Photodynamic sterilization material based on mechanoluminescent material driving, sterilization method and sterilization toothbrush assembly

Abstract

The invention provides a photodynamic sterilization material driven by a mechanoluminescent material, a sterilization method and a sterilization toothbrush assembly. The photodynamic bactericidal material based on mechanoluminescent material driving comprises a mechanoluminescent material and a photosensitizer, a mechanoluminescent material is used as an excitation source, rose-bengal is used as an efficient photosensitizer to generate active oxygen, and the active oxygen is used for sterilization, so that efficient photodynamic sterilization is realized; the method does not depend on an external light source, has the advantages of simplicity and convenience in operation, environment friendliness and the like, and can realize efficient and stable sterilization effect in a dynamic environment; according to the photodynamic sterilization method disclosed by the invention, the sterilization efficiency is remarkably improved, the chemical residue risk is effectively reduced, a brand new application path is opened up for the development of a real-time photodynamic sterilization technology, and wide market application prospects and industrialization potential are shown.

Description

Technical Field

[0001] The present invention relates to the technical field of sterilization materials, and in particular to a photodynamic sterilization material driven by a mechanoluminescent material, a sterilization method and a sterilization toothbrush assembly. Background Art

[0002] Currently, reactive oxygen species are widely used in numerous fields, including sterilization, environmental monitoring, medical diagnosis, and photodynamic therapy. However, traditional methods for generating reactive oxygen species typically rely on lasers or external power sources to excite photosensitizers, which presents numerous drawbacks. On the one hand, high energy consumption and complex equipment structures lead to expensive production costs; on the other hand, they can also place a significant burden on the environment. In recent years, mechanoluminescent materials have garnered widespread attention due to their unique advantages. Without the need for an external electric field or dedicated light source, mechanoluminescent materials can directly convert mechanical energy into optical signals simply through mechanical stimulation, such as friction, compression, or stretching. This property gives them enormous potential for application in green, low-consumption, and self-powered applications.

[0003] Based on the characteristics of mechanoluminescent materials, it is expected that photosensitizers can be stimulated to produce reactive oxygen species as bactericidal materials; however, there is currently no technical solution to utilize the luminescent properties of mechanoluminescent materials to produce reactive oxygen species as bactericidal materials. Summary of the Invention

[0004] In view of this, the present invention provides a photodynamic sterilization material, sterilization method and sterilization toothbrush assembly driven by a mechanoluminescent material; the photodynamic sterilization material driven by a mechanoluminescent material of the present invention utilizes the mechanoluminescent material to generate light emission under the action of an external mechanical force, thereby exciting a photosensitizer. After absorbing the energy of endogenous light, the photosensitizer will transition to an excited state, and then transform into a triplet excited state through intersystem crossing; Subsequently, the photosensitizer in the excited state reacts with the surrounding substrate to generate reactive oxygen species with high reactivity; Reactive oxygen species can oxidize unsaturated fatty acids in the cell membrane of microorganisms, triggering lipid peroxidation reactions and destroying the integrity of the cell membrane. In addition, reactive oxygen species can also react with proteins and nucleic acids in the cell, resulting in protein inactivation and DNA breakage, ultimately inhibiting the growth and reproduction of microorganisms, and achieving effective photodynamic sterilization; Compared with traditional antibacterial methods such as ultraviolet sterilization and chemical disinfectants, the present invention uses mechanical force-driven photodynamics to generate reactive oxygen species for sterilization without the need for external light sources or chemical reagents, avoiding chemical residues and secondary pollution, while improving the safety and convenience of sterilization.

[0005] In order to achieve the above object, the present invention adopts the following technical solutions:

[0006] In a first aspect, the present invention provides a photodynamic sterilization material driven by a mechanoluminescent material, comprising a mechanoluminescent material and a photosensitizer;

[0007] The force-induced luminescent material emits light under the action of force and excites the photosensitizer to generate active oxygen to perform photodynamic sterilization.

[0008] Preferably, the mechanoluminescent material comprises ZnS:Mn 2+ 、SrAl2O4:Eu 2+ and ZnS / CaZnOS:Mn 2+ At least one of;

[0009] The photosensitizer includes at least one of rose bengal and methylene blue.

[0010] Preferably, the ZnS / CaZnOS:Mn 2+ The method for preparing the material comprises the following steps:

[0011] By ZnS / CaZnOS:Mn 2+ Weighing raw materials according to the stoichiometric ratio of each element in the material, and mixing the raw materials to obtain a mixed raw material;

[0012] Adding anhydrous ethanol to the mixed raw materials, grinding and mixing them evenly, and then drying them in an oven to obtain a mixed powder;

[0013] The mixed powder was calcined in an inert atmosphere to obtain ZnS / CaZnOS:Mn 2+ Material.

[0014] Preferably, the mixed powder is heated to 1000-1200°C at a heating rate of 5-10°C / min in an inert atmosphere, calcined for 1-4 hours, and cooled naturally in the furnace to obtain ZnS / CaZnOS:Mn 2+ Material.

[0015] Preferably, the raw materials include calcium carbonate, zinc sulfide, and manganese carbonate;

[0016] The molar ratio of the calcium carbonate, zinc sulfide and manganese carbonate is (1-2):(2-4):(0.01-0.03).

