A preparation method for long-acting sustained-release amino acid micro-nano zinc material

Abstract

The present invention belongs to the field of sterilization technology, and specifically relates to a method for preparing a long-acting sustained-release amino acid micro-nano zinc material, wherein the amino acid micro-nano zinc material uses micro-nano zinc as a core and an amino acid zinc complex as a surface coating layer to form a shell-core structure, and the shell-core structure is encapsulated in γ-cyclodextrin, and a specific preparation method is provided. The present invention solves the defect problem of the existing zinc-based bactericide, uses amino acid zinc and micro-nano zinc to form an encapsulated complex structure, effectively reduces the amount of zinc used, not only meets the zinc limit regulations, but also uses amino acid zinc to form a stable complex structure, achieving long-term and high efficiency of sterilization.

Description

Technical Field

[0001] The invention belongs to the technical field of sterilization, and specifically relates to a method for preparing a long-acting sustained-release amino acid micro-nano zinc material. Background Art

[0002] Micro-nano zinc has a broad-spectrum bactericidal effect and can be widely used in aquaculture. For example, "black gill disease" and "saprolegniasis" caused by fungal infection in crayfish, "tail bubbles" and "ulceration" caused by chitin decomposing bacteria, "cephalothorax edema" and "enteritis" caused by Vibrio infection, etc.; "trembling disease", "ring claws", "rotten shells", "black gills", "rotten gills" and other diseases caused by bacterial infection in river crabs. It can also be used for environmental disinfection, and can be sprayed during livestock and poultry breeding and after market release. Spraying and oral administration can effectively kill bacteria and viruses in animals and water bodies. The most representative of micro-nano zinc is micro-nano zinc oxide material, which has great bactericidal value. However, with the implementation of zinc restriction regulations, the use of micro-nano zinc has dropped sharply, and the bactericidal performance has dropped sharply. Therefore, the market urgently needs an environmentally friendly antibacterial agent that can effectively control the zinc content and ensure the bactericidal and antibacterial effect. Summary of the invention

[0003] In view of the problems in the prior art, the present invention provides a method for preparing a long-acting sustained-release amino acid micro-nano zinc material, which solves the defects of the existing zinc-based fungicides. Amino acid zinc and micro-nano zinc are used to form an encapsulated complex structure, which effectively reduces the amount of zinc used. Not only does it meet the zinc limit regulations, but it also uses amino acid zinc to form a stable complex structure to achieve long-term and high efficiency in sterilization.

[0004] In order to achieve the above technical objectives, the technical solution of the present invention is:

[0005] A method for preparing a long-acting sustained-release amino acid micro-nano zinc material. The amino acid micro-nano zinc material uses micro-nano zinc as a core and an amino acid zinc complex as a surface coating to form a core-shell structure, and the core-shell structure is encapsulated in gamma-cyclodextrin.

[0006] In the amino acid micro-nano zinc with a core-shell structure, the internal micro-nano zinc is micro-nano zinc oxide, which has excellent astringency and bactericidal ability, as well as excellent anti-inflammatory ability. As the size of the micro-nano particles decreases, zinc oxide has higher activity, and even brings potential harm to the human body and the environment. To address this problem, amino acid zinc is used for encapsulation, and zinc ions form stable adsorption based on the surface defect activity of micro-nano zinc oxide, and attract amino acid zinc to the surface of micro-nano zinc oxide to form a connection. At the same time, amino acid zinc itself belongs to a complex system, forming its own complex fixed connection ; That is, on this structure, the amino acid molecules will chelate and fix the zinc ions adsorbed on the surface of micro-nano zinc oxide, and when the amino acid molecules form a chelate structure with the zinc ions, they are stably connected to the surface of zinc oxide, forming an excellent linkage curing effect; the surface defects of micro-nano zinc oxide itself attract zinc ions, so that the amino acid zinc is deposited on the surface of zinc oxide and forms self-chelation, achieving an internal and external encapsulation structure; based on the fact that zinc oxide and zinc ions belong to the same metal element, they have the same attraction to oxygen atoms, which can improve the activity of zinc ion-encapsulated zinc oxide materials, thereby achieving a better antibacterial effect on the surface. Cyclodextrin itself has an excellent inclusion effect, and the core-shell structure coating system is stabilized in the cyclodextrin to form an inclusion effect. In the entire inclusion system, γ-cyclodextrin can form a stable sustained-release structure, and the core-shell structure is located in the cyclodextrin to reduce the exposed area, achieving a slow release effect. Amino acid zinc and micro-nano zinc both have small particle sizes. When they are in a free state, they can bind to the cell wall or cell membrane of pathogens, directly enter the bacteria, denature the microbial cell protein, achieve the effect of sterilization, and cannot produce the next generation of drug resistance. After the bacteria die and self-dissolve, the bound amino acids will be released again and continue to bind to the next bacterium to continue to produce a bactericidal effect. Therefore, the combination of the three forms an inner complex package and an outer package composite structure, which can form a stable sustained-release performance. Combined with the long-term and sustainable bactericidal properties of the material itself, it greatly reduces the use of vena zinc and meets environmental protection requirements.

