A room temperature phosphor collagen composite film based on network synergistic enhancement and a preparation method and application thereof

Abstract

The application discloses a room temperature phosphorescent collagen composite film based on network synergistic enhancement and a preparation method and application thereof. The preparation method comprises the following steps: firstly, grafting phosphorescent molecules containing amino groups to the side chain of collagen molecules through an amide reaction; then, introducing a polymer containing hydroxyl groups and layered nanosheets into a collagen film forming solution; finally, fully combining the polymer and the layered nanosheets with the collagen matrix through non-covalent interactions such as hydrogen bonds by a solvent evaporation method to prepare the room temperature phosphorescent collagen composite film based on network synergistic enhancement. The preparation method is simple and easy to operate, raw materials are widely sourced and safe and environmentally friendly; the semi-rigid network of the polymer in the film and the network enhancement effect and oxygen blocking effect of the layered nanosheets can synergistically enhance the room temperature phosphorescent performance of the film, so that the film has high mechanical properties, self-supporting properties and processability, and therefore, the film has great application potential in the fields of anti-counterfeiting, information encryption, flexible sensing, intelligent labels and the like.

Description

A room-temperature phosphorescent collagen composite film based on network synergistic enhancement, its preparation method and application Technical Field

[0001] This invention belongs to the field of biomass functional materials technology, specifically relating to a room temperature phosphorescent collagen composite film based on network synergistic enhancement, its preparation method and application. Background Technology

[0002] Since the beginning of the 21st century, organic room-temperature phosphorescent materials have become a research hotspot in fields such as anti-counterfeiting patterns, information encryption, bioimaging, and oxygen sensors due to their excellent luminescence properties and diverse applications. Among these, constructing a phosphorescent protective matrix using polymers to build high-performance polymer-based organic room-temperature phosphorescent thin films is considered an effective strategy for constructing organic room-temperature phosphorescent materials with controllable and stable luminescence properties.

[0003] In existing technologies, to achieve this goal, Mu Yingxiao et al. from Guangdong University of Technology, based on the amide reaction principle, linked aromatic derivatives to cellulose chains and prepared cellulose-based phosphorescent films through hot pressing and drying. After 1 minute of UV irradiation, the film's lifetime reached 571.1 ms. Furthermore, by using different polycyclic aromatic hydrocarbons as grafting groups, the afterglow color of the film could be adjusted from blue-green to red (Chem. Eng. J., 2022, 446: 136935). Huang Huahua et al. from Sun Yat-sen University simply mixed chitosan and organic acid solutions and dried them thoroughly in a mold to obtain chitosan films doped with organic acids. The films reported a maximum lifetime of over 200 ms. The organic acid-modified chitosan films exhibited good room-temperature phosphorescence properties. Furthermore, the luminescence performance of the films could be adjusted by changing the type of organic acid used for doping (CN114605713 A). Collagen is the most abundant structural protein in mammals in nature. Thanks to its unique triple-helix structure, high biocompatibility, and excellent biodegradability, collagen is frequently used to construct functional membranes for various applications in pharmaceuticals, food, and daily chemicals. However, there are currently no reports on the design, fabrication, and application of collagen-based room-temperature phosphorescent thin films. Summary of the Invention

[0004] This invention enhances the room-temperature phosphorescence properties of collagen-based films through network synergistic enhancement effects, providing a theoretical and technical basis for their application in emerging fields such as anti-counterfeiting, information encryption, and smart labels.

[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0006] A method for preparing a room-temperature phosphorescent collagen composite film based on network synergistic enhancement includes the following steps:

[0007] (1) The amino-containing phosphorescent molecule was dissolved in N,N-dimethylformamide to obtain a phosphorescent molecule solution with a concentration of 10 mg / mL;

[0008] (2) In a 10 mg / mL collagen acetic acid solution, 1-ethyl-(3-dimethylaminopropyl)carbodiimide, N-hydroxysuccinimide aqueous solution and the above phosphorescent molecule solution were added sequentially and stirred at room temperature for 6 h to obtain a grafted phosphorescent molecule collagen solution.

[0009] (3) The hydroxyl-containing polymer aqueous solution and the layered nanosheet dispersion were added sequentially to the above grafted phosphorescent collagen solution. After stirring for 2 hours, a film-forming solution was obtained. The film-forming solution was then poured into a polytetrafluoroethylene mold and dried at room temperature for 24 hours to obtain a room temperature phosphorescent collagen composite film based on network synergistic enhancement.

