Core-shell structure antibacterial material as well as preparation method and application thereof
By loading Cu@Ag nanoparticles onto the core-shell structure antibacterial material prepared by loading Cu@Ag nanoparticles onto the carrier material, the problems of poor quality stability of the added flavors and easy contamination of microorganisms are solved, and efficient sterilization and convenient separation of flavors and fragrances are achieved, with good application prospects.
Patent Information
- Application Number
- CN202411706551.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-26
- Publication Date
- 2025-03-11
AI Technical Summary
The existing flavors of ingredients have a short shelf life due to poor quality stability and easy contamination of microorganisms, causing economic losses to cigarette companies.
The core-shell structure antibacterial material is used to load Cu@Ag nanoparticles onto carrier materials such as 3A molecular sieve, 4A molecular sieve, 13X molecular sieve, activated carbon balls or silica gel, and prepare through an impregnation process to achieve the sterilization treatment of tobacco flavors.
It has achieved an antibacterial material with excellent sterilization effect and easy separation from flavors and fragrances. It has a simple preparation process and good practical application prospects.
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Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of antibacterial materials, and in particular to a core-shell structure antibacterial material and a preparation method and application thereof. Background Art
[0002] The proportion of flavors and fragrances in the fine chemical industry has been increasing year by year, among which tobacco flavors and fragrances account for 12% of the market share. Tobacco flavors are made of a variety of spices, appropriate amounts of solvents and other ingredients. They are important raw materials in the production and processing of cigarettes. They have the functions of improving tobacco smell, increasing toughness and improving combustion, and are related to the composition of the characteristic flavor of cigarette brands. However, because added flavors contain a large amount of water and sugars and other substances, their quality stability is poor and difficult to control. They are easily contaminated by microorganisms and produce sourness and odor, which shortens the shelf life and causes serious economic losses to companies.
[0003] Antimicrobial agents are generally divided into inorganic antimicrobial agents, organic antimicrobial agents and natural antimicrobial agents. Inorganic antimicrobial agents use the antimicrobial ability of metals such as silver, copper and zinc. They have a series of advantages such as broad-spectrum antimicrobial, high temperature resistance, strong durability, excellent biocompatibility and formaldehyde degradation. They are widely used in various fields such as food, medicine, fabrics, building materials, and coatings. Among inorganic antimicrobial agents, silver has the strongest bactericidal ability, which mainly produces antimicrobial ability by destroying cell walls / cell membranes, inhibiting bacterial respiratory chains, inducing genetic toxicity, inducing reactive oxygen free radicals, and inducing photocatalytic protein damage.
[0004] In order to improve the safety performance of products, antibacterial materials should avoid introducing harmful substances to the human body as much as possible during design and production. Molecular sieves and silica gel are composed of completely harmless substances and are very suitable for use in the research and development of antibacterial products for food and daily chemicals. Core-shell antibacterial materials combine metallic silver with molecular sieves or silica gel as base materials, which can not only be efficiently used in the sterilization of tobacco flavors and fragrances, but also realize the convenient recycling of antibacterial materials. Summary of the invention
[0005] The technical problem to be solved by the present invention is to provide a core-shell structure antibacterial material and a preparation method and application thereof. The core-shell structured Cu@Ag nanoparticles are used as antibacterial active components and 3A molecular sieves, 4A molecular sieves, 13X molecular sieves, activated carbon balls, silica gel, etc. are used as carrier materials. The core-shell structured antibacterial material is prepared through an impregnation process, thereby obtaining an antibacterial material with excellent bactericidal effect and easy separation from flavors and fragrances. The preparation process of the antibacterial material is simple and has good practical application prospects.
[0006] The technical problem to be solved by the present invention is achieved through the following technical solutions:
[0007] A core-shell structure antibacterial material comprises: an antibacterial active material and a carrier material. The antibacterial active material is a nanoparticle with metal Ag as a shell and metal Cu as a core. The core-shell structure antibacterial material can be obtained by loading the antibacterial active component onto the carrier material.
[0008] Preferably, in the above technical solution, the mass fraction of Ag in the core-shell structure antibacterial material is 0.02% to 2%, and the mass fraction of Cu is 0.5% to 10%.