[0017] Preferably, it also includes a spherical matrix and a photosensitizer carrier;

[0018] The force-induced luminescent material is coated on the surface of the spherical substrate;

[0019] The photosensitizer is loaded on the photosensitizer carrier.

[0020] Preferably, the spherical matrix is ​​a zirconia spherical matrix;

[0021] The photosensitizer carrier is fabric.

[0022] In a second aspect, the present invention further provides a method for preparing the photodynamic sterilization material driven by the mechanoluminescent material, comprising:

[0023] mixing a mechanoluminescent material with polymethyl methacrylate to obtain a mixture;

[0024] The mixture is applied to the surface of the spherical substrate and dried;

[0025] The fabric is immersed in a photosensitizer solution, and the fabric is taken out and dried, so that the photosensitizer is loaded on the fabric.

[0026] In a third aspect, the present invention further provides a photodynamic sterilization method based on a mechanoluminescent material, comprising the following steps:

[0027] Providing the aforementioned photodynamic sterilization material driven by a mechanoluminescent material;

[0028] When force is applied to the force-induced luminescent material, the material emits light under the action of the force and excites the photosensitizer to generate active oxygen, thereby performing photodynamic sterilization.

[0029] In a fourth aspect, the present invention further provides a photodynamic sterilization toothbrush assembly driven by a mechanoluminescent material, comprising:

[0030] Toothbrush bristles, wherein the force-induced luminescent material is embedded in the toothbrush bristles;

[0031] Toothpaste containing the photosensitizer.

[0032] The photodynamic sterilization material, sterilization method, and sterilization toothbrush assembly driven by a mechanoluminescent material of the present invention have the following effects compared to the prior art:

[0033] 1. The present invention relates to a photodynamic sterilization material driven by a mechanoluminescent material, comprising a mechanoluminescent material and a photosensitizer. The mechanoluminescent material directly converts mechanical energy into a light signal, relying solely on mechanical stimulation, such as friction, compression, or stretching, without the need for an external electric field or dedicated light source. Upon absorbing the endogenous light generated by the mechanoluminescent material, the photosensitizer transitions to an excited state, which is then converted to a triplet excited state via intersystem crossing. Subsequently, the excited photosensitizer reacts with surrounding substrates to generate highly reactive oxygen species. As highly reactive oxidants, the reactive oxygen species can undergo oxidation reactions with biomacromolecules, such as proteins, lipids, and DNA, thereby achieving efficient photodynamic sterilization and pollutant degradation.

[0034] 2. The photodynamic sterilization material driven by the mechanoluminescent material of the present invention uses rose bengal as a photosensitizer; rose bengal has a significant main absorption peak at about 550nm and a broad and strong absorption band in the 400-600nm band; the absorption of methylene blue is mainly concentrated in the visible region (500-700nm), but the quantum yield is low and the photostability is poor. In comparison, ZnS / CaZnOS:Mn 2+ The material's mechanoluminescence emission covers the range of 500-700nm, which is not much different from the absorption bands of Rose Bengal and Methylene Blue. However, considering the efficiency, the present invention finally selected Rose Bengal as the photosensitizer due to its high quantum yield and strong photostability. 2+ The mechanoluminescence generated by the material can be effectively absorbed by Rose Bengal, which in turn stimulates it to produce reactive oxygen species, providing an energy basis for subsequent photodynamic reactions;

[0035] 3. The photodynamic sterilization method based on mechanoluminescent material driving of the present invention uses mechanoluminescent material as the excitation source and adopts rose bengal as the efficient photosensitizer to generate active oxygen, and utilizes the active oxygen for sterilization, thereby realizing efficient photodynamic sterilization; it does not rely on external light sources, has the advantages of simple operation, green and environmental protection, and can achieve efficient and stable sterilization effects in a dynamic environment; the photodynamic sterilization method of the present invention not only significantly improves the sterilization efficiency, but also effectively reduces the risk of chemical residues, opens up a new application path for the development of real-time photodynamic sterilization technology, and shows broad market application prospects and industrialization potential.

[0036] 4. The sterilizing toothbrush assembly driven by force-induced luminescent materials of the present invention comprises: toothbrush bristles and toothpaste, wherein the force-induced luminescent materials of the present invention are embedded in the toothbrush bristles; the toothpaste contains the photosensitizer of the present invention. Compared with the existing fluoride toothpaste, the toothpaste containing the photosensitizer of the present invention can reduce damage to teeth while improving the safety and convenience of sterilization. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] To more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present invention. Those skilled in the art can also derive other drawings based on these drawings without inventive effort.

