred at 500 rpm for 1 hour to obtain the final mixed solution for later use. (v) Then add sodium citrate and potassium sorbate to the final mixture from (iv) and continue stirring for 30 minutes; (vi) Packaging, warehousing, and production completed.

[0029] The preparation process described in this invention is simple and easy to implement. In the preparation of the herbal extract, specific ultrasonic treatment is applied. Through the unique ultrasonic effect, the activity of each active component is activated and maintained, and the extracted components are fully integrated. Experiments have shown that after treatment with the herbal extract described in this invention, the lead content of the sample to be tested decreased from 0.33 μg / g to 0.03 μg / g, the cadmium content decreased from 0.25 μg / g to undetectable, and the mercury content decreased from 0.05 μg / g to <0.01 μg / g.

[0030] This invention relates to a pesticide residue remover that combines an enzymatically hydrolyzed white hyacinth bean solution, traditional Chinese medicine extracts, and corresponding enzymes in a synergistic manner. The white hyacinth bean solution contains white hyacinth bean protein peptides, which can complex with heavy metal ions to form precipitates, thereby reducing their toxicity and minimizing harm to crops and fruits. The synergistic biological enzymes further reduce the toxicity of heavy metals through enzymatic catalysis. The extracted traditional Chinese medicine components have detoxification effects, and their chemical groups, in conjunction with the above components, can effectively address the pollution problems of heavy metals, chemical pesticide residues, and other harmful substances from environmental pollution on crops.

[0031] The method of using this invention is to spray the pesticide residue remover of Example 3 on the leaves of crops 5 to 10 days before harvest. The amount of remover used per acre is 125 to 250 ml of remover mixed with 30 kg to 50 kg of water and sprayed. Practical application has proven that the effect of this invention is quite obvious.

[0032] Verification Experiment I. Heavy Metal Removal 1. Spraying Five days before harvest, each crop to be tested was sprayed with the pesticide residue remover of Example 3. The amount of remover used per acre was 250 ml of remover mixed with 40 kg of water and sprayed.

[0033] 2. Heavy metal index The evaluation standards for the maximum residue limits of heavy metal elements in crops refer to the "National Food Safety Standard: Limits of Contaminants in Food" (GB2762-2022), as shown in the table below:

[0034] 3. Removal Results The tests were conducted according to the methods specified in the National Food Safety Standard "Determination of Multiple Elements in Food" (GB5009.268-2016), and the results are shown in the table below:

[0035] The heavy metal residue levels in each group did not exceed the maximum residue limits specified in the National Food Safety Standard for Limits of Contaminants in Food (GB2762-2022). The heavy metal content was within the safe range and the removal effect was relatively obvious.

[0036] II. Pesticide Residue Testing Detection method: The detection was carried out in accordance with the detection method specified in the standard "Determination of Residues of 208 Pesticides and Their Metabolites in Plant-Derived Foods by Gas Chromatography-Mass Spectrometry" (GB 23200.113-2018).

[0037] Sample: Pesticide residue remover prepared in Example 3.

[0038] Application method: Spray the leaves once 3 days before harvest. The dosage of the cleaner is 250ml per acre, mixed with 30kg of water and sprayed. The control group was treated with plain water.

[0039] The test results for different crops are shown in the table below.

[0040] 1. Rice pesticide residue testing The test data is shown in the table below:

[0041] Experiment Example 2: Detection of pesticide residues in tomatoes The test results are shown in the table below:

[0042] Experiment Example 3: Detection of pesticide residues in kumquats The test results are shown in the table below:

[0043] Experiment Example 4: Detection of Pesticide Residues in Apples The test results are shown in the table below:

[0044] Experiment Example 5: Detection of pesticide residues in melons The test results are shown in the table below:

[0045] Based on the above test results, the pesticide residue test results for five types of crops—rice, tomatoes, kumquats, apples, and melons—showed that over 99% of pesticide residues were ND (not detected), proving that the pesticide remover of this invention has high effectiveness and stability, and can effectively solve the problem of damage to crops and contamination of fruits caused by harmful substances produced by chemical pesticides.