[0009] Preferably, in the above technical solution, the Ag comes from a soluble Ag salt, and the Cu comes from a soluble Cu salt; the soluble Ag salt is selected from at least one of silver nitrate, diammine silver nitrate, and silver sulfate; the soluble Cu salt is selected from at least one of copper acetate, cupric chloride dihydrate, cupric bromide dihydrate, copper sulfate pentahydrate, copper nitrate trihydrate, and copper thiosulfate.
[0010] Preferably, in the above technical solution, the carrier material is selected from at least one of 3A molecular sieve, 4A molecular sieve, 13X molecular sieve, activated carbon balls and silica gel.
[0011] Preferably, in the above technical solution, the loading method is to load the antimicrobial active component onto the carrier material by an impregnation method, and the impregnation method is carried out at 20-80° C. under closed conditions.
[0012] A method for preparing a core-shell structure antibacterial material comprises the following steps:
[0013] (1) dispersing a certain amount of soluble copper salt and soluble silver salt in an appropriate amount of oleylamine and tri-n-octylphosphine at room temperature;
[0014] (2) Under argon atmosphere, the mixed solution was heated to 245°C at a heating rate of 5°C / min and maintained for 60 min, and the color of the solution changed;
[0015] (3) adding isopropanol to the mixed solution and centrifuging to obtain nanoparticles containing impurities;
[0016] (4) Re-dispersing and purifying in a mixed solution of n-hexane, ethanol and isopropanol to obtain an antibacterial active component (Cu@Ag NPs) for later use;
[0017] (5) The antibacterial active component (Cu@Ag NPs) is dispersed in ethanol, a certain amount of carrier material is added to the mixed solution, and the mixture is immersed at 20 to 80° C. for 8 to 12 hours to obtain the core-shell structure antibacterial material.
[0018] Preferably, in the above technical scheme, in step (1), the mass ratio of Ag salt to Cu salt is (0.02-2):(0.5-10), and the mass ratio of Ag salt to oleylamine and tri-n-octylphosphine is 1:(100-250):(1-10); in step (3), the mass ratio of isopropanol to the mixed solution is (2-5):1; in step (4), the volume ratio of n-hexane, ethanol and isopropanol is 1:(3-6):(2-7); in step (5), the mass ratio of the antibacterial active component (Cu@Ag NPs) to the carrier material is 1:100-200.
[0019] Preferably, in the above technical solution, the immersion temperature is selected from any value of 20°C, 40°C, 60°C, 80°C or a range between any two of them, and the immersion time is selected from any value of 8h, 10h, 12h or a range between any two of them.
[0020] Application of a core-shell structure antibacterial material in the antibacterial application of tobacco flavors and fragrances.
[0021] Preferably, in the above technical solution, the application is to sterilize tobacco flavors and fragrances using the core-shell structure antibacterial material, specifically including:
[0022] S1. Load 1 / 4 volume of the core-shell structure antibacterial material in the treatment tank;
[0023] S2. Add the prepared tobacco flavors and spices into the processing tank, stir for 1 hour, and let stand for 1 hour;
[0024] S3. After sterilization, filter and recover the core-shell structure antibacterial material, and reuse it after drying.
[0025] The above technical solution of the present invention has the following beneficial effects:
[0026] The silver-loaded glass antibacterial material provided in the present application can continuously exert antibacterial effects, is safe and non-toxic, has a low content of effective antibacterial components, has long-lasting antibacterial properties, and is easy to recycle and reuse. DETAILED DESCRIPTION
[0027] Various exemplary embodiments of the present invention will now be described in detail. It should be noted that the relative arrangement of components and steps, numerical expressions and numerical values set forth in these embodiments do not limit the scope of the present invention unless specifically stated otherwise.
[0028] Unless otherwise specified, the reagents used in this application are all commercially available or obtained through commercial channels, or can be prepared by referring to existing chemical methods.
[0029] Example 1
[0030] First, 1.57 g of copper acetate and 0.0786 g of silver nitrate were dispersed in 20 ml of oleylamine and 0.3 ml of tri-n-octylphosphine at room temperature;
[0031] Secondly, the mixed solution was heated to 245 °C at a heating rate of 5 °C / min under an argon atmosphere and maintained for 60 min, and the color of the solution changed;
[0032] Then, 2.5 times the mass of isopropanol was added to the mixed solution and centrifuged to obtain nanoparticles containing impurities;
[0033] Finally, the antibacterial active component (Cu@Ag NPs) was redispersed and purified in a mixed solution of n-hexane, ethanol and isopropanol in a volume ratio of 1:3:5 for later use.
