Preparation method of fluorescence-enhanced anti-counterfeiting material and application of fluorescence-enhanced anti-counterfeiting material in spatio-temporal information encryption
By using patterned design to splice different film materials, a multi-response fluorescent enhanced anti-counterfeiting material is formed, which solves the problem of weak fluorescence emission of existing anti-counterfeiting materials in the solid state and realizes efficient and stable information encryption and decryption operations.
Patent Information
- Application Number
- CN202511201786.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-08-26
- Publication Date
- 2025-12-12
AI Technical Summary
Existing anti-counterfeiting materials have weak fluorescence emission in the solid state, are easily affected by the environment, make it difficult to meet high security requirements, and are complex to operate and have a slow response speed.
Using metal-organic framework membrane materials containing sodium riboflavin monophosphate and loaded with cerium dioxide, membrane materials containing sodium riboflavin monophosphate and loaded with cerium dioxide, membrane materials containing sodium riboflavin monophosphate, and non-fluorescent membrane materials, a multi-response fluorescent enhanced anti-counterfeiting material is formed by patterned design and splicing. Combined with ultraviolet light, chemical stimulation and humidity changes, it realizes information encryption and decryption.
It achieves efficient fluorescence emission in the solid state, possesses multiple response capabilities, improves the stability and functionality of anti-counterfeiting materials, and enables customized decryption methods and encryption information destruction operations.
Smart Images
Figure CN121108971A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the technical field of fluorescent anti-counterfeiting, and more specifically, relates to a method for preparing fluorescent enhanced anti-counterfeiting materials and their application in spatiotemporal information encryption. Background Technology
[0002] Accelerating the information transformation and building a green and collaborative anti-counterfeiting system are important tasks for the development of the anti-counterfeiting industry. Anti-counterfeiting technology is not only related to the interests of enterprises, but also the core support for maintaining economic order and information security.
[0003] Existing anti-counterfeiting materials, such as rare-earth-doped nanomaterials and organic-inorganic composite systems, offer excellent performance but are costly and complex to manufacture. Organic small-molecule dyes, due to their wide availability, low cost, and high designability, have become a research hotspot; however, they are limited by the aggregation-induced quenching (ACQ) effect, making them prone to fluorescence quenching in the solid state. Furthermore, these materials generally lack environmental stability (susceptible to temperature and humidity fluctuations) and multimodal response capabilities, making it difficult to meet high security requirements.
[0004] Although the emission properties of small molecule dyes can be modulated through DA structures, the ACQ effect results in weak solid-state signals, and problems such as photobleaching and thermal degradation limit their applications. While aggregation-induced emission (AIE) materials proposed in recent years can alleviate ACQ, they are complex to operate and have slow response speeds, making them difficult to match the needs of practical applications.
[0005] Therefore, there is an urgent need to develop a novel anti-counterfeiting material that overcomes the limitations of the ACQ effect and achieves efficient fluorescence emission in the solid state. Firstly, this requires overcoming the ACQ effect limitations through material compositing to achieve efficient fluorescence emission in the solid state. This design direction will systematically address the current bottlenecks in the stability, functionality, and cost-effectiveness of small molecule dyes, providing an innovative path for high-security anti-counterfeiting technology. Summary of the Invention
[0006] To address the aforementioned deficiencies or improvement needs of existing technologies, this invention provides a method for preparing a fluorescence-enhanced anti-counterfeiting material and its application in spatiotemporal information encryption. The aim is to establish a novel anti-counterfeiting material with multiple responses by designing patterns using metal-organic framework membranes containing sodium riboflavin monophosphate and cerium dioxide, membranes containing sodium riboflavin monophosphate, and membranes without fluorescence response. This solves the problem of achieving efficient fluorescence emission in the solid state in existing anti-counterfeiting materials.
[0007] To achieve the objectives of this invention, according to a first aspect of the invention, a fluorescently enhanced anti-counterfeiting material is provided, comprising four different film materials spliced together according to a patterned design; the four different film materials are a metal-organic framework film material containing sodium riboflavin monophosphate and loaded with cerium dioxide, a film material containing sodium riboflavin monophosphate and loaded with cerium dioxide, a film material containing sodium riboflavin monophosphate, and a film material with no fluorescence response, and the four film materials have the same apparent color under visible light; wherein, the organic framework in the metal-organic framework film material containing sodium riboflavin monophosphate and loaded with cerium dioxide is an organic framework material containing cobalt or an organic framework material containing copper.