[0007] In one embodiment, the preparation method of the micro-nano zinc oxide comprises the following steps: a1, adding sodium chloride and zinc chloride to ethanol-ether solution and performing low-temperature ultrasonic treatment for 2-3 hours to form a glue solution, wherein the mass ratio of sodium chloride to zinc chloride is 5-7:2, the volume ratio of ethanol to ether in the ethanol-ether solution is 2:3-5, the mass ratio of sodium chloride to ethanol-ether solution is 2:3-4, and the ultrasonic frequency of the low-temperature ultrasonic treatment is 10-20°C; the ultrasonic frequency is 50-80kHz. This step utilizes the solubility of zinc chloride in ethanol and ether, and has its own liquid phase dispersion characteristics. Sodium chloride is insoluble in both ether and ethanol, and sodium chloride is in the form of colloidal fine particles in ethanol. particle structure, ensuring that the entire solution presents a colloidal structure with excellent uniform dispersibility, and at the same time, zinc chloride and sodium chloride form a homogenized dispersion in the system, and low-temperature ultrasound can further refine the sodium chloride particles to achieve particle miniaturization, that is, increase the specific surface area of ​​sodium chloride and increase the contact surface between zinc chloride and sodium chloride; a2, vacuum distill the colloid for 30-60 minutes, dry it to obtain a viscous colloid, then add ammonium carbonate and stir evenly, dry it and granulate it after low-temperature grinding to obtain prefabricated particles, the vacuum distillation temperature is 50-60°C, the pressure is 70-80% of the atmospheric pressure, the drying temperature is 50-60°C, the amount of ammonium carbonate added is 90-100% of the mass of zinc chloride, and the stirring speed is

[0008] 500-800r / min, the temperature of low-temperature grinding is 10-20℃; the pressure is 0.4-0.6MPa, the temperature of drying is 30-40℃, the temperature of granulation is 20-30℃, and the pressure is 0.5-0.6MPa. This step uses reduced pressure distillation to remove ether to form ethanol glue, and further removes ethanol during drying to achieve viscosity. When ammonium carbonate is added, the ammonium carbonate is broken during low-temperature grinding to form fine particles, and based on the granulation and structural stability of sodium chloride itself, during the grinding process, the ammonium carbonate particles are gradually refined under pressure and homogenized with the sodium chloride particles; a3, ethyl cellulose is added to ether and stirred evenly to form a coating liquid, and then the coating liquid is evenly coated on the surface of the prefabricated particles, and the coated particles are obtained by constant temperature drying. The concentration of ethyl cellulose in ether is 200-500g / L, the stirring speed is 100-200r / min, and the coating amount is 5-8mL / cm 2, the temperature of constant temperature drying is 30-40°C; this step utilizes the solubility of ethyl cellulose in ether. During the coating process, ether will dissolve and penetrate zinc chloride to a certain extent, thereby improving the adhesion and connection effect of ethyl cellulose. However, the dissolution is only on the surface of zinc chloride and will not affect other materials, thereby ensuring that ethyl cellulose forms a stable liquid film on the surface of the prefabricated particles. During the process of removing ether, the structure of ethyl cellulose is tightened to form a dense polymer film on the surface; a4, the coated particles are allowed to stand at a constant temperature and pressure for 2-4 hours, and then placed in an ether-glycerol mixture for ultrasonic dispersion for 20-30 minutes to obtain a suspension, and the temperature of the constant temperature and pressure is 8 0-90°C, pressure is 0.2-0.3MPa, the volume ratio of ether to glycerol in the ether-glycerol mixture is 3:5-7, the concentration of the coated particles in the ether-glycerol mixture is 100-200g / L, the ultrasonic frequency of ultrasonic dispersion is 50-70kHz, and the temperature is 5-10°C; this step forms the external pressure of the prefabricated particles in a constant temperature and pressure manner, and at the same time, ammonium carbonate decomposes at this temperature to form ammonia, water molecules and carbon dioxide, and ammonia and water molecules form ammonium hydroxide, and the ammonium hydroxide surface is promoted to react with zinc chloride in the presence of water molecules to form an in-situ hydrolysis reaction to obtain zinc hydroxide material; and in the ether-glycerol mixture , ethyl cellulose and sodium chloride will form a stable solution, and the unreacted zinc chloride will also dissolve in ether to form a stable solution system. At this time, in the solution system, the insoluble system of zinc hydroxide itself and the solubility of sodium chloride and ethyl cellulose form a sharp contrast; a5, centrifuge the suspension, remove the supernatant, then use ethanol ultrasonic cleaning, centrifuge, repeat 2-4 times and spray dry to obtain micro-nano zinc oxide particles, the ultrasonic frequency of ethanol ultrasonic cleaning is 40-60kHz, the temperature is 10-20°C; the temperature of spray drying is 130-140°C, and this step uses centrifugation to separate ether and glycerol from zinc hydroxide to form a precipitate. The solid-liquid separation is carried out, and the solubility of ethanol in glycerol and ether is used to perform ultrasonic cleaning to elute the residual ether and glycerol, so as to achieve the stable dispersion and homogenization effect of zinc hydroxide; at the same time, during the spray drying process, the slurry obtained after the final centrifugation is sprayed within 100-200cm2, and the temperature of spray drying is used to decompose the zinc hydroxide into micro-nano zinc oxide in situ, and based on the fact that water molecules are in a gaseous state at this temperature, a stable solid-gas sedimentation separation is formed, a6, the micro-nano zinc oxide particles are subjected to constant temperature light treatment for 30-40 minutes to obtain activated zinc oxide particles, and the constant temperature light treatment adopts visible light irradiation, and the temperature is 30-50℃, and the light intensity is 1-3W / cm 2This step utilizes the surface activity response of micro-nano zinc oxide under light conditions to produce a stable active structure on the surface of zinc oxide. The surface of the active structure system micro-nano zinc oxide contains defect activity, which can effectively adsorb zinc ions and form a stable complex for subsequent reaction with amino acids.