[0038] Figure 1 In order to mechanically vibrate the composite pellets, ZnS / CaZnOS:Mn 2+ A device that emits light and causes the photosensitizer to generate active oxygen;

[0039] Figure 2 Absorption spectra of different photosensitizers and ZnS / CaZnOS:Mn 2+ Mechanoluminescence spectrum of

[0040] Figure 3 is the absorption spectrum of the control group in Example 3;

[0041] Figure 4 is the absorption spectrum of the experimental group in Example 3;

[0042] Figure 5 The effects of the different experimental groups in Example 4 on Escherichia coli, Pseudomonas aeruginosa (both Gram-negative bacteria), Staphylococcus aureus, and Bacillus subtilis (both Gram-positive bacteria);

[0043] Figure 6 This is a schematic structural diagram of the photodynamic sterilization toothbrush assembly driven by a mechanoluminescent material according to the present invention. DETAILED DESCRIPTION

[0044] To facilitate understanding of the present invention, the present invention will be described more fully below in conjunction with the specific embodiments. Preferred embodiments of the present invention are provided in the specific embodiments. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to provide a more thorough and comprehensive understanding of the disclosure of the present invention.

[0045] The present invention provides a photodynamic sterilization material driven by a mechanoluminescent material, comprising a mechanoluminescent material and a photosensitizer;

[0046] Among them, the mechanoluminescent material emits light under the action of force and excites the photosensitizer to produce reactive oxygen for photodynamic sterilization.

[0047] The photodynamic sterilization material based on the force-induced luminescence material of the present invention comprises a force-induced luminescence material and a photosensitizer; wherein the force-induced luminescence material relies only on mechanical stimulation, such as friction, compression or stretching, without the need for an external electric field or a dedicated light source, such as the ZnS / CaZnOS:Mn used in the present invention. 2+The material is a material with excellent mechanoluminescent properties that can directly convert mechanical energy into light signals; the photosensitizer is a substance that absorbs light of a specific wavelength and becomes excited, thereby initiating a series of chemical reactions. In the present invention, Rose Bengal, for example, acts as a photosensitizer. After absorbing the endogenous light generated by the mechanoluminescent material, it transitions to an excited state and then transforms to a triplet excited state through intersystem crossing. Subsequently, the excited photosensitizer reacts with surrounding substrates to generate highly reactive oxygen species (a highly reactive form of oxygen molecules). In the present system, the energy transfer between the excited state photosensitizer, such as Rose Bengal, and the surrounding substrates can be used for photodynamic sterilization and pollutant degradation, and can undergo oxidation reactions with biomacromolecules such as proteins, lipids, and DNA.

[0048] Specifically, 1,3-diphenylisobenzofuran can be used as a detection probe to monitor the generation of reactive oxygen species (singlet oxygen, one of the main reactive oxygen species produced by Rose Bengal). When 1,3-diphenylisobenzofuran undergoes a cycloaddition reaction with reactive oxygen, its furan ring structure is destroyed, forming an unstable endoperoxide intermediate, which in turn causes a significant shift in its characteristic absorption peak (approximately 410 nm) in the UV-visible spectrum. The degree of the absorption peak decrease is closely related to the amount of reactive oxygen generated. By utilizing this characteristic, monitoring the absorption peak change can quantitatively or qualitatively analyze the reactive oxygen content.

[0049] This invention innovatively utilizes mechanical force to excite a mechanoluminescent material to activate the photosensitizer Rose Bengal to generate reactive oxygen species (ROS). This ROS generation is detected by monitoring changes in the absorption peak of a 1,3-diphenylisobenzofuran solution, thereby achieving a photodynamic sterilization effect. This technical solution eliminates the traditional system's reliance on external excitation light sources, reducing equipment energy consumption and production costs. This approach is more aligned with the concept of green and low-consumption design and meets environmental protection requirements, providing a new technological approach with broad application prospects in related fields. This mechanoluminescent-driven photodynamic sterilization material consists solely of the mechanoluminescent material and the photosensitizer, requiring no external excitation device. Its simple and clear overall structure, convenient operation, and accurate and reliable detection data fully demonstrate the practicality and reliability of this technology in practical applications. Based on the principle of mechanoluminescence, this technology not only enables the excitation of photosensitizers to generate ROS, but also opens up new technical approaches for a variety of fields, including environmental monitoring (such as pollutant degradation), material testing (such as stress-responsive sensors), and biomedical diagnostics (such as self-powered sterilization coatings). This approach demonstrates broad application potential in the generation and detection of ROS, significantly promoting technological development in related fields.

[0050] In some embodiments, the mechanoluminescent material includes but is not limited to ZnS:Mn 2+ (i.e. Mn doped ZnS), SrAl2O4:Eu 2+(i.e. Eu-doped SrAl2O4) and ZnS / CaZnOS:Mn 2+ (i.e., Mn-doped ZnS / CaZnOS);

[0051] The photosensitizer includes at least one of rose bengal and methylene blue.

[0052] Preferably, the mechanoluminescent material is ZnS / CaZnOS:Mn 2+ Materials, photosensitizer is rose bengal.

[0053] The present invention uses ZnS / CaZnOS:Mn with excellent mechanoluminescence properties 2+ The material serves as an excitation source, Rose Bengal is used as a highly effective photosensitizer to generate reactive oxygen species, and 1,3-diphenylisobenzofuran molecules are used to detect the generation of reactive oxygen species, thereby verifying the technology's photodynamic sterilization effectiveness. This technical solution requires no external light source, achieving photodynamic sterilization solely through mechanical stimulation, making it convenient to operate, cost-effective, and environmentally friendly.