[0008] Preferably, in the metal-organic framework membrane material containing sodium riboflavin monophosphate and loaded with cerium dioxide, the metal salt of the organic framework is one of cobalt nitrate, copper nitrate, cobalt chloride, copper sulfate, and cobalt sulfate, and the ligand is one or a mixture of two of 2-methylimidazole, bipyridine, aminoterephthalic acid, hydroxyterephthalic acid, terephthalic acid, triphenylcarboxylic acid, and naphthalic acid, and the molar ratio of the metal salt to the ligand is 5:1 to 1:5.
[0009] Preferably, the four different membrane materials have the same membrane substrate, which is a limited swelling polymer membrane; the limited swelling polymer membrane is a bacterial cellulose membrane, a cross-linked polyvinyl alcohol membrane, a cross-linked chitosan membrane, a nanocellulose composite membrane, or a zwitterionic functionalized membrane.
[0010] Preferably, the four different membrane materials have a flow channel structure at the bottom of the splice.
[0011] According to a second aspect of the present invention, a method for preparing a fluorescent anti-counterfeiting material as described in the first aspect of the present invention is provided, comprising: splicing together a metal-organic framework membrane material containing sodium riboflavin monophosphate and loaded with cerium dioxide, a membrane material containing sodium riboflavin monophosphate and loaded with cerium dioxide, a membrane material containing sodium riboflavin monophosphate and a membrane material without fluorescence response according to a patterned design to obtain a fluorescent anti-counterfeiting material based on cerium dioxide.
[0012] Preferably, the preparation of the cerium-loaded metal-organic framework membrane material containing sodium riboflavin monophosphate includes: S11: placing the membrane material in an organic framework dispersion, stirring, separating and washing the resulting product to obtain the cerium-loaded metal-organic framework membrane material; S12: placing the cerium-loaded metal-organic framework membrane material in a cerium source solution, adding a complexing precipitant, and then heating the reaction, separating and washing the product to obtain the cerium-loaded metal-organic framework membrane material; S13: placing the cerium-loaded metal-organic framework membrane material in a sodium riboflavin monophosphate solution, stirring thoroughly to obtain the cerium-loaded metal-organic framework membrane material containing sodium riboflavin monophosphate. The preparation of the cerium dioxide-loaded membrane material containing sodium riboflavin monophosphate includes: S21: placing the membrane material in a cerium source solution, adding a complexing precipitant, then heating the reaction, separating the product, washing it to obtain the cerium dioxide-loaded membrane material; S22: placing the cerium dioxide-loaded membrane material in a sodium riboflavin monophosphate solution, stirring the reaction thoroughly to obtain the cerium dioxide-loaded membrane material containing sodium riboflavin monophosphate. The preparation of the membrane material containing sodium riboflavin monophosphate includes: S31: placing the membrane material in a sodium riboflavin monophosphate solution, stirring and reacting thoroughly to obtain the membrane material containing sodium riboflavin monophosphate; The preparation of the non-fluorescent membrane material includes: S41: placing the membrane substrate in a non-fluorescent colorant and mixing thoroughly to obtain the non-fluorescent membrane material.
[0013] Preferably, in steps S13, S22 and S31, the concentration of riboflavin monophosphate sodium is 0.5~5 mM.
[0014] Preferably, in steps S12 and S21, the cerium source is one of cerium nitrate, cerium sulfate, and cerium ammonium nitrate, with a concentration of 1~15 g / L; the complexing precipitant is one of arginine, citric acid, sodium hydroxide, ammonium nitrate, and disodium ethylenediaminetetraacetate; the molar ratio of the cerium source to the complexing precipitant is 5:1~1:5; and the reaction temperature of the heating reaction is 75~90℃, and the reaction time is 2~6 h.
[0015] Preferably, in step S11, the solvent of the mechanical frame dispersion is one or more of ethanol, water, DMF, DMSO, and triethylamine in any proportion, and the stirring reaction is carried out at a temperature of 50~100℃ for 5~30 min.
[0016] According to a third aspect of the present invention, an application of a fluorescence-enhanced anti-counterfeiting material as described in the first aspect of the present invention is provided, wherein the fluorescence-enhanced anti-counterfeiting material, under ultraviolet light, firstly passes through a fluorescent anti-counterfeiting material containing S... 2- Inorganic salt solution or sulfate-reducing bacterial metabolic solution for S 2- Stimulation triggers a fluorescence response to obtain encrypted pattern information, thus completing decryption; then, the encrypted pattern information is destroyed by drying under ultraviolet light, completing the decryption process after reading the encrypted information.