[0009] Furthermore, the preparation method of the long-acting sustained-release micro-nano zinc material comprises the following steps:

[0010] Step 1, adding micro-nano zinc and zinc chloride to an ether-ethanol mixed solution for low-temperature ultrasonic dispersion for 20-30 minutes, then heating and standing for 20-30 minutes, and obtaining surface-adsorbed micro-nano zinc particles after centrifugal filtration, wherein the mass ratio of micro-nano zinc to zinc chloride is 3:1-2, the volume ratio of ether to ethanol in the ether-ethanol mixed solution is 3-5:2, the concentration of micro-nano zinc in the ether-ethanol mixed solution is 100-200 g / L, the temperature of the low-temperature ultrasonic dispersion is 5-10°C, the ultrasonic frequency is 40-70kHz, and the temperature of the heating and standing is 40-60°C ; This step utilizes the activity of the surface of micro-nano zinc itself to form a stable surface adsorption for zinc ions in zinc chloride, covers the zinc ions on the surface of micro-nano zinc, and ionizes the surface of micro-nano zinc; during the temperature rising and standing process, as the temperature rises and exceeds the boiling point of ether, the ether can be quickly evaporated and removed to form an ethanol slurry. At the same time, zinc chloride has good solubility in both ether and ethanol. As the ether evaporates, the entire solvent is converted into an ethanol solvent, which does not affect the adsorption of micro-nano zinc and the dissolution of zinc chloride. Excess zinc chloride is removed during centrifugal filtration to obtain a micro-nano zinc material with zinc ions adsorbed on the surface;

[0011] Step 2, adding aspartic acid and glycine to N,N-dimethylformamide and ultrasonically treating for 20-30 minutes to obtain a soaking solution, wherein the mass ratio of aspartic acid to glycine is 5:5-6, the mass ratio of glycine to N,N-dimethylformamide is 1:5-7, the ultrasonic frequency of the ultrasonic treatment is 50-70kHz, and the temperature is 20-30°C;

[0012] Step 3, placing the surface adsorbed micro-nano zinc particles into a soaking solution for microwave reaction for 20-30 minutes, filtering after centrifugation to obtain amino acid zinc-encapsulated micro-nano zinc, the temperature of the microwave reaction is 300-500W, the temperature is 20-30°C, the concentration of the micro-nano zinc and the soaking solution is 1:2-4, this step uses microwaves to enhance the group activity of aspartic acid and glycine, and uses the zinc ions and defect activity on the surface of the micro-nano zinc to form adsorption traction on aspartic acid and glycine, thereby achieving stable and encapsulated adsorption on the surface of the micro-nano zinc, thereby achieving the encapsulation of the amino acid zinc complex system formed on the surface of the micro-nano zinc;

[0013] Step 4, adding γ-cyclodextrin to distilled water and performing ultrasonic treatment until it is completely dispersed to obtain a dissolving solution, and then adding the amino acid zinc-wrapped micro-nano zinc to the dissolving solution and performing microwave stirring treatment for 2-4 hours to obtain an inclusion solution, wherein the mass ratio of the γ-cyclodextrin to distilled water is 1:5-8, the frequency of the ultrasound is 50-70kHz, and the temperature is 30-50°C; the mass ratio of the amino acid zinc-wrapped micro-nano zinc to the γ-cyclodextrin is 2:5-7, the microwave power of the microwave stirring treatment is 100-300W, the stirring speed is 100-400r / min, and the temperature is 20-30°C; in this step, the γ-cyclodextrin is dissolved in water by ultrasound to form a dissolving solution, and during the microwave stirring process, the amino acid zinc-wrapped micro-nano zinc material is coated in the cyclodextrin, and the hollow cylindrical three-dimensional ring structure in the cyclodextrin itself is used to achieve the enveloping effect;

[0014] Step 5, homogenizing the inclusion liquid and then concentrating it in vacuum, and vacuum freeze-drying it to obtain a long-acting sustained-release amino acid micro-nano zinc material, wherein the stirring speed of the homogenization treatment is 2000-3000r / min, the concentration temperature of the vacuum concentration is 60-70°C, the vacuum degree is -0.06 to -0.08MPa, and the vacuum freeze-drying is rapid freeze-drying at -35°C; in this step, the inclusion liquid is homogenized to form a homogeneous structure, and then the saturated liquid is concentrated in the vacuum concentration, and then vacuum freeze-dried to obtain particles of the amino acid micro-nano zinc material.