[0054] Specifically, to verify the ZnS / CaZnOS:Mn 2+ To investigate whether the light released by mechanoluminescent materials under mechanical stimulation can effectively excite photosensitizers, this study measured the UV-visible absorption spectra of two candidate photosensitizers: methylene blue and rose bengal (see Figure 2 The results showed that Rose Bengal had an obvious main absorption peak at about 550nm, and a broad and strong absorption band in the 400-600nm band; the absorption of methylene blue was mainly concentrated in the visible region (500-700nm), but the quantum yield was low and the photostability was poor. In contrast, ZnS / CaZnOS:Mn 2+ The material's mechanoluminescence emission covers the range of 500-700nm, which is not much different from the absorption bands of Rose Bengal and Methylene Blue. However, considering the efficiency, the present invention finally selected Rose Bengal as the photosensitizer due to its high quantum yield and strong photostability. 2+ The mechanoluminescence generated by the material can be effectively absorbed by rose bengal, which in turn stimulates it to produce active reactive oxygen species, providing an energy basis for subsequent photodynamic reactions.

[0055] In some embodiments, ZnS / CaZnOS:Mn 2+ The method for preparing the material comprises the following steps:

[0056] S1, according to ZnS / CaZnOS:Mn 2+ Weighing raw materials according to the stoichiometric ratio of each element in the material, and mixing the raw materials to obtain a mixed raw material;

[0057] S2. Add anhydrous ethanol to the mixed raw materials, grind and mix evenly, and then dry in an oven to obtain a mixed powder;

[0058] S3, calcining the mixed powder in an inert atmosphere to obtain ZnS / CaZnOS:Mn 2+ Material.

[0059] In some embodiments, the mixed powder is heated to 1000-1200°C at a heating rate of 5-10°C / min in an inert atmosphere, calcined for 1-4 hours, and then cooled naturally to obtain ZnS / CaZnOS:Mn 2+ Material.

[0060] In some embodiments, the raw materials include calcium carbonate, zinc sulfide, and manganese carbonate;

[0061] The molar ratio of calcium carbonate, zinc sulfide and manganese carbonate is (1-2):(2-4):(0.01-0.03).

[0062] In some embodiments, when prepared, ZnS / CaZnOS:Mn 2+ The raw materials include calcium carbonate (CaCO3), zinc sulfide (ZnS), and dopant: manganese carbonate (MnCO3). The specific preparation method includes:

[0063] S1, ZnS, CaCO3, and MnCO3 are mixed in a preset molar ratio to obtain a mixed raw material;

[0064] S2. Add anhydrous ethanol to the mixed raw materials, grind them thoroughly in an agate mortar for 30 minutes until they are evenly mixed, and dry them in an oven to obtain a mixed powder;

[0065] S3, calcining the mixed powder in an inert atmosphere, after calcination, the sample is cooled naturally to room temperature in the furnace, and the product is ground into fine powder again to obtain ZnS / CaZnOS:Mn with excellent mechanoluminescence performance. 2+ .

[0066] In some embodiments, the inert atmosphere includes, but is not limited to, nitrogen, helium, neon, and argon.

[0067] In some embodiments, the ZnS / CaZnOS:Mn 2+ The reaction mechanism of the material is:

[0068] CaCO3 decomposition:

[0069] CaCO3→CaO+CO2↑;

[0070] CaO reacts with ZnS to form CaZnOS: CaO + ZnS → CaZnOS;

[0071] The remaining unreacted ZnS forms a heterojunction with CaZnOS. After the decomposition of MnCO3, Mn 2+ doped into the lattice of ZnS and CaZnOS to obtain ZnS / CaZnOS:Mn 2+ Material.

[0072] In some embodiments, it further comprises a spherical matrix and a photosensitizer carrier;

[0073] The mechanoluminescent material is coated on the surface of the spherical substrate;

[0074] The photosensitizer is loaded on the photosensitizer carrier.

[0075] In some embodiments, the spherical substrate is a zirconia spherical substrate; and the sensitizer carrier is a fabric, such as cotton.

[0076] Based on the same inventive concept, the present invention also provides a method for preparing the above-mentioned photodynamic sterilization material driven by a mechanoluminescent material, comprising:

[0077] mixing a mechanoluminescent material with polymethyl methacrylate to obtain a mixture;

[0078] The mixture is applied to the surface of the spherical substrate and dried;

[0079] The fabric is soaked in a photosensitizer solution, and the fabric is taken out and dried, so that the photosensitizer is loaded on the fabric.

[0080] Specifically, the mass ratio of the mechanoluminescent material to the polymethyl methacrylate is (1-2):(1-2).

[0081] Specifically, the photosensitizer solution is an aqueous solution, wherein the concentration of the photosensitizer solution is 6-10% owf; that is, based on the weight of the fabric, it usually means that the amount of dye used is 6% to 10% of the weight of the fabric; for example, if there are 100 grams of fabric, then the amount of dye used is between 6 grams and 10 grams.

[0082] Based on the same inventive concept, the present invention also provides a photodynamic sterilization method driven by a mechanoluminescent material, comprising the following steps:

[0083] Providing the above-mentioned photodynamic sterilization material driven by mechanoluminescent material;

[0084] When force is applied to the mechanoluminescent material, it emits light under the action of the force and excites the photosensitizer to produce active oxygen for photodynamic sterilization.