[0017] In summary, compared with the prior art, the above-described technical solutions conceived by this invention mainly possess the following technical advantages: 1. The fluorescence-enhanced anti-counterfeiting material of this invention is based on the fluorescence responses of four different film materials under different conditions. This establishes a novel anti-counterfeiting material with multiple responses, achieving ingenious design in spatiotemporal information encryption and providing an innovative path for high-security anti-counterfeiting technology. Specifically, riboflavin monophosphate sodium can achieve fluorescence enhancement of small molecule dyes under both semi-solid and solid-state conditions, while the cerium dioxide-loaded metal-organic framework enhances the fluorescence of S... 2- The stimulation elicits a very significant fluorescent response, enabling pattern decryption. Then, drying the fluorescently enhanced anti-counterfeiting material allows for the decryption of the encrypted information after reading. Four types of film materials (a cerium-loaded metal-organic framework film material containing sodium riboflavin monophosphate, a cerium-loaded film material containing sodium riboflavin monophosphate, a film material containing sodium riboflavin monophosphate, and a film material with no fluorescent response) appear uniformly in color under visible light. However, chemical stimulation and drying under ultraviolet light result in different fluorescent responses, enabling the decryption of pattern or spatiotemporal information.
[0018] 2. In anti-counterfeiting applications, the fluorescent enhanced anti-counterfeiting material of the present invention combines multi-modal response characteristics such as photochromism, chemical response color change, and humidity change, and preferably adopts a flow channel structure to avoid decryption effect under early chemical stimulation, thereby improving the stability and functionality of the fluorescent enhanced anti-counterfeiting material in application.
[0019] 3. The fluorescent enhanced anti-counterfeiting material of the present invention utilizes the fluorescence response of four different film materials under different conditions to customize the design of decryption methods, decryption stages and encrypted pattern information, thereby realizing the decryption operation after reading the encrypted information. Attached Figure Description
[0020] Figure 1 This is a schematic diagram illustrating the response functions of four different membrane materials as examples of the present invention.
[0021] Figure 2 This is an example of the design of fluorescent enhanced anti-counterfeiting material and the decryption process of the corresponding material in Embodiment 2 of the present invention.
[0022] Figure 3 These are the visible light state diagrams and ultraviolet light state diagrams of the fluorescent enhanced anti-counterfeiting material under different humidity levels without chemical stimulation, as exemplified in Embodiment 2 of the present invention. (a) is the visible light state diagram when the material is not dried without chemical stimulation, (b) is the ultraviolet light state diagram when the material is not dried without chemical stimulation, (c) is the visible light state diagram when the material is dried without chemical stimulation, and (d) is the ultraviolet light state diagram when the material is dried without chemical stimulation.
[0023] Figure 4 The fluorescent enhanced anti-counterfeiting material exemplified in Example 2 of this invention is subjected to chemical stimulation (S... 2-Visible light and ultraviolet light state diagrams before and after different humidity levels are shown. (a) is the visible light state diagram of the undried state without chemical stimulation, (b) is the ultraviolet light state diagram of the undried state without chemical stimulation, (c) is the visible light state diagram of the undried state after chemical stimulation, (d) is the ultraviolet light state diagram of the undried state after chemical stimulation, (e) is the visible light state diagram of the dried state after chemical stimulation, and (f) is the ultraviolet light state diagram of the dried state after chemical stimulation.
[0024] Figure 5 This is an example of the fluorescence response of the cerium dioxide-loaded membrane material BC@CeO2@FMN loaded with different concentrations of fluorescent dye (riboflavin monophosphate, FMN) in this invention. Detailed Implementation
[0025] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention. Furthermore, the technical features involved in the various embodiments of this invention described below can be combined with each other as long as they do not conflict with each other.
[0026] To address the inherent shortcomings or improvement needs of existing technologies, the present invention aims to provide a fluorescence-enhanced anti-counterfeiting material, which is mainly composed of a limited-swelling polymer film loaded with different types of fluorescence-enhancing composite materials based on small-molecule fluorescent dyes, spliced according to a patterned design. Furthermore, this anti-counterfeiting material exhibits different fluorescence responses to ultraviolet light excitation, chemical stimulation, and humidity changes, enabling the reading and decryption of encrypted information.
