Rare earth composite material with oral antibacterial activity as well as preparation method and application of rare earth composite material
By combining gold and copper nanoclusters with rare earths and glutathione, the rare earth composite material RE-AuCuNCs@GSH in the prior art solves the environmental and health risks of chemical antibacterial agents, achieving efficient antibacterial effect on E. coli, and maintaining oral ecological balance.
Patent Information
- Application Number
- CN202510376847.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-28
- Publication Date
- 2025-06-27
AI Technical Summary
In the prior art, when solving the problem of antibiotic resistance, the chemical antibacterial agents used pose pollution and health risks to the environment, and it is difficult to effectively inhibit stubborn bacteria in the oral cavity.
The rare earth composite material RE-AuCuNCs@GSH is used. This material forms a complex with high-efficiency antibacterial function by compounding gold-copper nanoclusters with rare earths and glutathione, and applies it to antibacterial rare earth oral wash.
This material has efficient antibacterial properties for E. coli, can effectively deal with stubborn bacteria in the oral cavity, maintain oral ecological balance, and its antibacterial properties are relatively time-consuming.
Smart Images
Figure CN120204070A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of antibacterial materials, and in particular relates to a rare earth composite material with oral antibacterial activity, a preparation method thereof and an application thereof. Background Art
[0002] Antimicrobial resistance (AMR) is one of the biggest problems faced by industrialized countries in the world. It has a significant impact on the ecosystem and a negative impact on human health. The use of personal care products containing antimicrobials plays an important role in the spread of antibiotic resistance. In addition, the overuse of antibiotics in the healthcare and agricultural food industries is also a major factor. Facial cleansers, creams, shampoos, soaps, body washes, toothpastes, perfumes and other items are used for daily beauty and hygiene. These substances escape from traditional wastewater treatment and are released into the environment, where they come into contact with the microbial community, promoting the spread of resistance. Among them, parabens, triclocarban and triclosan are the main chemical pollutant substances.
[0003] One of the key issues of industrial concern is to provide consumers with risk-free products while ensuring the preservation of their chemical, physical and microbial properties. Additives play an important role in regulating the bacterial load of products when producing edible products or products for personal hygiene and cleaning. Without them, these materials will quickly expire, and more importantly, it will expose consumers to unpredictable dangers. Antibacterial agents are also added to the formulations of medical lotions, soaps, creams or sprays used for daily hygiene or the treatment of local bacterial infections. Some of the most well-known chemicals include parabens, triclocarban and triclosan. Since the mid-1920s, parabens (parabens) have been commonly added to cosmetics, foods and pharmaceuticals; their widespread application is related to low cost and good stability. Triclocarban and triclosan are present in a variety of personal care products such as toothpastes, detergents, shampoos, deodorants and body washes. These substances are considered emerging pollutants because they appear in outdoor and even indoor environments. Their persistence in several environmental matrices is also the result of incomplete elimination by traditional wastewater treatment processes. Summary of the Invention
[0004] In view of this, the present invention aims to overcome the defects in the prior art and proposes a rare earth composite material with oral antibacterial activity, a preparation method thereof and an application thereof.
[0005] To achieve the above object, the technical solution of the present invention is realized as follows:
[0006] In a first aspect, the present invention provides a rare earth composite material RE-AuCuNCs@GSH with oral antibacterial activity. The rare earth composite material includes chloroauric acid (HAuCl4), copper sulfate (CuSO4), glutathione (GSH), and rare earth salts, and the rare earth salts are one or more of lanthanum chloride heptahydrate, cerium chloride heptahydrate, lanthanum nitrate hexahydrate, cerium nitrate hexahydrate, lanthanum cerium phosphate, and lanthanum cerium carbonate.
[0007] In some embodiments of the present invention, the mass ratio of gold ions (Au 3+ ), rare earth ions, copper ions (Cu 2+ ) to glutathione (GSH) in the rare earth composite material is 1:(3 - 5):(6 - 9):(50 - 70).