[0085] Based on the same inventive concept, the present invention also provides a photodynamic sterilization toothbrush assembly driven by a mechanoluminescent material, comprising toothbrush bristles, wherein the mechanoluminescent material is embedded in the toothbrush bristles;

[0086] A toothpaste containing the above-mentioned photosensitizer.

[0087] Traditional toothbrushes are prone to breeding bacteria during use, affecting oral health. The present invention proposes a light-powered sterilization toothbrush driven by a mechanoluminescent material, wherein the toothbrush bristles are embedded with a mechanoluminescent material (such as ZnS / CaZnOS:Mn 2 + ), toothpaste containing the photosensitizer of the present invention forms an integrated photodynamic system. The friction generated by brushing stimulates the photoluminescent material to produce light, which in turn activates the photosensitizer Rose Bengal to generate reactive oxygen species, achieving real-time sterilization of the bristles and oral environment. Compared to existing fluoride-containing toothpastes, the toothpaste containing the photosensitizer of the present invention reduces damage to teeth while improving the safety and convenience of sterilization.

[0088] The principles involved in the present invention are as follows:

[0089] 1. Mechanical excitation and endogenous light generation: Based on the special physical properties of mechanoluminescent materials, the present invention uses mechanical forces (such as friction, compression, and stretching) to induce luminescence. The core principle of mechanoluminescence is that external force induces lattice distortion or defect recombination of the material, causing the internal electron energy level transition of the material, thereby releasing photons. By accurately screening materials with excellent mechanoluminescent properties, such as ZnS:Mn 2+ 、SrAl2O4:Eu 2+ and ZnS / CaZnOS:Mn 2+ Under appropriate mechanical stimulation, a stable and controllable optical radiation signal can be obtained. The mechanoluminescent light source of the present invention does not require an external electric field or light source, which not only reduces system energy consumption but also conforms to the concept of green environmental protection. By manipulating the emission spectrum of the mechanoluminescent material to match the absorption range of a specific photosensitizer, an efficient optical excitation process is achieved.

[0090] 2. Photosensitizer Excitation to Generate Reactive Oxygen Species: Under the action of endogenous light generated by mechanoluminescence, the present invention uses the photosensitizer Rose Bengal as the excited molecule. Upon absorbing photons of a specific wavelength, Rose Bengal transitions to an excited state, which then transforms to a triplet excited state via intersystem crossing. Subsequently, the excited photosensitizer reacts with surrounding substrates, generating highly reactive reactive oxygen species. As highly active oxidants, reactive oxygen species can undergo oxidative reactions with biomacromolecules such as proteins, lipids, and DNA, thereby achieving efficient photodynamic sterilization and pollutant degradation.

[0091] 3. Detection of the generation of reactive oxygen species using 1,3-diphenylisobenzofuran molecules: In order to qualitatively and quantitatively monitor the generation of reactive oxygen species, the present invention uses a 1,3-diphenylisobenzofuran solution as a specific probe molecule. 1,3-diphenylisobenzofuran can undergo a cycloaddition reaction with reactive oxygen species to form unstable endoperoxides, which eventually decompose into non-conjugated products, resulting in the attenuation of its characteristic absorption peak (approximately 410 nm) in the ultraviolet-visible spectrum. By measuring the changes in the absorption peak of 1,3-diphenylisobenzofuran, the generation of reactive oxygen species can be effectively quantified. This detection method has the characteristics of high sensitivity and high selectivity, and can monitor the dynamic changes of reactive oxygen species in real time, providing a scientific basis for the effectiveness of the photodynamic sterilization process.

[0092] 4. Photodynamic sterilization process: The active oxygen generated by the present invention can oxidize unsaturated fatty acids in the cell membrane of microorganisms, trigger lipid peroxidation reactions, and destroy the integrity of the cell membrane. In addition, active oxygen can also react with proteins and nucleic acids in the cells, leading to protein inactivation and DNA breakage, and ultimately inhibiting the growth and reproduction of microorganisms, achieving effective photodynamic sterilization. Compared with traditional antibacterial methods, such as ultraviolet sterilization and chemical disinfectants, the present invention uses mechanical force-driven photodynamic sterilization technology that does not require external light sources or chemical reagents, avoids chemical residues and secondary pollution, and improves the safety and convenience of sterilization.

[0093] The following further illustrates the photodynamic sterilization material, sterilization method, and sterilizing toothbrush based on the power-induced luminescent material of the present invention with specific examples. This section further illustrates the content of the present invention in conjunction with specific examples, but should not be construed as limiting the present invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. Unless otherwise specified, the reagents, methods, and equipment used in the present invention are conventional reagents, methods, and equipment in the art.

[0094] In the following examples, rose red is specifically bengal (rose red) dye (Bengal), CAS: 632-69-9, brand: Solarbio.