[0015] The amino acid micro-nano zinc can be used in a disinfection solution, and the mass proportion of the amino acid micro-nano zinc in the disinfection solution is 2.5-5%.

[0016] Furthermore, the disinfectant solution also includes a stabilizer and a reducing agent, wherein the stabilizer accounts for 3-7% by weight and the reducing agent accounts for 0.8-5% by weight. The stabilizer is polyethylene oxide, ethylene oxide or propylene oxide, and the reducing agent is citric acid, ascorbic acid, formic acid or sodium borohydride.

[0017] It can be seen from the above description that the present invention has the following advantages:

[0018] 1. The present invention solves the defects of existing zinc-based fungicides, and uses amino acid zinc and micro-nano zinc to form an encapsulated complex structure, which effectively reduces the amount of zinc used. It not only meets the zinc limit regulations, but also uses amino acid zinc to form a stable complex structure to achieve long-term and high efficiency of sterilization.

[0019] 2. The present invention uses γ-cyclodextrin as an encapsulating agent to restrict the encapsulation of micro-nano zinc and amino acid zinc, thereby achieving an excellent sustained-release effect. At the same time, the material is stable in the disinfection solution, and there will be no macromolecular aggregation and product decomposition.

[0020] 3. The amino acid micro-nano zinc material prepared by the present invention presents a multiple-wrapping system, which not only effectively controls the exposed area of ​​the active group, but also internalizes the zinc element, and utilizes the non-toxicity and environmental stability of amino acids to ensure the safety and environmental protection of the material. DETAILED DESCRIPTION

[0021] The present invention is described in detail with reference to the embodiments, but no limitation is imposed on the claims of the present invention.

[0022] Example 1

[0023] A method for preparing a long-acting sustained-release amino acid micro-nano zinc material. The amino acid micro-nano zinc material uses micro-nano zinc as a core and an amino acid zinc complex as a surface coating to form a core-shell structure, and the core-shell structure is encapsulated in gamma-cyclodextrin.

[0024] The preparation method of the long-acting sustained-release micro-nano zinc material comprises the following steps:

[0025] Step 1, adding micro-nano zinc and zinc chloride to an ether-ethanol mixed solution for low-temperature ultrasonic dispersion for 20 minutes, then heating and standing for 20 minutes, and obtaining surface-adsorbed micro-nano zinc particles after centrifugal filtration, the mass ratio of micro-nano zinc and zinc chloride is 3:1, the volume ratio of ether and ethanol in the ether-ethanol mixed solution is 3:2, the concentration of micro-nano zinc in the ether-ethanol mixed solution is 100g / L, the temperature of the low-temperature ultrasonic dispersion is 5°C, the ultrasonic frequency is 40kHz, and the temperature of the heating and standing is 40°C; the preparation method of micro-nano zinc oxide comprises the following steps: a1, adding sodium chloride and zinc chloride to an ethanol-ether solution for low-temperature ultrasonic treatment for 2 hours to form a glue solution, the mass ratio of sodium chloride to zinc chloride is 5:2, the volume ratio of ethanol to ether in the ethanol-ether solution is 2:3, the mass ratio of sodium chloride to ethanol-ether solution is 2:3, and the low-temperature ultrasonic treatment The ultrasonic frequency is 10°C; the ultrasonic frequency is 50kHz; a2, the colloid is vacuum distilled for 30 minutes, dried to obtain a viscous colloid, and then ammonium carbonate is added and stirred evenly, and then low-temperature grinding is dried and granulated to obtain prefabricated particles. The vacuum distillation temperature is 50°C, the pressure is 70% of the atmospheric pressure, the drying temperature is 50°C, the amount of ammonium carbonate added is 90% of the mass of zinc chloride, the stirring speed is 500r / min, the low-temperature grinding temperature is 10°C; the pressure is 0.4MPa, the drying temperature is 30°C, the granulation temperature is 20°C, and the pressure is 0.5MPa; a3, ethyl cellulose is added to ether and stirred evenly to form a coating liquid, and then the coating liquid is evenly coated on the surface of the prefabricated particles, and the coating particles are dried at a constant temperature to obtain coated particles. The concentration of ethyl cellulose in ether is 200g / L, the stirring speed is 100r / min, and the coating amount is 5mL / cm 2, the temperature of constant temperature drying is 30℃; a4, the coated particles are kept at constant temperature and pressure for 2h, and then placed in an ether-glycerol mixture for ultrasonic dispersion for 20min to obtain a suspension, the temperature of the constant temperature and pressure is 80℃, the pressure is 0.2MPa, the volume ratio of ether to glycerol in the ether-glycerol mixture is 3:5, the concentration of the coated particles in the ether-glycerol mixture is 100g / L, the ultrasonic frequency of ultrasonic dispersion is 50kHz, and the temperature is 5℃; a5, the suspension is centrifuged, and the supernatant is removed, and then ultrasonic cleaning with ethanol and centrifugal separation are repeated twice and then spray-dried to obtain micro-nano zinc oxide particles, the ultrasonic frequency of ethanol ultrasonic cleaning is 40kHz, and the temperature is 10℃; the temperature of spray drying is 130℃, and finally the slurry is sprayed at 100cm after centrifugation. 2 In a6, the micro-nano zinc oxide particles are treated with constant temperature light for 30 minutes to obtain activated zinc oxide particles. The constant temperature light treatment is irradiated with visible light, and the temperature is 30°C and the light intensity is 1W / cm 2 ;