[0027] The fluorescent enhanced anti-counterfeiting material of the present invention comprises four different film materials spliced together according to a patterned design to form a solid or semi-solid material; The four different membrane materials are: a metal-organic framework membrane material containing sodium riboflavin monophosphate and cerium dioxide, a membrane material containing sodium riboflavin monophosphate and cerium dioxide, a membrane material containing sodium riboflavin monophosphate, and a membrane material without fluorescence response. To meet anti-counterfeiting requirements, all four membrane materials have a consistent appearance color under visible light; therefore, there are slight differences in the sodium riboflavin monophosphate content among the three membrane materials. The concentration of non-fluorescent colorant was adjusted to make the color of the non-fluorescent membrane material close to that of the membrane material containing sodium riboflavin monophosphate, so that the apparent color of the four membrane materials was consistent under visible light. There was a slight difference in the cerium loading in the cerium-loaded metal-organic framework membrane material containing sodium riboflavin monophosphate and the cerium-loaded membrane material containing sodium riboflavin monophosphate. The organic framework in the cerium-loaded metal-organic framework membrane material containing sodium riboflavin monophosphate was an organic framework material containing cobalt or an organic framework material containing copper.
[0028] A cerium dioxide-loaded metal-organic framework (MOF) membrane material containing sodium riboflavin monophosphate is obtained by coating cerium dioxide with MOFs containing cobalt or copper as metal sites, followed by adsorption of the fluorescent dye sodium riboflavin monophosphate (FMN). This probe enhances the fluorescence signal, solves the ACQ problem of semi-solid and solid materials, and achieves decryption and destruction of encrypted information under ultraviolet light through chemical stimulation (sulfide ion and sulfate-reducing bacteria (SRB) metabolic solution). In the cerium dioxide-loaded MOF membrane material containing sodium riboflavin monophosphate, the metal salt of the organic framework is one of cobalt nitrate, copper nitrate, cobalt chloride, copper sulfate, or cobalt sulfate, and the ligand is one or a mixture of two of 2-methylimidazole, bipyridine, aminoterephthalic acid, hydroxyterephthalic acid, terephthalic acid, tribenzoic acid, or naphthalic acid (mixing ratio of 5:1 to 1:5), and the molar ratio of metal salt to ligand is 5:1 to 1:5.
[0029] The cerium dioxide-loaded membrane material containing sodium riboflavin monophosphate is obtained by combining a cerium-source membrane material with the fluorescent dye sodium riboflavin monophosphate (FMN). This probe can enhance the fluorescence signal and can exhibit fluorescence response under ultraviolet light and ultraviolet light + drying conditions. Furthermore, since no metal-organic framework is introduced, it responds to chemical stimulation (S... 2- It also retains the original fluorescence signal.
[0030] A membrane material containing sodium riboflavin monophosphate (FMN) is obtained by adsorbing the fluorescent dye FMN into the membrane material. This probe can enhance the fluorescence signal and exhibit a fluorescence response under ultraviolet light. Furthermore, since no metal-organic framework is introduced, it responds to chemical stimulation (S... 2- It also retains the original fluorescence signal.
[0031] The non-fluorescent membrane material is obtained by adsorbing a yellow non-fluorescent colorant onto the membrane material. This probe cannot achieve a fluorescent response under any condition.
[0032] In this invention, the degree of fluorescence enhancement is altered by adjusting the concentration of cerium dioxide and the loading of the fluorescent dye riboflavin monophosphate (FMN), thereby achieving a small-molecule fluorescent dye-enhanced anti-counterfeiting material. Adjusting the cerium dioxide loading and fluorescent dye concentration in the anti-counterfeiting material allows for customization of encryption information and encryption methods.
[0033] In this invention, the substrates of the four different membrane materials are all limited-swelling polymer membranes, possessing high water retention capacity, chemical modifiability, shape stability, and biodegradability, such as bacterial cellulose membranes, cross-linked polyvinyl alcohol membranes, cross-linked chitosan membranes, nanocellulose composite membranes, and zwitterionic functionalized membranes. Among these, bacterial cellulose membranes are preferred, as they benefit from a unique combination of nanostructure fineness, natural hydrophilicity, biocompatibility, and high mechanical strength, which is advantageous for cost control and efficiency improvement in large-scale production.