[0095] Example 1

[0096] This embodiment provides a mechanoluminescent material ZnS / CaZnOS:Mn 2+ The method for preparing the material comprises the following steps:

[0097] S1. Mix ZnS, CaCO3, and MnCO3 in a molar ratio of 2:1:0.02 to obtain a mixed raw material;

[0098] S2. Add anhydrous ethanol to the mixed raw materials (the mass of anhydrous ethanol is 30% of the mass of the mixed raw materials), grind thoroughly in an agate mortar for 30 minutes until the mixture is uniform, and dry in an oven at 90°C to obtain a mixed powder;

[0099] S3, the mixed powder was heated to 1100℃ in nitrogen atmosphere at a heating rate of 5℃ / min, calcined for 3 hours, cooled naturally with the furnace, and ground through a 400 mesh sieve to obtain ZnS / CaZnOS:Mn 2+ Material.

[0100] Example 2

[0101] In this example, photosensitizers methylene blue and rose bengal were screened. Specifically, methylene blue and rose bengal were prepared into aqueous solutions with a concentration of 600-700 μmol / L, and the UV-visible absorption spectra were tested. The results are as follows: Figure 2 As shown; at the same time, the power luminescent material ZnS / CaZnOS:Mn prepared in Example 1 2+ Apply 20N force and test its mechanoluminescence emission spectrum. The results are as follows Figure 2 shown.

[0102] Figure 2 The absorption spectra of photosensitizers methylene blue and rose bengal and the mechanoluminescent material ZnS / CaZnOS:Mn 2+ emission spectrum.

[0103] from Figure 2 It can be seen that Rose Bengal has an obvious main absorption peak at about 550nm, and presents a broad and strong absorption band in the 400-600nm band; the absorption of methylene blue is mainly concentrated in the visible region (500-700nm), but the quantum yield is low and the photostability is poor. In contrast, ZnS / CaZnOS:Mn 2+ The material's mechanoluminescence emission covers the range of 500-700nm, which is not much different from the absorption bands of Rose Bengal and Methylene Blue. However, considering the efficiency, this study finally selected Rose Bengal as the photosensitizer due to its high quantum yield and strong photostability. 2+ The mechanoluminescence generated by the material can be effectively absorbed by rose bengal, which in turn stimulates it to produce active reactive oxygen species, providing an energy basis for subsequent photodynamic reactions.

[0104] Example 3

[0105] This embodiment provides a photodynamic sterilization material driven by a mechanoluminescent material, the preparation of which includes:

[0106] The mechanoluminescent material ZnS / CaZnOS:Mn prepared in Example 1 2+ The composite material was uniformly mixed with polymethyl methacrylate (PMMA) at a mass ratio of 1:1 and coated on the surface of zirconia spheres to prepare composite material spheres with mechanoluminescence properties.

[0107] The cotton cloth was soaked in a rose bengal aqueous solution with a concentration of 6% owf (based on the weight of the cotton cloth) for dyeing. After dyeing, the cotton cloth was soaked in methanol until the washing solution was completely colorless to ensure that the dye would not fall off during subsequent testing. Finally, the treated cotton cloth was placed in a 70°C oven and dried for 10 hours to ensure complete drying, thereby obtaining a cotton cloth loaded with rose bengal.

[0108] In a dark environment, the composite material beads with mechanoluminescence properties in Example 3 and the cotton cloth loaded with rose bengal were added to the transparent acrylic spheres, and a 1,3-diphenylisobenzofuran (DPBF) aqueous solution with a concentration of 74 μmol / L was added to the spheres. The composite material beads were mechanically vibrated to make the ZnS / CaZnOS:Mn 2+ Luminous, vibrating devices such as Figure 1 As shown; after vibrating for different times (10 to 150 s), the 1,3-diphenylisobenzofuran (DPBF) aqueous solution was taken out and its absorption spectrum was tested (experimental group). The results are shown as follows Figure 4 shown.

[0109] According to the same method as above, the zirconia beads were replaced with the composite material beads with mechanoluminescence properties in Example 3. After vibrating for different times (10 to 150 seconds), the 1,3-diphenylisobenzofuran (DPBF) aqueous solution was taken out and its absorption spectrum was tested (control group). The results are as follows: Figure 3 shown.

[0110] Figures 3-4 The absorbance changes of 1,3-diphenylisobenzofuran (DPBF) aqueous solution at 410nm wavelength under different conditions are shown, which directly reflects the promoting effect of the mechanoluminescent material on the generation of active oxygen and its time dependence. Figure 3 and Figure 4 As can be seen, the absorbance of the DPBF aqueous solution with the addition of the mechanoluminescent composite beads was significantly lower than that with the addition of zirconia beads, indicating that the addition of the mechanoluminescent composite beads generated reactive oxygen species. This verifies that the mechanoluminescent material can generate light emission under mechanical vibration, thereby stimulating Rose Bengal and effectively promoting the generation of reactive oxygen species. As the vibration time increases, the absorbance of the experimental group continues to decrease, while the change in the control group is not significant. This further demonstrates that the photodynamic effect of the mechanoluminescent material is significantly time-dependent, capable of stably stimulating the reaction system under continuous vibration and continuously driving the generation of reactive oxygen species, demonstrating excellent potential for photodynamic applications.

[0111] Example 4

[0112] This embodiment provides a new method for achieving self-powered photodynamic sterilization using mechanoluminescent materials; by mechanical stimulation, ZnS / CaZnOS:Mn 2+ The mechanoluminescent material generates light, activating the photosensitizer Rose Bengal to generate reactive oxygen species, effectively inactivating bacteria. The system's simple design and lack of external light sources make it particularly suitable for real-time sterilization in dynamic environments.