[0034] The antibacterial active component (Cu@Ag NPs) is dispersed in ethanol, 10.0 g of 3A molecular sieve is added to the mixed solution, and the mixture is immersed at 20 to 80° C. for 8 to 12 hours to obtain the core-shell structure antibacterial material.
[0035] Example 2
[0036] First, 2.69 g of copper chloride dihydrate and 0.1572 g of silver nitrate were dispersed in 20 ml of oleylamine and 0.3 ml of tri-n-octylphosphine at room temperature;
[0037] Secondly, the mixed solution was heated to 245 °C at a heating rate of 5 °C / min under an argon atmosphere and maintained for 60 min, and the color of the solution changed;
[0038] Then, 3 times the mass of isopropanol was added to the mixed solution and centrifuged to obtain nanoparticles containing impurities;
[0039] Finally, the antibacterial active component (Cu@Ag NPs) was redispersed and purified in a mixed solution of n-hexane, ethanol and isopropanol in a volume ratio of 1:4:2 for later use.
[0040] The antibacterial active component (Cu@Ag NPs) is dispersed in ethanol, 10.0 g of 4A molecular sieve is added to the mixed solution, and the mixture is immersed at 20 to 80° C. for 8 to 12 hours to obtain the core-shell structure antibacterial material.
[0041] Example 3
[0042] First, 1.57 g of copper acetate and 0.0786 g of silver nitrate were dispersed in 20 ml of oleylamine and 0.3 ml of tri-n-octylphosphine at room temperature;
[0043] Secondly, the mixed solution was heated to 245 °C at a heating rate of 5 °C / min under an argon atmosphere and maintained for 60 min, and the color of the solution changed;
[0044] Then, 4 times the mass of isopropanol was added to the mixed solution and centrifuged to obtain nanoparticles containing impurities;
[0045] Finally, the antibacterial active component (Cu@Ag NPs) was redispersed and purified in a mixed solution of n-hexane, ethanol and isopropanol in a volume ratio of 1:5:6 for later use.
[0046] The antibacterial active component (Cu@Ag NPs) is dispersed in ethanol, 10.0 g of 13X molecular sieve is added to the mixed solution, and the mixture is immersed at 20 to 80° C. for 8 to 12 hours to obtain the core-shell structure antibacterial material.
[0047] Example 4
[0048] First, 1.57 g of copper acetate and 0.0786 g of silver nitrate were dispersed in 20 ml of oleylamine and 0.3 ml of tri-n-octylphosphine at room temperature;
[0049] Secondly, the mixed solution was heated to 245 °C at a heating rate of 5 °C / min under an argon atmosphere and maintained for 60 min, and the color of the solution changed;
[0050] Then, 5 times the mass of isopropanol was added to the mixed solution and centrifuged to obtain nanoparticles containing impurities;
[0051] Finally, the antibacterial active component (Cu@Ag NPs) was redispersed and purified in a mixed solution of n-hexane, ethanol and isopropanol in a volume ratio of 1:4:7 for later use.
[0052] The antibacterial active component (Cu@Ag NPs) is dispersed in ethanol, 10.0 g of silica gel particles are added to the mixed solution, and the mixture is immersed at 20 to 80° C. for 8 to 12 hours to obtain the core-shell structure antibacterial material.
[0053] Application Examples
[0054] First, load 1 / 4 volume of the core-shell antibacterial material in the treatment tank; secondly, add the prepared golden leaf (mango) finished flavor and fragrance (provided by Henan Zhongyan Zhumadian Cigarette Factory) into the treatment tank, stir for 1 hour, and let stand for 1 hour; then, separate the tobacco flavor and fragrance for antibacterial test. The results are shown in Table 1 and Table 2; finally, filter and recover the core-shell antibacterial material, dry and reuse it. The above flavors and fragrances are not limited to this, and common products in the field can also be used instead.