[0046] Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A pesticide residue remover, characterized in that, It is made from the following components in parts by weight: 90-110 parts white hyacinth bean, 9-11 parts papain, 90-110 parts licorice, 45-55 parts indigo leaf, 25-35 parts perilla leaf, 25-35 parts forsythia, 25-35 parts honeysuckle, 15-25 parts smilax glabra, 15-25 parts ginkgo leaf, 4-6 parts soybean protease, 9-11 parts glutathione, 9-11 parts amylase, 7-9 parts jujube peptide, 1-3 parts chitosan oligosaccharide, 0.5-1 part sodium citrate, and 1-3 parts alkyl glycoside.

2. The pesticide residue remover according to claim 1, characterized in that, It is made from the following components in parts by weight: 100 parts white hyacinth bean, 10 parts papain, 100 parts licorice, 50 parts indigo leaf, 30 parts perilla leaf, 30 parts forsythia, 30 parts honeysuckle, 20 parts smilax glabra, 20 parts ginkgo leaf, 5 parts soybean protease, 10 parts glutathione, 10 parts amylase, 8 parts jujube peptide, 2 parts chitosan oligosaccharide, 0.8 parts sodium citrate, and 1 part alkyl glycoside.

3. A method for preparing a pesticide residue remover according to any one of claims 1-2, characterized in that, The steps involved are as follows: (a) Preparation of enzymatic hydrolysis of white hyacinth bean solution 1. Take 90-110 parts of white hyacinth beans, add 180-200 parts of water and soak for 7-8 hours; 2. After soaking, blend the white hyacinth bean solution into a pulp, filter and discard the residue, then collect the filtered pulp.

3. Add 800-1000 parts of water to the reactor and heat it to 55-65℃. Then add the filtered slurry to the reactor and add 9-11 parts of papain. Stir for 1-3 hours.

4. Maintain the temperature at 55-65℃, and after 2 hours, raise the temperature of the reactor to 90℃ to inactivate the enzyme for 15 minutes, then lower the temperature to 40℃ to obtain the enzymatic hydrolysed white hyacinth bean solution. (II) Preparation of Chinese herbal medicine extracts 1. Take 90-110 parts of licorice root, 45-55 parts of Isatis leaf, 25-35 parts of Perilla leaf, 25-35 parts of Forsythia, 25-35 parts of honeysuckle, 15-25 parts of Smilax glabra, and 15-25 parts of Ginkgo leaf. Crush them and pass them through a 60-100 mesh sieve to make Chinese herbal medicine powder for later use.

2. Add the above Chinese herbal powder to an ultrasonic extraction tank containing 400-600 parts of ethanol solution with a volume ratio of 50-55% for extraction. During extraction, the ultrasonic frequency is 20-50kHz, the ultrasonic power is 100-500W, the temperature is 40-60℃, and the time is 20-40min. The released extract is the Chinese herbal extract. (iii) Mix the enzymatically hydrolyzed white hyacinth bean solution with the extract of traditional Chinese medicine, stir for 0.5-2 hours to prepare a mixture; (iv) Add 4-6 parts of soybean protease, 9-11 parts of glutathione, 9-11 parts of amylase, 7-9 parts of jujube peptide, 1-3 parts of chitosan oligosaccharide, and 1-3 parts of alkyl glycoside to the mixed solution prepared in step (iii), stir for 0.5-2 hours, and prepare the final mixed solution for later use. (v) Then add 0.5-1 parts sodium citrate and 0.5-2 parts potassium sorbate to the final mixture in (iv), and continue stirring for 20-50 minutes.

4. The method for preparing a pesticide residue remover according to claim 3, characterized in that, In step (ii), the volume ratio concentration of the ethanol solution is 55%, the ultrasonic frequency is 30kHz, the ultrasonic power is 300W, and the extraction temperature is 50℃.

5. The method for preparing a pesticide residue remover according to claim 3, characterized in that, The mixture in step (iii) is centrifuged at 5000–6000 rpm for 3–8 min, and the supernatant is collected.

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