Products for the removal of pesticide residues

Abstract

The invention relates to nanotechnological products for the removal of pesticides and methods for the production and application of these products. These products offer the opportunity to be used in the agriculture and food sector to protect the environment and human health and they are based on the adsorption of pesticides to nanopolymers.

Description

[0001] PRODUCTS FOR THE REMOVAL OF PESTICIDE RESIDUES

[0002] Technical Field of the Invention

[0003] The invention relates to nanotechnological products for the removal of pesticides and methods for the production and application of these products.

[0004] State of the Art of the Invention (Prior Art)

[0005] Chemical residues represent a problem that can be caused by all sectors related to chemistry and its importance and awareness are increasing today. It creates pollution in these lands, especially in the lands where agricultural products are processed, by means of wastewater, etc., or as a result of disinfection processes. These pollutions, which participate in the ecological cycle, affect the environment and animal health and eventually constitute a factor that threatens human health. Agricultural products or animal products contaminated with these chemical pollutants can reach our tables through food. In this process, it is of great importance for many sectors such as chemistry, medicine, medicine, agriculture and food to develop responsibility for chemical residues in terms of environmental safety and health worldwide. International organizations such as the EPA who also focus on this issue and work on the development of the necessary regulations. Therefore, it is necessary to develop different strategies to further reduce the amount of chemical residues.

[0006] Pesticides are substances or mixtures of substances used to prevent, control, or reduce the damage of harmful organisms. The pesticide may be a chemical agent, a biological agent such as a virus or bacteria, an antimicrobial, a disinfectant, or any other means.

[0007] Pesticide applications on plants are carried out in accordance with the prescriptions stating the application times and amounts on the packaging. For these pesticide amounts to decrease on the plant, the degradation periods specified on the prescription are expected. However, the size of the applied plant, the use of spreading and adhesive products, the addition of different pesticides and their synergistic effects, and the difference in conditions during the application such as the environment and air can cause the degradation times specified in the prescriptions to differ. The Ministry of Food, Agriculture and Livestock has a project called EKUY (Integrated and Controlled Product Management) for this problem. With this project, the amount of pesticides is examined before collecting the product from the plant. In this application, it has been understood that the degradation periods specified on the prescriptions differ. It is often not possible to predict the degradation times due to reasons such as the dispersion effect in the product. If sufficient degradation is not achieved, the product is kept a little longer to be collected, but this time, problems such as more maturation than desired are encountered, and there may be a problem in terms of timing between the producer and the buyer.

[0008] Pesticide removal studies carried out during the period of approximately 100 years of pesticides are in the form of prohibition of pesticides, stopping their production, waiting for the period between expiration and harvest, washing with water or water with additives (vinegar water, etc.). Current removal studies have focused on reducing rather than eliminating residues. In the studies conducted for complete removal, negativities such as deterioration of the products due to washing, and change in taste and / or smell in the products occur.

[0009] In addition, it is possible to encounter pesticides even in our network waters through the passage of pesticides from the soil to underground waters and stream resources as a result of agricultural practices. In this context, the removal of pesticides from washing waters, wastewater, industrial wastes, and environments containing pesticides is also important for the health of the environment and living creatures.