[0008] Preferably, the mass ratio of gold ions, rare earth ions, copper ions to glutathione in the rare earth composite material is 1:4:8:60.
[0009] In a second aspect, the present invention also provides a preparation method of the above rare earth composite material with oral antibacterial activity, including the following steps:
[0010] S1: Mix a glutathione solution, a copper sulfate solution, and chloroauric acid, and then add an alkali solution to obtain a mixed solution;
[0011] S2: Stir the mixed solution at a temperature of 80 - 100°C for 6 - 9 h to obtain AuCuNCs@GSH, and store it at 0 - 4°C;
[0012] S3: Add a rare earth salt to AuCuNCs@GSH and adjust the pH value to 6.5 - 7.0 for reaction;
[0013] S4: After the reaction is completed, centrifuge the reaction solution, collect the centrifuged precipitate, and obtain the rare earth composite material RE-AuCuNCs@GSH after freeze-drying.
[0014] In a third aspect, the present invention also provides an application of the above rare earth composite material in the preparation of an antibacterial rare earth oral rinse.
[0015] In some embodiments of the present invention, the addition amount of the rare earth composite material in the antibacterial rare earth oral rinse is 2% - 3%.
[0016] In some embodiments of the present invention, the antibacterial rare earth oral rinse further includes one or more of a humectant, a sweetener, a solvent, an odor inhibitor, a cooling agent, a preservative, a thickener, a sweetener, a pigment, a flavoring agent, and a solvent as an auxiliary agent.
[0017] In some embodiments of the present invention, the auxiliary agent comprises components in the following parts by mass: 1-10 parts by weight of sorbitol, 1-3 parts by weight of ethanol, 5-10 parts by weight of thymol, 5-10 parts by weight of menthol, 3-5 parts by weight of sodium benzoate, 5-10 parts by weight of benzoic acid, 5-10 parts by weight of poloxamer 407, 5-10 parts by weight of sodium saccharin, 5-10 parts by weight of CI42053, 5-10 parts by weight of edible essence, and 20-30 parts by weight of water.
[0018] Compared with the prior art, the present invention has the following advantages:
[0019] (1) After the rare earth composite material of the present invention composites glutathione-protected gold-copper nanoclusters with rare earth, it has a high antibacterial function against E. coli, can effectively deal with stubborn bacteria that are prone to grow in the oral cavity, and maintain the ecological balance of the oral cavity.
[0020] (2) The rare earth composite material of the present invention has high antibacterial performance against Escherichia coli (E. coli), mainly because of the structural difference in the interaction between the gold-copper nanoclusters - AuCuNCs and rare earth composite material on the surface of the bacterial cell wall. The cell wall of Escherichia coli consists of a thin layer of peptidoglycan and lipopolysaccharide (15 - 20 nm), and the overall hardness and strength are insufficient. The presence of a thick peptidoglycan layer in the cell wall of Gram-positive bacteria may provide better resistance for bacteria. Description of the Drawings
[0021] Figure 1 It is the fluorescence spectrogram of AuCuNCs@GSH, LaCe-AuCuNCs@GSH prepared in Example 1, and La-AuCuNCs@GSH prepared in Example 2;
[0022] Figure 2 It is the agar plate experiment photos of the rare earth composite materials synthesized in different examples against Escherichia coli;
[0023] Figure 3 It is the agar plate experiment photos of LaCe-AuCuNCs@GSH described in Example 1 against Escherichia coli at concentrations of 0, 10, 50, and 100 mg / L. Detailed Embodiments
[0024] The embodiments of the present invention are described in detail below. The following described embodiments are exemplary and are only used to explain the present invention, and should not be construed as a limitation to the present invention.
[0025] In this article, unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the technical field to which this application belongs.
[0026] In this text, when a value is described as a range, it should be understood that such disclosure includes the disclosure of all possible sub-ranges within that range, as well as the specific numerical values falling within that range, regardless of whether the specific numerical values or specific sub-ranges are explicitly indicated.
[0027] In this text, when referring to "multiple", etc., unless otherwise specified, it means greater than 2 or equal to 2 in quantity. For example, "one or more" means one or greater than or equal to two.