[0034] In this invention, four different membrane materials have flow channel structures at the bottom of the splicing points to prevent cross-contamination of fluorescent dyes from affecting the decryption effect. The flow channel structure can be a parallel straight groove, a biomimetic fractal flow channel, or a serpentine hybrid channel. Alternatively, when using this anti-counterfeiting material, a substrate with a flow channel structure can be selected to form a flow channel structure at its bottom, such as acrylic / glass laser-engraved flow channels, microfluidic substrates, or capillary drive plates.
[0035] The present invention also provides a method for preparing a fluorescent enhanced anti-counterfeiting material, comprising the following steps: splicing the above four different film materials according to a patterned design to obtain a cerium dioxide-based fluorescent anti-counterfeiting material.
[0036] The preparation of the cerium-loaded metal-organic framework membrane material containing sodium riboflavin monophosphate includes: S11: mixing the membrane material in an organic framework dispersion, stirring to obtain the product, separating and washing to obtain the cerium-loaded metal-organic framework membrane material; S12: placing the cerium-loaded metal-organic framework membrane material in a cerium source solution, adding a complexing precipitant, and then heating the reaction, separating the product, washing to obtain the cerium-loaded metal-organic framework membrane material; S13: placing the cerium-loaded metal-organic framework membrane material in a sodium riboflavin monophosphate solution, stirring thoroughly to obtain the cerium-loaded metal-organic framework membrane material containing sodium riboflavin monophosphate. The preparation of the cerium dioxide-loaded membrane material containing sodium riboflavin monophosphate includes: S21: placing the membrane material in a cerium source solution, adding a complexing precipitant, then heating the reaction, separating the product, washing it to obtain the cerium dioxide-loaded membrane material; S22: placing the cerium dioxide-loaded membrane material in a sodium riboflavin monophosphate solution, stirring the reaction thoroughly to obtain the cerium dioxide-loaded membrane material containing sodium riboflavin monophosphate. The preparation of the membrane material containing sodium riboflavin monophosphate includes: S31: placing the membrane material in a sodium riboflavin monophosphate solution and stirring thoroughly to obtain the membrane material containing sodium riboflavin monophosphate; The preparation of the non-fluorescent membrane material includes: S41: placing the membrane material in a non-fluorescent colorant and stirring thoroughly to obtain a non-fluorescent membrane material.
[0037] Preferably, in steps S13, S22 and S31, the concentration of riboflavin monophosphate sodium is 0.5~5 mM.
[0038] Preferably, in steps S12 and S21, the cerium source is one of cerium nitrate, cerium sulfate, and cerium ammonium nitrate, with a concentration of 1~15 g / L; the complexing precipitant is one of arginine, citric acid, sodium hydroxide, ammonium nitrate, and disodium ethylenediaminetetraacetate; the molar ratio of cerium source to complexing precipitant is 5:1~1:5; the reaction temperature is 75~90℃; and the reaction time is 2~6h.
[0039] Preferably, in step S11, the solvent of the mechanical frame dispersion is one or more of ethanol, water, DMF, DMSO, and triethylamine in any proportion, and the stirring reaction temperature is 50~100℃ for 5~30 min.
[0040] This invention also provides an application of a fluorescence-enhanced anti-counterfeiting material, whose encrypted pattern information is designed and defined by the encryptor. The following example illustrates the application of this fluorescence-enhanced anti-counterfeiting material: The fluorescence-enhanced anti-counterfeiting material was placed under a 350-400 nm ultraviolet lamp, and a 0.1-1 M solution of S was prepared. 2- Spray an appropriate amount of solution (sulfide ion solution and sulfate-reducing bacteria (SRB) metabolic solution) onto the membrane material and react for 2-4 minutes until the color of the membrane material no longer changes, thus obtaining the encrypted pattern information and completing the decryption. After the membrane material is dried, the encryption can be destroyed. Specifically, the encrypted information cannot be obtained under a 350-400 nm ultraviolet light environment after the membrane material is dried, thus achieving the destruction of the encryption.
[0041] The present invention will be further described in detail below with reference to specific embodiments.