[0010] In patent document US3660071A, the materials are attached to water-soluble hydroxyalkyl acrylate or methacrylate polymers. It is mentioned that these substances may be drugs, pesticides, aromatic and fragrant substances. It is mentioned that it is useful in terms of attaching the drug, pesticide, ascorbic acid, vitamin A, vitamin DI, D2, D3 and Vitamin E to the synthesized polymer. Hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, and hydroxyethyl methacrylate are used as solid, water-soluble copolymer members. Water-soluble polymer synthesis is carried out by mixing hydroxyethyl methacrylate, methacrylic acid, methanol, and t-butyl peroctoate, heating at 80°C and stirring for 6 hours. Patent document US5674514A mentions stable aqueous emulsions that can be stored in high amounts and environmentally acceptable structures that reduce inflammation or toxicity. Aqueous emulsions are defined as structures containing hydrophobic pesticides and pesticide mixtures dissolved in the organic solvent. Compound classes such as urease, triazine, triazole, carbamates, phosphoric acid esters, dinitroanilines, and diphenylethers were selected as pesticides in emulsions. The invention subject to the patent includes pesticides such as cis, trans-(±)-2-ethyl-5-(4-phenoxy-phenoxymethyl)l,3-dioxolan, 0,0-diethyl O-2-isopropyl-6- methylpyrimidin-4-yl phosphorothionate as pesticides. The polymer and polymer mixture used in the emulsion are polymers that are insoluble in water, stable in hydrolysis, and soluble in the pesticide or pesticide mixture. It has been stated that the viscosity or light scattering of the polymers used in the emulsion is between 10,000 and 1,000,000 daltons and between 30,000 and 300,000 daltons. Polymers from polymer classes such as hydrocarbon residues, polystyrene, polyacrylates, polyesters, polycarbonates, polyphenylenes, and polyurethanes are used as polymers in the emulsion. The polymers used are used in a ratio ranging from 1% to 30% and from 1% to 10% by weight of the pesticides. Structures such as ammonium sulfate salt, sulfonated polystyrene salt, lignin sulfonic acid ammonium, potassium, magnesium, sodium, and calcium are used as surfactants. As a non-ionic dispersant, it comprises structures such as polyvinyl alcohol, polyvinyl methyl ether, poly(2-hydroxyethyl) methacrylate, and hydroxypropylmethyl cellulose. This method is intended to combat insect infestation in plant species and to regulate plant growth. They have developed aqueous spray emulsions containing effective amounts of pesticides in aqueous emulsions. Spray emulsions may contain between 0.01 and 1% of pesticides as the effective amount of pesticides.

[0011] Pesticides pose a danger in terms of both human health and environmental protection, while increasing and / or protecting agricultural production. It is a globally accepted fact that pesticides have significant side effects on the environment and human health because they are carcinogenic, mutagenic, and adversely affect the nervous system. Although agricultural products contribute to the production of our foods, which are indispensable for our lives, drug residues are the initiators of dozens of diseases, both acute and chronic (especially cancer). When agricultural products are offered to the market, significant amounts of pesticide residues are detected on these products. The presence of these residues causes significant problems, especially in the field of export, as well as its effects on the environment and human health. The production and use of pesticides should be strictly controlled. It is necessary to trust the farmer or the officials with a relationship based on interest with the farmer for follow-up. Since the studies carried out on the final product are predominant, if there is not enough removal, the entire product is wasted or if it is not controlled, human recruitment occurs. Criminal proceedings are applied if it is determined that the food placed on the market contains residues above the limits specified in the inspection. However, at the same time, the fact that the food in question has now reached the end user makes it impossible to undo / prevent the damage to human health. Even if the residual product on the product is noticed before entering the market, all of the product is disposed of because effective removal cannot be made. In this case, both the seller and the buyer face a great loss. Since the penalties are paid retrospectively, the damage is reflected to the producers as well as the buyers. Agricultural production is negatively affected throughout the country with the fmancial / moral impact of producers who face great damages, and the motivation of the producer decreases. In addition to all these, the damage received in terms of the health of the consumer is irreversible.

[0012] It will also be an advantage in terms of health to remove pesticides from environmental water sources and to carry out a treatment process for pesticides in the water of the municipalities, in the mains water of the municipalities, and even in the tap water of the houses.

[0013] Brief Description of the Invention and Objects

[0014] In said invention, a synthesis method different from previous studies is used to reduce the amount of pesticide residues below the determined international limits and to reduce them significantly. This method does not contain surfactants and therefore the post-synthesis washing process is easier and in a small number of steps compared to the methods containing surfactants. In the invention, amino acid-based monomers such as phenylalanine, alanine, histidine, tryptophan, and 2-hydroxyethyl methacrylate (HEMA) monomers are used as monomers. The nanopolymers used in the invention are hydrophilic structures that are insoluble in water but dispersed very well and suspended in the solution. After the nanopolymer is synthesized, it is ensured that the pesticides are bound to the nanopolymer by adsorption. In the invention, a nanotechnological approach has been developed to remove pesticide residues, and pesticide removal is provided by the adsorption of pesticides to the waterinsoluble nanopolymer. The basis of the invention is that the residues of pesticides on agricultural products interact with the nanoparticles in a short time and are collected in a different place by separating from the nanopolymers in a very short time. The object of the presented art is to ensure the continuity of the production of agricultural products with pesticides that can be removed and to protect the environment and human health by collecting the pesticides used. Therefore, effective removal of pesticide residues from foods / plants / waters, which are of great importance due to their effects on the environment and human health, can be achieved thanks to the product developed in the invention.