[0028] In this text, when referring to "preferred" and "more preferred", they are only used to describe the embodiments or examples with better effects. It should be understood that they do not constitute a limitation on the protection scope of the present invention.
[0029] In this text, when referring to "further", etc., which is used for descriptive purposes, it indicates a difference in content, but should not be understood as a limitation on the protection scope of the present invention.
[0030] In this text, the term "and / or" is a description of the associative relationship of an object, indicating that there can be three relationships. For example, A and / or B means: A or B, or the three relationships of A and B.
[0031] In this text, the term "about" means + / - 10% of the specified value, preferably + / - 5%, and more preferably + / - 1%.
[0032] In this text, the terms "comprising", "including", "having", "containing", etc. are all open-ended terms, that is, they are meant to include but not be limited to.
[0033] Unless otherwise specified, all technical and scientific terms used in this text have the same meaning as commonly understood by those of ordinary skill in the art to which the present invention pertains. Although the present invention only describes preferred methods and materials, any methods and materials similar or equivalent to those described in this text can also be used in the implementation or testing of the present invention.
[0034] The present invention will be described in detail below in conjunction with embodiments.
[0035] Example 1
[0036] (1) Preparation of AuCuNCs@GSH
[0037] Mix 2 mL of 0.1 M GSH solution with 0.5 mL of CuSO4 solution of the same concentration, and then add 0.3 mL of 0.01 M HAuCl4 to it. The above solution is mixed with 8 mL of 1 M NaOH solution. Dilute the resulting mixture to 20 mL, stir and heat it vigorously at 90 °C for 8 hours, and store the obtained solution at 4 °C.
[0038] (2) Preparation of LaCe-AuCuNCs@GSH
[0039] Take 20 mL of AuCuNCs@GSH in a 50 mL beaker, add 8.5 mL of 1 mM LaCe(PO4)2 dispersion to it, adjust the pH to 6.5 - 7.0 with NaOH, wrap the beaker with tin foil, and stir overnight at room temperature. Centrifuge the above reaction solution at 5000 rpm for 15 - 20 min, discard the supernatant, collect the centrifuged precipitate, and lyophilize it to obtain LaCe - AuCuNCs@GSH.
[0040] Example 2
[0041] (1) Preparation of AuCuNCs@GSH
[0042] Mix 2 mL of 0.1 M GSH solution with 0.5 mL of CuSO4 solution of the same concentration, then add 0.3 mL of 0.01 M HAuCl4 to it. Mix the above solution with 8 mL of 1 M NaOH solution to enhance the reducing ability of GSH. Dilute the resulting mixture to 20 mL, stir and heat it vigorously at 90 °C for 8 hours, and store the obtained solution at 4 °C.
[0043] (2) Preparation of La - AuCuNCs@GSH
[0044] Take 20 mL of AuCuNCs@GSH in a 50 mL beaker, add 12 mL of 1 mM LaCl3·7H2O solution to it, adjust the pH to 6.5 - 7.0 with NaOH, wrap the beaker with tin foil, and stir overnight at room temperature. Centrifuge the above reaction solution at 5000 rpm for 15 - 20 min, discard the supernatant, collect the centrifuged precipitate, and lyophilize it to obtain La - AuCuNCs@GSH.
[0045] Example 3
[0046] (1) Preparation of AuCuNCs@GSH
[0047] Mix 2 mL of 0.1 M GSH solution with 0.5 mL of CuSO4 solution of the same concentration, then add 0.3 mL of 0.01 M HAuCl4 to it. Mix the above solution with 8 mL of 1 M NaOH solution. Dilute the resulting mixture to 20 mL, stir and heat it vigorously at 90 °C for 8 hours, and store the obtained solution at 4 °C.