[0042] Example 1: 1.1: Preparation of BC@CeO2@FMN metal-organic framework membrane material containing riboflavin sodium monophosphate and cerium dioxide: A suitable amount of 6 mm diameter circular bacterial cellulose membrane BC was added to a cerium nitrate solution, followed by the addition of L-arginine. The reaction was carried out at 80 °C. After separation and washing of the product, the corresponding membrane material BC@CeO2 loaded with cerium dioxide particles was obtained. BC@CeO2 was then added to a mixture of ethanol and water containing riboflavin sodium monophosphate (FMN), and stirred overnight at room temperature to obtain the fluorescence-enhancing membrane material BC@CeO2@FMN.
[0043] 1.2: Preparation of cerium dioxide-loaded membrane material BC@Co-CeO2@FMN containing riboflavin sodium monophosphate: A circular bacterial cellulose membrane BC with a diameter of 6 mm was placed in a cobalt nitrate solution and rapidly mixed with a 2-methylimidazole solution (1:1) at 50 °C. After stirring for 10 min, the product was separated and washed to obtain the corresponding ZIF-67 loaded membrane material. The membrane material was then added to a cerium nitrate solution followed by L-arginine and reacted at 80 °C. After separating and washing the product, the corresponding cerium dioxide loaded membrane material BC@Co-CeO2 was obtained. This membrane material was then placed in a mixture of ethanol and water containing riboflavin sodium monophosphate (FMN) and stirred overnight at room temperature to obtain the fluorescence-enhanced membrane material BC@Co-CeO2@FMN.
[0044] 1.3: Preparation of membrane material BC@FMN containing riboflavin sodium monophosphate: An appropriate amount of circular bacterial cellulose membrane BC with a diameter of 6 mm was added to a mixture of ethanol and water containing riboflavin sodium monophosphate (FMN), and stirred at room temperature overnight to obtain the fluorescent membrane material BC@FMN.
[0045] 1.4: Preparation of BC@P membrane material containing non-fluorescent colorant: An appropriate amount of circular bacterial cellulose membrane BC with a diameter of 6 mm was added to a solution containing a yellow non-fluorescent colorant and stirred overnight at room temperature to obtain membrane material BC@P.
[0046] Fluorescence response and S-response were measured for the four different membrane materials mentioned above. 2- The fluorescence response after treatment and after drying are tested in detail below: like Figure 1As shown, under UV conditions, the three membrane materials loaded with FMN (BC@CeO2@FMN, BC@Co-CeO2@FMN, and BC@FMN) all exhibit strong green fluorescence, while the membrane material soaked in a non-fluorescent colorant (BC@P) shows no fluorescence. Under chemical stimulation + UV conditions, BC@Co-CeO2@FMN loses its original strong green fluorescence and becomes weak due to a chemical reaction, while BC@CeO2@FMN and BC@FMN retain strong green fluorescence, and BC@P remains non-fluorescent. After drying and under UV conditions, BC@CeO2@FMN and BC@Co-CeO2@FMN exhibit strong yellow fluorescence after drying, while BC@FMN shows only weak fluorescence after drying, and BC@P shows no fluorescence after drying.
[0047] Example 2: The four film materials from Example 1 were spliced together according to a patterned design to prepare a fluorescently enhanced anti-counterfeiting material: Arrange the anti-counterfeiting film materials from 1.1, 1.2, 1.3, and 1.4 in a 4x4 pattern to obtain the partial material of the anti-counterfeiting QR code (4x4 matrix), such as... Figure 2 As shown, 1, 2, 3, and 4 correspond to materials BC@CeO2@FMN, BC@Co-CeO2@FMN, BC@FMN, and BC@P, respectively.
[0048] The fluorescence response and S of the above-mentioned fluorescent enhanced anti-counterfeiting materials were tested. 2- The decryption is achieved by testing the fluorescence response after processing and after drying. (Refer to...) Figure 3-4 Specifically as follows: Fluorescence response of a 4x4 matrix: The pre-arranged membrane material is placed under a 350-400 nm UV lamp for fluorescence detection to obtain the current fluorescence response pattern information.
[0049] 4x4 matrix pairs S 2- Fluorescence response: Prepare 0.1~1 M S 2- The solution is sprayed onto the membrane material using a spray bottle, and the reaction is allowed to proceed for 2-4 minutes until the membrane material no longer changes color. The membrane material is then placed under a 350-400 nm UV lamp for fluorescence detection to obtain the current fluorescence response pattern information, which is displayed as an encrypted pattern information.
[0050] Fluorescence response of 4*4 matrix after drying: The membrane material is air-dried and then placed under a 350~400 nm ultraviolet lamp for fluorescence detection. The fluorescence response pattern information is invalidated, thus decrypting the encrypted pattern information.