[0015] The fact that the residues can be removed allows the producer to use pesticides more easily and reduces the restrictions for the producer. The producer can grow better quality products as it can use the removable pesticides it wants to protect against diseases and pests. In addition, since the producer will not have to wait for the degradation of the pesticide used in the collection of the product, it is more comfortable in terms of time. Thus, the agreement of the producer with the seller is easier and more profitable in terms of timing. The invention provides many advantages such as the fact that the producer does not have time-related problems, can grow better quality products and knows that it will remove the pesticide it uses. The intermediaries and sellers who buy the product and offer it to the market have the freedom to choose the product in question, where the pesticide residues can be removed, thus the risk of punishment has been eliminated and they do not have any timing problems for shopping.

[0016] In short, with the said invention, many advantages are provided for both the producer (farmer), the intermediary, the market (seller) and the consumer. Thanks to the invention, due to the high residue, the reduction of risk factors such as penalties, destruction of the product, etc., therefore, since there will be no time restriction on harvesting, the commercial planning is relieved, thus the agreements between the producer, the intermediary and the seller are facilitated. In addition, since it is stated that the product is free of pesticide residues by using nanopolymer, therefore the end user / consumer will prefer this safer product, the demand for the offered product increases and production increases with the increase in demand. Definitions of Figures Describing the Invention

[0017] Figure 1. The stages of synthesis in the preparation of the nanopolymer

[0018] Figure 2. A schematic diagram of the treatment of the product containing the pesticide with the nanopolymer

[0019] Figure 3. A schematic representation of pesticide binding on the nanopolymer surface Figure 4. The results of case studies on pesticide removal from raisins

[0020] Detailed Description of the Invention

[0021] The invention is a nanopolymer that removes pesticide residues, characterized in that it comprises the following: i) amino acid-based monomer containing hydrophobic side chain groups with hydroxyethyl methacrylate (HEMA) monomer or Hydroxyethyl methacrylate (HEMA) monomer, or ii) Poly(HEMA) nanopolymer with L-amino acids on its surface.

[0022] In the said invention, a method of reducing the amount of pesticide residues below the determined international limits and the pesticide removal product obtained by this method are disclosed. This method does not contain surfactants and therefore the post-synthesis washing processes are easier and in a small number of steps compared to the methods containing surfactants. (Figure 1).

[0023] Different methods that do not contain surfactants or are modified (inoculated) after synthesis are used in the synthesis of pesticide removal products. In particular, the method does not contain surfactants and therefore the post-synthesis washing processes are easier and in a small number of steps compared to the methods containing surfactants. Furthermore, the nanopolymer synthesized with the 2-hydroxyethyl methacrylate (HEMA) monomer can then be modified or inoculated with amino acids, as amino acid-based monomers are used during pesticide removal product synthesis.

[0024] After the nanopolymer is synthesized with the method of the invention, it is ensured that the pesticides are bound to the nanopolymer. In the invention, 2-hydroxyethyl methacrylate monomers or monomers based on amino acids such as phenylalanine, alanine, histidine, tryptophan, or 2-hydroxyethyl methacrylate (HEMA) monomers are used as monomers. Or, L-amino acid molecules are inoculated directly on the poly(HEMA) nanopolymer synthesized without using these amino acid-containing monomers by a separate process. HEMA was selected because it is an FDA-approved polymer, is used in many biological commercial products, and does not provide additional pollution to the body and the environment in this sense. Said polymerization takes place at 50-70°C, and the nanopolymers used in the invention are hydrophilic structures that are insoluble in water but dispersed very well and suspended in the solution. After nanopolymer synthesis, it is ensured that the pesticides are bound to the nanopolymer by adsorption.