[0048] (2) Preparation of LaCe - AuCuNCs@GSH
[0049] Take 20 mL of AuCuNCs@GSH in a 50 mL beaker, add 7.2 mL of 1 mM LaCe(CO3)2 dispersion solution thereto, adjust the pH to 6.5 - 7.0 with NaOH, wrap the beaker with tinfoil, and stir overnight at room temperature. Centrifuge the above reaction solution at 5000 rpm for 15 - 20 min, discard the supernatant, collect the centrifuged precipitate, and freeze-dry it to obtain LaCe-AuCuNCs@GSH, denoted as LaCe-AuCuNCs@GSH-1.
[0050] Example 4
[0051] (1) Preparation of AuCuNCs@GSH
[0052] Mix 2 mL of 0.1 M GSH solution with 0.5 mL of CuSO4 solution of the same concentration, then add 0.3 mL of 0.01 M HAuCl4 thereto, and mix the above solution with 8 mL of 1 M NaOH solution. Dilute the obtained mixture to 20 mL, stir and heat it vigorously at 90 °C for 8 hours, and store the resulting solution at 4 °C.
[0053] (2) Preparation of LaCe-AuCuNCs@GSH
[0054] Take 20 mL of AuCuNCs@GSH in a 50 mL beaker, add 12 mL of a mixed solution of 1 mM LaCl3·7H2O and Ce(NO3)3·6H2O (the mass ratio of LaCl3·7H2O to Ce(NO3)3·6H2O is 1:1.17) thereto, adjust the pH to 6.5 - 7.0 with NaOH, wrap the beaker with tinfoil, and stir overnight at room temperature. Centrifuge the above reaction solution at 5000 rpm for 15 - 20 min, discard the supernatant, collect the centrifuged precipitate, and freeze-dry it to obtain LaCe-AuCuNCs@GSH, denoted as LaCe-AuCuNCs@GSH-2.
[0055] Example 5
[0056] (1) Preparation of AuCuNCs@GSH
[0057] Mix 2 mL of 0.1 M GSH solution with 0.5 mL of CuSO4 solution of the same concentration, then add 0.3 mL of 0.01 M HAuCl4 thereto, and mix the above solution with 8 mL of 1 M NaOH solution. Dilute the obtained mixture to 20 mL, stir and heat it vigorously at 90 °C for 8 hours, and store the resulting solution at 4 °C.
[0058] (2) Preparation of LaCe-AuCuNCs@GSH
[0059] Take 20 mL of AuCuNCs@GSH in a 50 mL beaker, add 6.4 mL of 1 mM LaCe(PO4)2 dispersion to it, adjust the pH to 6.5 - 7.0 with NaOH, wrap the beaker with tin foil, and stir overnight at room temperature. Centrifuge the above reaction solution at 5000 rpm for 15 - 20 min, discard the supernatant, collect the centrifuged precipitate, and freeze-dry it to obtain LaCe-AuCuNCs@GSH, denoted as LaCe-AuCuNCs@GSH-3..
[0060] Example 6
[0061] (1) Preparation of AuCuNCs@GSH
[0062] Mix 2.3 mL of 0.1 M GSH solution with 0.56 mL of CuSO4 solution of the same concentration, then add 0.3 mL of 0.01 M HAuCl4 to it. Mix the above solution with 8 mL of 1 M NaOH solution to enhance the reducing ability of GSH. Dilute the resulting mixture to 20 mL, stir and heat it vigorously at 90 °C for 8 hours, and store the obtained solution at 4 °C.
[0063] (2) Preparation of La-AuCuNCs@GSH
[0064] Take 20 mL of AuCuNCs@GSH in a 50 mL beaker, add 10.6 mL of 1 mM LaCe(PO4)2 dispersion to it, adjust the pH to 6.5 - 7.0 with NaOH, wrap the beaker with tin foil, and stir overnight at room temperature. Centrifuge the above reaction solution at 5000 rpm for 15 - 20 min, discard the supernatant, collect the centrifuged precipitate, and freeze-dry it to obtain LaCe-AuCuNCs@GSH, denoted as LaCe-AuCuNCs@GSH-4..