[0026] Step 2, adding aspartic acid and glycine to N,N-dimethylformamide and ultrasonically treating for 20 minutes to obtain a soaking solution, wherein the mass ratio of aspartic acid to glycine is 5:5, the mass ratio of glycine to N,N-dimethylformamide is 1:5, the ultrasonic frequency of the ultrasonic treatment is 50 kHz, and the temperature is 20°C;

[0027] Step 3, placing the surface adsorbed micro-nano zinc particles into a soaking solution for microwave reaction for 20 minutes, filtering after centrifugation to obtain amino acid zinc-encapsulated micro-nano zinc, the temperature of the microwave reaction is 300W, the temperature is 20°C, and the concentration of the micro-nano zinc to the soaking solution is 1:2;

[0028] Step 4, adding γ-cyclodextrin to distilled water and ultrasonically dispersing it completely to obtain a dissolved solution, and then adding amino acid zinc-wrapped micro-nano zinc to the dissolved solution and stirring it in a microwave for 2 hours to obtain an inclusion solution, wherein the mass ratio of the γ-cyclodextrin to distilled water is 1:5, the frequency of the ultrasound is 50 kHz, and the temperature is 30°C; the mass ratio of the amino acid zinc-wrapped micro-nano zinc to γ-cyclodextrin is 2:5, and the microwave power of the microwave stirring treatment is 100 W, the stirring speed is 100 r / min, and the temperature is 20°C;

[0029] Step 5, homogenize the inclusion liquid and then concentrate it in vacuum, and then freeze-dry it in vacuum to obtain a long-acting sustained-release amino acid micro-nano zinc material. The stirring speed of the homogenization treatment is 2000r / min, the concentration temperature of the vacuum concentration is 60°C, the vacuum degree is -0.06MPa, and the vacuum freeze-drying is rapid freeze-drying at -35°C.

[0030] The amino acid micro-nano zinc can be used in a disinfection solution, and the amino acid micro-nano zinc accounts for 2.5% by weight in the disinfection solution. The disinfection solution also includes a stabilizer and a reducing agent, the stabilizer accounts for 3% by weight, and the reducing agent accounts for 0.8% by weight. The stabilizer is polyethylene oxide, and the reducing agent is citric acid; the remainder is water.

[0031] Example 2

[0032] A method for preparing a long-acting sustained-release amino acid micro-nano zinc material. The amino acid micro-nano zinc material uses micro-nano zinc as a core and an amino acid zinc complex as a surface coating to form a core-shell structure, and the core-shell structure is encapsulated in gamma-cyclodextrin.

[0033] The preparation method of the long-acting sustained-release micro-nano zinc material comprises the following steps:

[0034] Step 1, adding micro-nano zinc and zinc chloride to an ether-ethanol mixed solution for low-temperature ultrasonic dispersion for 30 minutes, then heating and standing for 30 minutes, and obtaining surface-adsorbed micro-nano zinc particles after centrifugal filtration, the mass ratio of micro-nano zinc and zinc chloride is 3:2, the volume ratio of ether and ethanol in the ether-ethanol mixed solution is 5:2, the concentration of micro-nano zinc in the ether-ethanol mixed solution is 200g / L, the temperature of the low-temperature ultrasonic dispersion is 10°C, the ultrasonic frequency is 70kHz, and the temperature of the heating and standing is 60°C; the preparation method of micro-nano zinc oxide comprises the following steps: a1, adding sodium chloride and zinc chloride to an ethanol-ether solution for low-temperature ultrasonic treatment for 3 hours to form a glue solution, the mass ratio of sodium chloride to zinc chloride is 7:2, the volume ratio of ethanol to ether in the ethanol-ether solution is 2:5, the mass ratio of sodium chloride to ethanol-ether solution is 2:4, and the low-temperature ultrasonic treatment The ultrasonic frequency is 20°C; the ultrasonic frequency is 80kHz; a2, the colloid is vacuum distilled for 60 minutes, dried to obtain a viscous colloid, and then ammonium carbonate is added and stirred evenly, and then low-temperature grinding is dried and granulated to obtain prefabricated particles. The vacuum distillation temperature is 60°C, the pressure is 80% of the atmospheric pressure, the drying temperature is 60°C, the amount of ammonium carbonate added is 100% of the mass of zinc chloride, the stirring speed is 800r / min, the low-temperature grinding temperature is 20°C; the pressure is 0.6MPa, the drying temperature is 40°C, the granulation temperature is 30°C, and the pressure is 0.6MPa; a3, ethyl cellulose is added to ether and stirred evenly to form a coating liquid, and then the coating liquid is evenly coated on the surface of the prefabricated particles, and the coating particles are dried at a constant temperature to obtain coated particles. The concentration of ethyl cellulose in ether is 500g / L, the stirring speed is 200r / min, and the coating amount is 8mL / cm 2, the temperature of constant temperature drying is 40℃; a4, the coated particles are kept at constant temperature and pressure for 4h, and then placed in an ether-glycerol mixture for ultrasonic dispersion for 30min to obtain a suspension, the temperature of the constant temperature and pressure is 90℃, the pressure is 0.3MPa, the volume ratio of ether and glycerol in the ether-glycerol mixture is 3:7, the concentration of the coated particles in the ether-glycerol mixture is 200g / L, the ultrasonic frequency of ultrasonic dispersion is 70kHz, and the temperature is 10℃; a5, the suspension is centrifuged, and the supernatant is removed, and then ultrasonic cleaning with ethanol and centrifugal separation are repeated 4 times and then spray-dried to obtain micro-nano zinc oxide particles, the ultrasonic frequency of ethanol ultrasonic cleaning is 60kHz, and the temperature is 20℃; the temperature of spray drying is 140℃, and finally the slurry is sprayed at 200cm after centrifugation. 2 In a6, the micro-nano zinc oxide particles are treated with constant temperature light for 40 minutes to obtain activated zinc oxide particles. The constant temperature light treatment is irradiated with visible light, and the temperature is 50°C and the light intensity is 3W / cm 2 ;