[0051] Figure 3 Based on Figure 2Undecrypted process diagram: Figure 3 (a) is a diagram showing the state of the membrane material under visible light. Figure 3 (b) The state diagram of the membrane material under ultraviolet light cannot decipher the transmitted message; Figure 3 (c) is Figure 3 (a) The membrane material in which no chemical stimulation (S) is applied 2- Visible light state diagram after processing and natural air drying; Figure 3 (d) is Figure 3 (a) The membrane material in which no chemical stimulation (S) is applied 2- The image under UV light after processing (natural air drying) still shows that it cannot be decrypted.
[0052] Figure 4 Based on Figure 2 A diagram illustrating the successful decryption process. Figure 4 (a) is a diagram showing the state of the membrane material under visible light. Figure 4 (b) is Figure 4 (a) is a diagram showing the state of the membrane material under ultraviolet light; Figure 4 (c) is Figure 4 (a) The membrane material under the applied chemical stimulus (S) 2- (Processing) + State diagram under visible light shows that membrane material No. 2 turns significantly black in the absence of ultraviolet light, while other materials show no change. At this time, the code cannot be deciphered. Figure 4 (d) is Figure 4 (a) The membrane material under the applied chemical stimulus (S) 2- (Processing) + State diagram under ultraviolet light, showing that the secret message conveyed by the 4*4 matrix of the film material under ultraviolet light can be deciphered; Figure 4 (e) is Figure 4 (a) The membrane material under the applied chemical stimulus (S) 2- (Processed) + The state diagram under visible light after drying shows that only film material No. 2 turns obviously black in the absence of ultraviolet light, while other materials remain unchanged. At this point, the code cannot be deciphered. Figure 4 (f) in the middle is Figure 4 The membrane material in (a) is subjected to chemical stimulation (S) 2- (Processing) + a state image under ultraviolet light after drying weakens the decryption effect, thus destroying the encrypted information.
[0053] Example 3: A cerium dioxide-loaded membrane material BC@CeO2@FMN containing riboflavin monophosphate was prepared as described in Example 1.1. Fluorescence tests were conducted under different conditions by varying the concentration of the fluorescent dye.
[0054] like Figure 5As shown, the membrane material without FMN showed no fluorescence under UV light; the membrane material with an FMN concentration of 0.25 g / L showed no fluorescence under UV light; the membrane material with an FMN concentration of 0.5 g / L showed weak green fluorescence under UV light; and the membrane material with an FMN concentration of 1~2.5 g / L showed strong green fluorescence under UV light.
[0055] Obviously, those skilled in the art can make various modifications and variations to this invention without departing from its spirit and scope. Therefore, if these modifications and variations fall within the scope of protection of this invention and its equivalents, this invention also intends to include these modifications and variations. The above-described embodiments are merely preferred embodiments given to fully illustrate this invention, and their scope of protection is not limited thereto. Equivalent substitutions or modifications made by those skilled in the art based on this invention are all within the scope of protection of this invention.
Claims
1. A fluorescently enhanced anti-counterfeiting material, characterized in that, It consists of four different membrane materials, which are spliced together according to a patterned design. The four different membrane materials are a metal-organic framework membrane material containing sodium riboflavin monophosphate and loaded with cerium dioxide, a membrane material containing sodium riboflavin monophosphate and loaded with cerium dioxide, a membrane material containing sodium riboflavin monophosphate, and a membrane material without fluorescence response, and the four membrane materials have the same apparent color under visible light; wherein, the organic framework in the metal-organic framework membrane material containing sodium riboflavin monophosphate and loaded with cerium dioxide is an organic framework material containing cobalt or an organic framework material containing copper.
2. The fluorescent enhanced anti-counterfeiting material as described in claim 1, characterized in that, In the metal-organic framework membrane material containing sodium riboflavin monophosphate and loaded with cerium dioxide, the metal salt of the organic framework is one of cobalt nitrate, copper nitrate, cobalt chloride, copper sulfate, and cobalt sulfate, and the ligand is one or a mixture of two of 2-methylimidazole, bipyridine, aminoterephthalic acid, hydroxyterephthalic acid, terephthalic acid, triphenylcarboxylic acid, and naphthalic acid, and the molar ratio of the metal salt to the ligand is 5:1 to 1:
5.