[0065] Comparative Example 1
[0066] (1) Preparation of AuNCs@GSH
[0067] Mix 2 mL of 0.1 M GSH solution with 0.3 mL of 0.01 M HAuCl4, and mix the above solution with 8 mL of 1 M NaOH solution. Dilute the resulting mixture to 20 mL, stir and heat it vigorously at 90 °C for 8 hours, and store the obtained solution at 4 °C.
[0068] (2) Preparation of La-AuNCs@GSH
[0069] Take 20 mL of AuCuNCs@GSH in a 50 mL beaker, add 8.5 mL of 1 mM LaCe(PO4)2 dispersion to it, adjust the pH to 6.5 - 7.0 with NaOH, wrap the beaker with tin foil, and stir overnight at room temperature. Centrifuge the above reaction solution at 5000 rpm for 15 - 20 min, discard the supernatant, collect the centrifuged precipitate, and freeze-dry it to obtain LaCe-AuNCs@GSH.
[0070] Comparative Example 2
[0071] (1) Preparation of CuNCs@GSH
[0072] Mix 2 mL of 0.1 M GSH solution with 0.5 mL of CuSO4 solution of the same concentration. Mix the above solution with 8 mL of 1 M NaOH solution. Dilute the resulting mixture to 20 mL, stir and heat it vigorously at 90 °C for 8 hours, and store the obtained solution at 4 °C.
[0073] (2) Preparation of La-CuNCs@GSH
[0074] Take 20 mL of AuCuNCs@GSH in a 50 mL beaker, add 8.5 mL of 1 mM LaCe(PO4)2 dispersion to it, adjust the pH to 6.5 - 7.0 with NaOH, wrap the beaker with tin foil, and stir overnight at room temperature. Centrifuge the above reaction solution at 5000 rpm for 15 - 20 min, discard the supernatant, collect the centrifuged precipitate, and freeze-dry it to obtain LaCe-CuNCs@GSH.
[0075] Application Example Antibacterial Rare Earth Oral Lotion
[0076] Prepare 6 1-L graduated cylinders, and introduce 2 g of the rare earth composite materials prepared in Examples 1 - 6 into each of them, and introduce 20 g of water, 2 g of glycerol, 3 g of propylene glycol, 3 g of sorbitol, 6 g of menthol, 3 g of poloxamer 407, 5 g of sodium saccharin, 5 g of sodium fluoride, 3 g of potassium sorbate, 6 g of lemon oil, 6 g of CI42053, 6 g of CI42051, 9 g of CI17200, and 3 g of essence into each graduated cylinder.
[0077] Mix the above components in proportion, stir at room temperature for 1 - 2 h, transfer the mixed solution to an ultraviolet disinfection cabinet, irradiate it with an ultraviolet lamp for 3 - 5 h, seal it after filling, and thus obtain the rare earth highly antibacterial oral lotion.
[0078] Test Example 1
[0079] (1) Cultivation of Escherichia coli E.coli
[0080] Add 10 g of peptone, 5 g of yeast extract, and 10 g of sodium chloride to 1 L of water. After stirring evenly, place it in an autoclave for disinfection and sterilization. Let it stand and cool to room temperature, then seal the outer opening with a sealing film and place it in a 4°C refrigerator for standby to prepare Luria-Bertani (LB) agar medium.
[0081] Inoculate a single colony of MRSA into Luria-Bertani (LB) agar medium and culture it at 37°C and 180 rpm for 14 - 16 h to obtain suspensions of different types of bacteria. The ultraviolet absorption value at 600 nm (OD 600 ) is used to evaluate the growth of E. coli. In this invention, OD 600 is controlled to be 0.4 - 0.6.
[0082] (2) Agar plate experiment
[0083] Dilute the rare earth composite materials synthesized in Examples 1 - 6 and Comparative Examples 1 - 2 with deionized water respectively. After diluting to 100 mg / L, mix them with the E. coli suspension (OD 600 = 0.2) respectively. After incubating at 37°C for 3 h, spread 0.2 mL of the diluted bacterial suspension on LB agar and incubate at 37°C for 18 h. The results are shown in the figure.