[0035] Step 2, adding aspartic acid and glycine to N,N-dimethylformamide and ultrasonically treating for 30 minutes to obtain a soaking solution, wherein the mass ratio of aspartic acid to glycine is 5:6, the mass ratio of glycine to N,N-dimethylformamide is 1:7, the ultrasonic frequency of the ultrasonic treatment is 70 kHz, and the temperature is 30° C.;

[0036] Step 3, placing the surface adsorbed micro-nano zinc particles into a soaking solution for microwave reaction for 30 minutes, filtering after centrifugation to obtain amino acid zinc-encapsulated micro-nano zinc, the temperature of the microwave reaction is 500W, the temperature is 30°C, and the concentration of the micro-nano zinc to the soaking solution is 1:4;

[0037] Step 4, adding γ-cyclodextrin to distilled water and performing ultrasonic treatment until it is completely dispersed to obtain a dissolved solution, and then adding amino acid zinc-wrapped micro-nano zinc to the dissolved solution and performing microwave stirring treatment for 4 hours to obtain an inclusion solution, wherein the mass ratio of the γ-cyclodextrin to distilled water is 1:8, the frequency of the ultrasound is 70 kHz, and the temperature is 50°C; the mass ratio of the amino acid zinc-wrapped micro-nano zinc to γ-cyclodextrin is 2:7, and the microwave power for the microwave stirring treatment is 300 W, the stirring speed is 400 r / min, and the temperature is 30°C;

[0038] Step 5, homogenizing the inclusion liquid and then concentrating it in vacuum, and vacuum freeze-drying it to obtain a long-acting sustained-release amino acid micro-nano zinc material, the stirring speed of the homogenization treatment is 3000r / min, the concentration temperature of the vacuum concentration is 70°C, the vacuum degree is -0.08MPa, and the vacuum freeze-drying is rapid freeze-drying at -35°C.

[0039] The amino acid micro-nano zinc can be used in a disinfection solution, and the amino acid micro-nano zinc accounts for 5% by weight in the disinfection solution. The disinfection solution also includes a stabilizer and a reducing agent, the stabilizer accounts for 7% by weight, and the reducing agent accounts for 5% by weight. The stabilizer is ethylene oxide, and the reducing agent is ascorbic acid; the remainder is water.

[0040] Example 3

[0041] A method for preparing a long-acting sustained-release amino acid micro-nano zinc material. The amino acid micro-nano zinc material uses micro-nano zinc as a core and an amino acid zinc complex as a surface coating to form a core-shell structure, and the core-shell structure is encapsulated in gamma-cyclodextrin.

[0042] The preparation method of the long-acting sustained-release micro-nano zinc material comprises the following steps:

[0043] Step 1, adding micro-nano zinc and zinc chloride to an ether-ethanol mixed solution for low-temperature ultrasonic dispersion for 25 minutes, then heating and standing for 25 minutes, and obtaining surface-adsorbed micro-nano zinc particles after centrifugal filtration, the mass ratio of micro-nano zinc and zinc chloride is 3:1, the volume ratio of ether and ethanol in the ether-ethanol mixed solution is 2:1, the concentration of micro-nano zinc in the ether-ethanol mixed solution is 150g / L, the temperature of the low-temperature ultrasonic dispersion is 8°C, the ultrasonic frequency is 60kHz, and the temperature of the heating and standing is 50°C; the preparation method of micro-nano zinc oxide comprises the following steps: a1, adding sodium chloride and zinc chloride to an ethanol-ether solution for low-temperature ultrasonic treatment for 2 hours to form a glue solution, the mass ratio of sodium chloride to zinc chloride is 3:1, the volume ratio of ethanol to ether in the ethanol-ether solution is 1:2, the mass ratio of sodium chloride to ethanol-ether solution is 2:3, and the low-temperature ultrasonic treatment The ultrasonic frequency is 15°C; the ultrasonic frequency is 70kHz; a2, the colloid is vacuum distilled for 50 minutes, dried to obtain a viscous colloid, and then ammonium carbonate is added and stirred evenly, and then low-temperature grinding is dried and granulated to obtain prefabricated particles. The vacuum distillation temperature is 55°C, the pressure is 75% of the atmospheric pressure, the drying temperature is 55°C, the amount of ammonium carbonate added is 95% of the mass of zinc chloride, the stirring speed is 700r / min, the low-temperature grinding temperature is 15°C; the pressure is 0.5MPa, the drying temperature is 35°C, the granulation temperature is 25°C, and the pressure is 0.6MPa; a3, ethyl cellulose is added to ether and stirred evenly to form a coating liquid, and then the coating liquid is evenly coated on the surface of the prefabricated particles, and the coating particles are dried at a constant temperature to obtain coated particles. The concentration of ethyl cellulose in ether is 400g / L, the stirring speed is 150r / min, and the coating amount is 7mL / cm 2, the temperature of constant temperature drying is 35℃; a4, the coated particles are allowed to stand at constant temperature and pressure for 3h, and then placed in an ether-glycerol mixture for ultrasonic dispersion for 25min to obtain a suspension, the temperature of the constant temperature and pressure is 85℃, the pressure is 0.2MPa, the volume ratio of ether to glycerol in the ether-glycerol mixture is 1:2, the concentration of the coated particles in the ether-glycerol mixture is 150g / L, the ultrasonic frequency of ultrasonic dispersion is 60kHz, and the temperature is 8℃; a5, the suspension is centrifuged, and the supernatant is removed, and then ultrasonic cleaning with ethanol and centrifugal separation are repeated 3 times and then spray-dried to obtain micro-nano zinc oxide particles, the ultrasonic frequency of ethanol ultrasonic cleaning is 50kHz, and the temperature is 15℃; the spray drying temperature is 135℃, and finally the slurry is sprayed at 150cm after centrifugation. 2 In a6, the micro-nano zinc oxide particles are treated with constant temperature light for 35 minutes to obtain activated zinc oxide particles. The constant temperature light treatment is irradiated with visible light, and the temperature is 40°C and the light intensity is 2W / cm 2 ;

[0044] Step 2, adding aspartic acid and glycine to N,N-dimethylformamide and ultrasonically treating for 25 minutes to obtain a soaking solution, wherein the mass ratio of aspartic acid and glycine is 1:1, the mass ratio of glycine to N,N-dimethylformamide is 1:6, and the ultrasonic frequency of the ultrasonic treatment is 60 kHz and the temperature is 25° C.;

[0045] Step 3, placing the surface adsorbed micro-nano zinc particles into a soaking solution for microwave reaction for 25 minutes, filtering after centrifugation to obtain amino acid zinc-encapsulated micro-nano zinc, the microwave reaction temperature is 400W, the temperature is 25°C, and the concentration of the micro-nano zinc to the soaking solution is 1:3;

[0046] Step 4, adding γ-cyclodextrin to distilled water and ultrasonically dispersing it completely to obtain a dissolving solution, and then adding the amino acid zinc-wrapped micro-nano zinc to the dissolving solution and stirring it with microwaves for 3 hours to obtain an inclusion solution, wherein the mass ratio of the γ-cyclodextrin to distilled water is 1:7, the frequency of the ultrasound is 60kHz, and the temperature is 40°C; the mass ratio of the amino acid zinc-wrapped micro-nano zinc to the γ-cyclodextrin is 1:3, and the microwave power of the microwave stirring treatment is 200W, the stirring speed is 300r / min, and the temperature is 25°C;

[0047] Step 5, homogenizing the inclusion liquid and then concentrating it in vacuum, and vacuum freeze-drying it to obtain a long-acting sustained-release amino acid micro-nano zinc material, the stirring speed of the homogenization treatment is 2500r / min, the concentration temperature of the vacuum concentration is 65°C, the vacuum degree is -0.07MPa, and the vacuum freeze-drying is rapid freeze-drying at -35°C.

[0048] The amino acid micro-nano zinc can be used in a disinfection solution, and the amino acid micro-nano zinc accounts for 4% by weight in the disinfection solution. The disinfection solution also includes a stabilizer and a reducing agent, the stabilizer accounts for 6% by weight, and the reducing agent accounts for 3% by weight. The stabilizer is propylene oxide, and the reducing agent is formic acid; the remainder is water.

[0049] Performance Testing

[0050] Escherichia coli and Staphylococcus aureus were used as bacterial species for antibacterial experiments, and the disinfectant solutions prepared in Examples 1-3 were used as test examples for water sterilization tests. Escherichia coli and Staphylococcus aureus were diluted with bacterial solution (0.9×10 6 cfu / mL), then add the disinfectant solution and stir evenly, let it stand for 2 hours to test the initial antibacterial rate, and let it stand for 15 days to test the long-term antibacterial rate.