[0025] In the nanopolymer synthesis, 10-50 mL of polyvinyl alcohol (PVA) solution is prepared as a stabilizer. 0.4-1.0 mL of HEMA alone or in a 6: 1 (v / v) ratio with other monomers is added to the previously prepared stabilizer PVA solution and mixed gently. It is incubated for 12-24 hours at 50-70°C in a stirred water bath by adding 0.1-0.6 mL of ethylene glycol dimethacrylate (EGDMA) as a crosslinker and 20-90 mL of potassium persulfate (KPS) as a starter. The obtained nanopolymers are washed with distilled water and ethanol, respectively, to remove the media components that do not participate in polymerization. When amino acids do not participate in the structure in monomer forms, that is, it is ensured that water is removed from the structure to directly inoculate amino acids to the poly(HEMA) nanopolymer obtained by HEMA alone. For this, poly(HEMA) is washed several times with anhydrous methanol. 80 g of poly(HEMA) is dispersed in a 0.01-5 g / mL amino acid solution prepared in tetrahydrofuran and stirred for 5-48 hours at 30-60°C in a magnetic stirrer with 0.1-5 g of NaH catalyst. After the inoculation reaction, it is washed with distilled water and ethanol, respectively, to remove the amino acids that do not participate in the structure. After synthesis, rigid, water-insoluble but well-dispersed hydrophilic nanopolymers are obtained.

[0026] The synthesis of the modified (inoculated) nanopolymers is synthesized by HEMA without the addition of other monomers, similar to the synthesis of the nanopolymer. After synthesis, the nanopolymers are washed with distilled water and ethanol, respectively, to remove the media components that do not participate in polymerization. The obtained nanopolymers are dried in an oven. It is mixed with the amino acid solution prepared in a concentration of 0.01- 5 g / mL prepared in tetrahydrofuran with 0.1-5 g of NaH catalyst. It is stirred for 5-48 hours at 30-60°C in a magnetic stirrer. At the end of the period, distilled water and methanol washing are performed to remove the unbound amino acids.

[0027] With the obtained nanopolymers, the specific groups and high surface area of the nanopolymers are used to remove wet and / or dry pesticides on various fruits and vegetables. The nanopolymer solution to be used in pesticide removal is prepared by synthesizing and distributing the washed nanopolymers in water. However, there may be pH regulators such as ethanol or carbonate salts, citric acid, acetic acid, etc. depending on the structure of the fruit or vegetable, when there are no conditions such as abrasion, breakdown, damage to the fruit or vegetable on which pesticide removal will be made. It was determined that the pesticide on the fruit or vegetable in question was removed in varying proportions of 10-99% after the vegetable or fruit was kept in the solution containing the pesticide-removing nanopolymer for about 0-30 minutes, then rinsed with water and the nanopolymers were removed from the relevant fruit or vegetable (Figure 2). With this method, residual pesticides in fruits and vegetables are quickly and easily removed at a high rate. Figure 4 shows the results of case studies on pesticide removal from raisins. In addition, studies were carried out for pesticide removal with different products such as grape leaves, spinach, fresh grapes, peaches, and tomatoes. It is seen that the success of the removal of the deltamethrin pesticide made with three different nanopolymers synthesized with different amino acid derivatives is over 90%.

[0028] The product of the invention is a nanotechnological material that can range in size with an average of 50-400 nm and has a high specific surface area in the range of 1000-3000 m2 / g. The advantage of being nano-sized is that it has a large surface area and allows for the removal of more pesticides. Thanks to this, it can interact with the environment at the maximum level and bind high amounts of pesticides. In the structure proposed by the invention, first of all, the superior properties of polymeric materials such as resistance to mechanical force, high temperature and pressure, acid, base, metal ions and organic solvents and their long storage life are used. In addition, polymers can be stored at room temperature (25°C) for several years without any decrease in their performance. In addition, there are amino acids on said nanomaterial containing specific side groups such as phenyl, methyl, indole ring and imidazole ring, which bind to the relevant pesticides with high interest (Figure 3). It is expected to increase the chemical regions that will bind with pesticides through secondary interactions on the surface of the nanopolymers obtained here; thus, it is expected to provide efficient removal processes by providing more stable bonding with the help of high chemical interaction.