[0055] Table 1 Test results of core-shell structure antibacterial materials
[0056]
[0057] Table 2 Test results of core-shell structure antibacterial materials
[0058]
[0059]
[0060] Although the present invention has been disclosed as above by the embodiments, it is not intended to limit the present invention. Any person skilled in the art may make various choices and modifications without departing from the spirit and scope of the present invention. Therefore, the protection scope of the present invention is limited by the claims and their equivalents.
Claims
1. A core-shell structure antibacterial material, characterized in that: include: Antibacterial active material and carrier material, the antibacterial active material is a nanoparticle with metal Ag as the shell and metal Cu as the core, and the core-shell structure antibacterial material can be obtained by loading the antibacterial active component onto the carrier material.
2. The core-shell structure antibacterial material according to claim 1, characterized in that: The mass fraction of Ag in the core-shell structure antibacterial material is 0.02% to 2%, and the mass fraction of Cu is 0.5% to 10%.
3. The core-shell structure antibacterial material according to claim 2, characterized in that: The Ag comes from a soluble Ag salt, and the Cu comes from a soluble Cu salt; the soluble Ag salt is selected from at least one of silver nitrate, diammine silver nitrate, and silver sulfate; the soluble Cu salt is selected from at least one of copper acetate, cupric chloride dihydrate, cupric bromide dihydrate, copper sulfate pentahydrate, copper nitrate trihydrate, and copper thiosulfate.
4. The core-shell structure antibacterial material according to claim 1, characterized in that: The carrier material is selected from at least one of 3A molecular sieve, 4A molecular sieve, 13X molecular sieve, activated carbon balls and silica gel.
5. The core-shell structure antibacterial material according to claim 1, characterized in that: The loading method is to load the antibacterial active components onto the carrier material by an impregnation method, wherein the impregnation method is performed at 20-80° C. under a closed condition.
6. The method for preparing the core-shell structure antibacterial material according to any one of claims 1 to 5, characterized in that: The following steps are involved: (1) dispersing a certain amount of soluble copper salt and soluble silver salt in an appropriate amount of oleylamine and tri-n-octylphosphine at room temperature; (2) Under argon atmosphere, the mixed solution was heated to 245°C at a heating rate of 5°C / min and maintained for 60 min, and the color of the solution changed; (3) adding isopropanol to the mixed solution and centrifuging to obtain nanoparticles containing impurities; (4) Re-dispersing and purifying in a mixed solution of n-hexane, ethanol and isopropanol to obtain an antibacterial active component (Cu@AgNPs) for later use; (5) The antibacterial active component (Cu@Ag NPs) is dispersed in ethanol, a certain amount of carrier material is added to the mixed solution, and the mixture is immersed at 20 to 80° C. for 8 to 12 hours to obtain the core-shell structure antibacterial material.
7. The method for preparing a core-shell structure antibacterial material according to claim 6, characterized in that: In step (1), the mass ratio of Ag salt to Cu salt is (0.02-2):(0.5-10), and the mass ratio of Ag salt to oleylamine and tri-n-octylphosphine is 1:(100-250):(1-10); in step (3), the mass ratio of isopropanol to the mixed solution is (2-5):1; in step (4), the volume ratio of n-hexane, ethanol and isopropanol is 1:(3-6):(2-7); in step (5), the mass ratio of the antibacterial active component (Cu@Ag NPs) to the carrier material is 1:100-200.
8. The method for preparing a core-shell structure antibacterial material according to claim 6, characterized in that: The immersion temperature is selected from any value among 20°C, 40°C, 60°C, 80°C or any range between two values, and the immersion time is selected from any value among 8h, 10h, 12h or any range between two values.
9. Application of a core-shell structure antibacterial material in the antibacterial application of tobacco flavors and fragrances, characterized in that: The core-shell structure antibacterial material is a core-shell structure antibacterial material according to any one of claims 1 to 5 or a core-shell structure antibacterial material prepared by the preparation method according to any one of claims 6 to 8.
10. The use according to claim 9, characterized in that: The application is to sterilize tobacco flavors and fragrances using core-shell structure antibacterial materials, specifically including: S1. Load 1 / 4 volume of the core-shell structure antibacterial material in the treatment tank; S2. Add the prepared tobacco flavors and spices into the processing tank, stir for 1 hour, and let stand for 1 hour; S3. After sterilization, filter and recover the core-shell structure antibacterial material, and reuse it after drying.