3. The fluorescent enhanced anti-counterfeiting material as described in claim 1, characterized in that, The four different membrane materials share the same substrate, which is a limited swelling polymer membrane; the limited swelling polymer membrane is a bacterial cellulose membrane, a cross-linked polyvinyl alcohol membrane, a cross-linked chitosan membrane, a nanocellulose composite membrane, or a zwitterionic functionalized membrane.
4. The fluorescent enhanced anti-counterfeiting material as described in claim 1, characterized in that, The four different membrane materials have flow channel structures at the bottom of the splice joint.
5. The method for preparing the fluorescent enhanced anti-counterfeiting material according to any one of claims 1-4, characterized in that, include: A cerium dioxide-based fluorescent anti-counterfeiting material is obtained by splicing together a metal-organic framework membrane material containing sodium riboflavin monophosphate, a cerium dioxide-based membrane material containing sodium riboflavin monophosphate, a membrane material containing sodium riboflavin monophosphate, and a non-fluorescent membrane material according to a patterned design.
6. The method for preparing the fluorescent enhanced anti-counterfeiting material as described in claim 5, characterized in that, The preparation of the cerium-loaded metal-organic framework membrane material containing sodium riboflavin monophosphate includes: S11: placing the membrane substrate in an organic framework dispersion, stirring, separating and washing the resulting product to obtain the cerium-loaded metal-organic framework membrane material; S12: placing the cerium-loaded metal-organic framework membrane material in a cerium source solution, adding a complexing precipitant, and then heating the reaction, separating and washing the product to obtain the cerium-loaded metal-organic framework membrane material; S13: placing the cerium-loaded metal-organic framework membrane material in a sodium riboflavin monophosphate solution, stirring thoroughly to obtain the cerium-loaded metal-organic framework membrane material containing sodium riboflavin monophosphate. The preparation of the cerium dioxide-loaded membrane material containing sodium riboflavin monophosphate includes: S21: placing the membrane substrate in a cerium source solution, adding a complexing precipitant, then heating the reaction, separating the product, washing it to obtain the cerium dioxide-loaded membrane material; S22: placing the cerium dioxide-loaded membrane material in a sodium riboflavin monophosphate solution, stirring the reaction thoroughly to obtain the cerium dioxide-loaded membrane material containing sodium riboflavin monophosphate. The preparation of the membrane material containing sodium riboflavin monophosphate includes: S31: placing the membrane substrate in a sodium riboflavin monophosphate solution, stirring and reacting thoroughly to obtain the membrane material containing sodium riboflavin monophosphate; The preparation of the non-fluorescent membrane material includes: S41: placing the membrane substrate in a non-fluorescent colorant and mixing thoroughly to obtain the non-fluorescent membrane material.
7. The method for preparing the fluorescent enhanced anti-counterfeiting material as described in claim 6, characterized in that, In steps S13, S22 and S31, the concentration of riboflavin monophosphate sodium is 0.5~5 mM.
8. The method for preparing the fluorescent enhanced anti-counterfeiting material as described in claim 6, characterized in that, In steps S12 and S21, the cerium source is one of cerium nitrate, cerium sulfate, and cerium ammonium nitrate, with a concentration of 1~15 g / L; the complexing precipitant is one of arginine, citric acid, sodium hydroxide, ammonium nitrate, and disodium ethylenediaminetetraacetate; the molar ratio of the cerium source to the complexing precipitant is 5:1~1:5; and the reaction temperature of the heating reaction is 75~90℃, and the reaction time is 2~6 h.
9. The method for preparing the fluorescent enhanced anti-counterfeiting material as described in claim 6, characterized in that, In step S11, the solvent of the mechanical frame dispersion is one or more of ethanol, water, DMF, DMSO, and triethylamine in any proportion, and the stirring reaction is carried out at a temperature of 50~100℃ for 5~30 min.
10. The application of the fluorescent enhanced anti-counterfeiting material as described in any one of claims 1-4, characterized in that, The fluorescent enhanced anti-counterfeiting material, under ultraviolet light, first passes through a substance containing S... 2- Inorganic salt solution or sulfate-reducing bacterial metabolic solution for S 2- Stimulation triggers a fluorescent response, which yields encrypted pattern information, thus completing the decryption process. Then, it is dried under ultraviolet light to destroy the encrypted pattern information, thus completing the decryption process after reading the encrypted information.