[0113] Experimental steps:

[0114] S1. Bacterial culture: Escherichia coli and Pseudomonas aeruginosa (both Gram-negative bacteria), as well as Staphylococcus aureus and Bacillus subtilis (both Gram-positive bacteria) were selected. The strains were then inoculated into LB medium and cultured overnight at 37°C and 120 rpm. The bacterial strains were cultured to an initial concentration of 5×10 8 Colony forming units (CFU) / mL; culture concentration was monitored by optical density measurement at 600 nm. Cultures were collected after 10 min of centrifugation (10,000 rpm) and resuspended in phosphate-buffered saline for further experiments.

[0115] S2. Experimental setup: Composite material beads with mechanoluminescence properties were prepared according to the method in Example 3; cotton cloth loaded with rose bengal;

[0116] The following three groups of control conditions were set up in the experiment to exclude interfering factors such as exogenous light and dark toxicity:

[0117] Dark control group: In a completely dark environment, ordinary zirconium oxide beads and rose red cotton cloth were added to the transparent acrylic spheres, without any excitation light.

[0118] Illumination control group: Under external light illumination, ordinary zirconium oxide beads and rose bengal-loaded cotton cloth were added to the transparent acrylic spheres to evaluate the effect of exogenous light on the system.

[0119] Experimental group: Under dark conditions, small balls of composite materials with mechanoluminescent properties and cotton cloth loaded with rose bengal were added to transparent acrylic spheres. The rose bengal was activated by the light generated by excitation, thereby inducing the occurrence of photodynamic reaction.

[0120] S3. Mechanical stimulation: Use a vibration table to vibrate each group of samples to stimulate the mechanoluminescent material to emit light.

[0121] S4. Add bacteria: Add bacterial solution into the acrylic ball while mechanically stimulating.

[0122] S5. Bactericidal Detection Technique: After a certain reaction time, remove each sample group, rinse thoroughly with sterile saline, and then add 0.9 mL of sterile phosphate-buffered saline. Remove 100 μL of the mixture and dilute it according to a specific ratio to ensure that the bacterial concentration in each sample level is within the countable range. Spread each diluted sample on a nutrient agar plate and incubate in the dark at 37°C for 15–24 hours. The CFU (colony-forming units) of each sample are then calculated by colony counting.

[0123] S6. Data Analysis: Calculate the sterilization rate based on the colony counts in the control and treatment groups (using the CFU count in the control group as 100% survival) and convert it to a logarithmic inactivation value. This method can accurately detect sterilization effects up to 6 log units and effectively verify the photodynamic sterilization efficiency of the system.

[0124] The test results are as follows Figure 5 Specifically, Figure 5 The effects of different experimental groups on Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus and Bacillus subtilis; Figure 5 The three bar graphs corresponding to Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus, and Bacillus subtilis are from left to right: dark control group, light control group, and experimental group.

[0125] Figure 5 The figure shows the survival percentage of four bacteria under different experimental treatments.

[0126] Experimental results and analysis: From the results of colony counting, the experimental group had a significantly higher sterilization rate than the dark control after mechanical stimulation, and had reached the sterilization detection limit, and was comparable to the control group with only external light, proving that the method of using mechanoluminescence to achieve photodynamic sterilization has good sterilization efficiency. Overall, the experimental results and quantitative analysis have demonstrated the feasibility of photodynamic sterilization technology based on mechanoluminescence self-powered system to achieve efficient sterilization in a dynamic environment, and provide an effective way to solve the problem of dependence on external light sources. This method not only has a high sterilization efficiency, but also exhibits good safety and stability, showing broad prospects in practical applications.

[0127] Example 5

[0128] This embodiment provides a light-powered sterilizing toothbrush assembly driven by a force-induced luminescent material. Traditional toothbrushes are prone to breeding bacteria during use, affecting oral health. The present invention proposes a light-powered sterilizing toothbrush driven by a force-induced luminescent material, such as Figure 6 As shown, the toothbrush comprises bristles, wherein the toothbrush bristles are embedded with the force-induced luminescent material ZnS / CaZnOS:Mn prepared in Example 1. 2+, also includes toothpaste containing photosensitizer (Rose Bengal).

[0129] When in use, mechanical friction excites the mechanoluminescent material to generate endogenous light, which in turn activates the photosensitizer rose bengal to generate reactive oxygen, achieving real-time sterilization of the bristles and oral environment.

[0130] A suspension containing bacteria such as Escherichia coli is applied to the surface of the tooth model. The friction between the toothbrush and the tooth surface can stimulate the electroluminescent material to produce light, which in turn activates the photosensitizer to generate active oxygen to achieve a sterilization effect.

[0131] Practical Application Results: This toothbrush eliminates the need for external power or chemical disinfectants, relying solely on mechanical force to sterilize. Compared to traditional toothbrushes, this design significantly reduces the risk of bacterial growth and improves oral hygiene. It offers advantages such as ease of use, safety, environmental protection, and low cost.