[0051]

[0052] It is understood that the above specific description of the present invention is only used to illustrate the present invention and is not limited to the technical solutions described in the embodiments of the present invention. Those skilled in the art should understand that the present invention can still be modified or replaced by equivalents to achieve the same technical effects; as long as the use requirements are met, they are within the protection scope of the present invention.

Claims

1. A method for preparing a long-acting sustained-release amino acid micro-nano zinc oxide material, characterized in that: The amino acid micro-nano zinc oxide material has micro-nano zinc oxide as the core and an amino acid zinc complex as the surface coating to form a core-shell structure, and the core-shell structure is encapsulated in γ-cyclodextrin; The preparation method of the long-acting sustained-release amino acid micro-nano zinc oxide material comprises the following steps: Step 1, adding micro-nano zinc oxide and zinc chloride to an ether-ethanol mixed solution and dispersing them by ultrasonic at low temperature for 20-30 minutes, then heating and standing for 20-30 minutes, and centrifugally filtering to obtain surface-adsorbed micro-nano zinc oxide particles; Step 2, adding aspartic acid and glycine to N,N-dimethylformamide and ultrasonically treating for 20-30 minutes to obtain a soaking solution; Step 3, placing the surface-adsorbed micro-nano zinc oxide particles into a soaking solution for microwave reaction for 20-30 minutes, and filtering after centrifugation to obtain amino acid zinc-coated micro-nano zinc oxide; Step 4, adding γ-cyclodextrin to distilled water and performing ultrasonic treatment until it is completely dispersed to obtain a dissolving solution, and then adding amino acid zinc-encapsulated micro-nano zinc oxide to the dissolving solution and performing microwave stirring for 2-4 hours to obtain an inclusion solution; Step 5, homogenizing the inclusion liquid, concentrating it in vacuum, and freeze-drying it in vacuum to obtain a long-acting sustained-release amino acid micro-nano zinc oxide material.

2. The method for preparing the long-acting sustained-release amino acid micro-nano zinc oxide material according to claim 1, characterized in that: The mass ratio of the micro-nano zinc oxide to the zinc chloride in the step 1 is 3:1-2, the volume ratio of ether to ethanol in the ether-ethanol mixture is 3-5:2, the concentration of the micro-nano zinc oxide in the ether-ethanol mixture is 100-200 g / L, the temperature of the low-temperature ultrasonic dispersion is 5-10°C, the ultrasonic frequency is 40-70 kHz, and the temperature of the heating and standing is 40-60°C.

3. The method for preparing the long-acting sustained-release amino acid micro-nano zinc oxide material according to claim 1, characterized in that: The mass ratio of aspartic acid to glycine in step 2 is 5:5-6, the mass ratio of glycine to N,N-dimethylformamide is 1:5-7, the ultrasonic frequency of the ultrasonic treatment is 50-70 kHz, and the temperature is 20-30°C.

4. The method for preparing the long-acting sustained-release amino acid micro-nano zinc oxide material according to claim 1, characterized in that: The temperature of the microwave reaction in step 3 is 300-500W, the temperature is 20-30°C, and the concentration of the micro-nano zinc oxide and the soaking solution is 1:2-4.

5. The method for preparing the long-acting sustained-release amino acid micro-nano zinc oxide material according to claim 1, characterized in that: The mass ratio of γ-cyclodextrin to distilled water in step 4 is 1:5-8, the frequency of ultrasound is 50-70kHz, and the temperature is 30-50°C; the mass ratio of amino acid zinc-encapsulated micro-nano zinc oxide to γ-cyclodextrin is 2:5-7, the microwave power of microwave stirring treatment is 100-300W, the stirring speed is 100-400r / min, and the temperature is 20-30°C.

6. The method for preparing the long-acting sustained-release amino acid micro-nano zinc oxide material according to claim 1, characterized in that: The stirring speed of the homogenization treatment in step 5 is 2000-3000 r / min, the concentration temperature of the vacuum concentration is 60-70°C, the vacuum degree is -0.06 to -0.08 MPa, and the vacuum freeze drying is rapid freeze drying at -35°C.

7. The method for preparing the long-acting sustained-release amino acid micro-nano zinc oxide material according to claim 1, characterized in that: The amino acid micro-nano zinc oxide can be used in an aqueous disinfection solution, and the mass proportion of the amino acid micro-nano zinc oxide in the disinfection solution is 2.5-5%.

8. The method for preparing the long-acting sustained-release amino acid micro-nano zinc oxide material according to claim 7, characterized in that: The disinfection solution also includes a stabilizer and a reducing agent, wherein the stabilizer accounts for 3-7% by weight and the reducing agent accounts for 0.8-5% by weight.

9. The method for preparing the long-acting sustained-release amino acid micro-nano zinc oxide material according to claim 8, characterized in that: The stabilizer is polyethylene oxide, ethylene oxide or propylene oxide, and the reducing agent is citric acid, ascorbic acid, formic acid or sodium borohydride.

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