[0029] It is possible to use the nanopolymer produced in the invention in different places to remove pesticide residues. It can be used especially in fresh fruit and vegetable processing plants. The product of the invention can be added to the washing waters of fruits and / or vegetables, where the washing process does not affect the shelf life. In products where the washing process affects the shelf life, it can be offered to the market in nanopolymer solutions to be applied by the end user / consumer. Since the removal studies on the products are carried out with solutions of nanopolymers, the end user does not need an additional requirement for the application. In this system, a market department can also be created, and products that have not been removed from the pesticide residue and packaged can be displayed in this department. The product can be stored in these departments in the form of nanopolymer solutions for the end user.

[0030] It is aimed to ensure food safety in these uses. In addition, it is possible to apply pesticideremoving nanopolymers while the fruit or vegetable is on the plant, without being torn from the branch, that is, while it is still in the plant category. Vegetables plucked from the fruit or soil are now considered food, but they are alive on the plant and pesticides can break down faster. If the nanopolymer is applied before it is separated from the plant, it is possible to remove it faster by removing the pesticide in addition to breaking it down. With this application, the producer may have the opportunity to collect fruits or vegetables that have not yet fallen within the limit range of the pesticide but have reached sufficient maturity earlier. In other words, the invention in question falls within the field of application not only of foods but also of plants.

Claims

CLAIMS1. A nanopolymer that removes pesticide residues, characterized in that: i) an amino acid-based monomer comprising hydrophobic side chain groups with hydroxyethyl methacrylate (HEMA) monomer or Hydroxyethyl methacrylate (HEMA) monomer, or ii) Poly(HEMA) nanopolymer having L-amino acids on its surface.

2. The nanopolymer according to Claim 1, characterized in that the particle size is within the range of 50-400 nm.

3. The nanopolymer according to Claim 1, characterized in that it has a high specific surface area of 1000-3000 m2 / g.

4. The nanopolymer according to Claim 1, characterized in that the hydrophobic side chain groups are phenyl, methyl, indole ring or imidazole ring.

5. The nanopolymer according to Claim 1, characterized in that amino acid-based monomers are phenylalanine, alanine, histidine or tryptophan.

6. The nanopolymer according to Claim 1, characterized in that the L-amino acid is L-lysine, L-valine, L-leucine, L-isoleucine or L-threonine.

7. A product removing pesticide residues, characterized in that it comprises a nanopolymer according to any one of the preceding claims.

8. The nanopolymer synthesis method of removing pesticide residues, characterized in that it comprises the following process steps:• Preparing 10-50 mL of polyvinyl alcohol (PVA) solution as a stabilizer,• Adding 0.4-1.0 mL of Hama alone or in a 6: 1 (v / v) ratio with other monomers to the previously prepared stabilizer PVA solution and mixing,• Adding 0.1-0.6 mL of ethylene glycol dimethacrylate (EGDMA) as a crosslinker and 20-90 mL of potassium persulfate (KPS) as a starter,• Incubating for 12-24 hours at 50-70°C in a stirred water bath,• Removing the media components that do not participate in polymerization by washing the obtained nanopolymers with distilled water and ethanol, respectively.

9. The nanopolymer synthesis method that removes pesticide residues, characterized in that it comprises the following process steps: • Completely removing water molecules from poly(HEMA) nanopolymers to directly inoculate amino acids to the poly(HEMA) nanopolymer,• Dispersing the poly(HEMA) tetrahydrofuran in a 0.01-5 g / mL amino acid solution,• Stirring for 5-48 hours at 30-60°C in a magnetic stirrer with 0.1-5 g of NaH catalyst, • After the inoculation reaction, washing with distilled water and ethanol, respectively, is performed to remove the amino acids that do not participate in the structure.

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