[0132] Through experimental research and case analysis, the present invention fully verifies that under mechanical vibration excitation, ZnS / CaZnOS:Mn 2+ The mechanoluminescent material effectively activates Rose Bengal, generating reactive oxygen species. Experimental results showed that in the photodynamic reaction system, the DPBF absorbance of the mechanically excited experimental group decreased significantly, indicating the production of reactive oxygen species. Furthermore, bactericidal experiments demonstrated a significantly higher bacterial inactivation rate compared to the dark control group, and comparable to the external light control group.

[0133] The self-powered photodynamic sterilization method proposed in this paper, based on mechanoluminescence, does not rely on external light sources, offers advantages such as ease of operation and environmental friendliness, and can achieve efficient and stable sterilization in dynamic environments. This technology not only significantly improves sterilization efficiency but also effectively reduces the risk of chemical residues, opening up a new application path for the development of real-time photodynamic sterilization technology and demonstrating broad market application prospects and industrial potential.

[0134] The photodynamic sterilization toothbrush assembly designed based on this photodynamic mechanism further demonstrates its feasibility and advantages in practical applications. Compared with traditional chemical sterilization methods, the technical solution provided by this invention demonstrates many significant advantages in reducing chemical residues, improving safety, simplifying operational procedures, reducing costs, and achieving environmental protection and high efficiency. It provides a new solution for photodynamic technology driven by no external light source, and shows broad promotion value and application prospects.

[0135] It can be understood that the various technical features of the above-described embodiments can be combined arbitrarily. In order to make the description concise, not all possible combinations of the various technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0136] The above are merely preferred embodiments of the present application and only specifically describe the technical principles of the present application. These descriptions are intended only to explain the principles of the present application and should not be construed in any way as limiting the scope of protection of the present application. Based on the explanations herein, any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present application, as well as other specific implementations of the present application that can be conceived by those skilled in the art without inventive effort, shall be included within the scope of protection of the present application.

Claims

1. A photodynamic sterilization material driven by a mechanoluminescent material, characterized in that: Including mechanoluminescent materials and photosensitizers; The force-induced luminescent material emits light under the action of force and excites the photosensitizer to generate active oxygen to perform photodynamic sterilization.

2. The photodynamic sterilization material driven by mechanoluminescent material according to claim 1, characterized in that: The mechanoluminescent material includes ZnS:Mn 2+ 、SrAl2O4:Eu 2+ and ZnS / CaZnOS:Mn 2+ At least one of; The photosensitizer includes at least one of rose bengal and methylene blue.

3. The photodynamic sterilization material driven by mechanoluminescent material according to claim 1, characterized in that: The ZnS / CaZnOS:Mn 2+ The method for preparing the material comprises the following steps: By ZnS / CaZnOS:Mn 2+ Weighing raw materials according to the stoichiometric ratio of each element in the material, and mixing the raw materials to obtain a mixed raw material; Adding anhydrous ethanol to the mixed raw materials, grinding and mixing them evenly, and then drying them in an oven to obtain a mixed powder; The mixed powder was calcined in an inert atmosphere to obtain ZnS / CaZnOS:Mn 2+ Material.

4. The photodynamic sterilization material driven by mechanoluminescent material according to claim 3, characterized in that: The mixed powder is heated to 1000-1200℃ in an inert atmosphere at a heating rate of 5-10℃ / min, calcined for 1-4 hours, and cooled naturally to obtain ZnS / CaZnOS:Mn 2+ Material.

5. The photodynamic sterilization material driven by mechanoluminescent material according to claim 3, characterized in that: The raw materials include calcium carbonate, zinc sulfide, and manganese carbonate; The molar ratio of the calcium carbonate, zinc sulfide and manganese carbonate is (1-2):(2-4):(0.01-0.03).

6. The photodynamic sterilization material driven by mechanoluminescent material according to claim 1, characterized in that: Also included are a spherical matrix and a photosensitizer carrier; The mechanoluminescent material is coated on the surface of the spherical substrate; The photosensitizer is loaded on the photosensitizer carrier.

7. The photodynamic sterilization material driven by mechanoluminescent material according to claim 6, characterized in that: The spherical matrix is ​​a zirconia spherical matrix; The photosensitizer carrier is fabric.

8. A method for preparing a photodynamic sterilization material driven by a mechanoluminescent material according to any one of claims 6 to 7, characterized in that: include: mixing a mechanoluminescent material with polymethyl methacrylate to obtain a mixture; The mixture is applied to the surface of the spherical substrate and dried; The fabric is immersed in a photosensitizer solution, and the fabric is taken out and dried, so that the photosensitizer is loaded on the fabric.

9. A photodynamic sterilization method based on mechanoluminescent material, characterized in that: The following steps are involved: Providing a photodynamic sterilization material driven by a mechanoluminescent material according to any one of claims 1 to 7; When force is applied to the force-induced luminescent material, the material emits light under the action of the force and excites the photosensitizer to generate active oxygen, thereby performing photodynamic sterilization.

10. A photodynamic sterilization toothbrush assembly driven by mechanoluminescent materials, characterized in that: include: Toothbrush bristles, wherein the toothbrush bristles are embedded with the mechanoluminescent material according to any one of claims 1 to 7; A toothpaste comprising the photosensitizer according to any one of claims 1 to 7.

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