[0084] It can be seen from the figure that compared with the blank group, the rare earth composite materials synthesized in Examples 1 - 6 all have different degrees of inhibitory effects on E. coli. Among them, the antibacterial effect of LaCe-AuCuNCs@GSH is the best, and there are no colonies in the plate medium. Followed by LaCe-AuCuNCs@GSH-1.
[0085] Furthermore, mix different concentrations of LaCe-AuCuNCs@GSH (0, 10, 50, 100 mg / L) with the suspension of E. coli (OD 600 = 0.2) respectively. After incubating at 37°C for 3 h, spread 0.2 mL of the diluted bacterial suspension on LB agar and incubate at 37°C for 18 h. Use the standard plate counting method to determine the survival rate of bacteria.
[0086] It is clearly observed from the figure that when 10 mg / L of LaCe-AuCuNCs@GSH is present, the survival rate of E. coli bacteria is 50%; when the material concentration is increased to 50 mg / L, the bacterial survival rate is 30%; when the material concentration is 100 mg / L, the bacterial survival rate is 0. Transfer the above plates to the fume hood for antibacterial timeliness evaluation. After the plates are placed for 3 months, only the plaque area of the original surviving bacteria expands, and there is no further bacterial growth, indicating that the antibacterial performance of this rare earth composite material has a long timeliness.
[0087] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.
Claims
1. A rare earth composite material with oral antibacterial activity, characterized in that: The rare earth composite material comprises chloroauric acid, copper sulfate, glutathione and a rare earth salt, wherein the rare earth salt is one or more of lanthanum chloride heptahydrate, cerium chloride heptahydrate, lanthanum nitrate hexahydrate, cerium nitrate hexahydrate, lanthanum cerium phosphate and lanthanum cerium carbonate.
2. The rare earth composite material with oral antibacterial activity according to claim 1, characterized in that: The mass ratio of gold ions, rare earth ions, copper ions and glutathione in the rare earth composite material is 1:(3-5):(6-9):(50-70).
3. The rare earth composite material with oral antibacterial activity according to claim 1, characterized in that: The mass ratio of gold ions, rare earth ions, copper ions and glutathione in the rare earth composite material is 1:4:8:
60.
4. The method for preparing the rare earth composite material having oral antibacterial activity according to any one of claims 1 to 3, characterized in that: The steps include: S1: mixing glutathione solution, copper sulfate solution and chloroauric acid, and then adding alkali solution to obtain a mixed solution; S2: Stir the mixed solution at 80-100°C for 6-9h to obtain AuCuNCs@GSH, and store it at 0-4°C; S3: adding rare earth salt to AuCuNCs@GSH and adjusting the pH value to 6.5-7.0 for reaction; S4: After the reaction is completed, the reaction solution is centrifuged, the centrifugal precipitate is collected, and the rare earth composite material RE-AuCuNCs@GSH is obtained after freeze-drying.
5. Use of the rare earth composite material according to any one of claims 1 to 3 in the preparation of antibacterial rare earth oral wash.
6. The use according to claim 5, characterized in that: The added amount of the rare earth composite material in the antibacterial rare earth oral wash is 2%-3%.
7. The use according to claim 5, characterized in that: The antibacterial rare earth oral wash also includes one or more of moisturizers, sweeteners, solvents, odor inhibitors, cooling agents, preservatives, preservatives, thickeners, sweeteners, pigments, flavoring agents, and solvents as auxiliary agents.
8. The use according to claim 5, characterized in that: The auxiliary agent includes the following components in parts by weight: 1-10 parts by weight of sorbitol, 1-3 parts by weight of ethanol, 5-10 parts by weight of thymol, 5-10 parts by weight of menthol, 3-5 parts by weight of sodium benzoate, 5-10 parts by weight of benzoic acid, 5-10 parts by weight of poloxamer 407, 5-10 parts by weight of saccharin sodium, 5-10 parts by weight of CI42053, 5-10 parts by weight of edible flavors, and 20-30 parts by weight of water.