[0010] The amino-containing phosphorescent molecule is any one of 3-amino-N-ethylcarbazole, 4-aminopyridine, 4-aminobenzophenone, 4-aminobiphenyl, and 1-naphthylamine.

[0011] The hydroxyl-containing polymer is any one of polyvinyl alcohol, carboxymethyl cellulose, and chitosan.

[0012] The layered nanosheets are any one of layered zirconium phosphate, layered bimetallic hydroxide, and montmorillonite.

[0013] The mass ratio of the collagen to the amino-phosphorescent molecule, 1-ethyl-(3-dimethylaminopropyl)carbodiimide, and N-hydroxysuccinimide is 1:(0.01~0.1):(0.15~0.2):(0.15~0.2).

[0014] The mass ratio of the grafted phosphorescent collagen to the hydroxyl-containing polymer and layered nanosheet assembly is 1:(0.5~1):(0.1~0.5).

[0015] A room-temperature phosphorescent collagen composite film based on network synergistic enhancement was prepared by the method described above.

[0016] The above-mentioned room-temperature phosphorescent collagen composite film based on network synergistic enhancement is applied in the field of room-temperature phosphorescent materials.

[0017] The specific application is for manufacturing anti-counterfeiting patterns, which are used in the fields of anti-counterfeiting, information encryption, flexible sensing, and smart labels.

[0018] Compared with the prior art, the present invention has the following beneficial effects:

[0019] This invention employs an amide reaction method to introduce phosphorescent molecules into collagen molecules. This method is not only simple and easy to implement but also highly reproducible. Furthermore, all raw materials used are sourced from safe and non-toxic origins, and the preparation process complies with environmental protection requirements, ensuring no negative impact on the environment or human health. Therefore, this method guarantees both the effectiveness of the preparation and environmental friendliness and safety.

[0020] The preparation method of this invention successfully yielded a collagen composite film with phosphorescent properties. The unique feature of this film lies in the synergistic effect of the semi-rigid network reinforcement of the internal polymer and the oxygen barrier effect of the layered nanosheets, significantly enhancing the film's room-temperature phosphorescence performance. This synergistic enhancement effect allows the film to maintain its phosphorescence properties while also possessing higher stability and durability.

[0021] The collagen composite film prepared by this invention not only possesses phosphorescent properties but also exhibits high mechanical properties, self-supporting properties, and processability. These superior properties make this film a promising candidate for manufacturing anti-counterfeiting patterns that are difficult to replicate. By utilizing this film, product safety and reliability can be significantly improved, effectively preventing the emergence of counterfeit and substandard products.

[0022] The successful implementation of this invention provides a new method for developing robust, durable, and flexible room-temperature phosphorescent materials. This material has broad application prospects in various fields such as anti-counterfeiting, information encryption, flexible sensing, and smart tags. Through further research and development, it is hoped that this material can be applied to even more fields, making a greater contribution to social progress and development. Attached Figure Description

[0023] Figure 1 shows photographs of the composite film of the embodiment under sunlight, 254nm UV lamp, and 365nm UV lamp. Detailed implementation methods

[0024] The following specific embodiments illustrate the room-temperature phosphorescent collagen composite film based on network synergistic enhancement, its preparation method, and its application, as described in this invention. It should be noted that these embodiments are only for further explanation of the invention and should not be construed as limiting the scope of protection of this invention. Those skilled in the art can make some non-essential improvements and adjustments based on the above description of the invention.

[0025] Example 1

[0026] First, 4-aminobiphenyl was dissolved in N,N-dimethylformamide to obtain a phosphorescent molecular solution with a concentration of 10 mg / mL. Next, 0.5 mL of 16 mg / mL 1-ethyl-(3-dimethylaminopropyl)carbodiimide aqueous solution, 0.5 mL of 16 mg / mL N-hydroxysuccinimide aqueous solution, and the aforementioned 0.5 mL 4-aminobiphenyl molecular solution were added sequentially to 5 mL of 10 mg / mL collagen acetate solution. The mixture was stirred at room temperature for 6 h to obtain a grafted phosphorescent collagen solution. Then, 3 mL of 10 mg / mL polyvinyl alcohol aqueous solution and 4 mL of 8 mg / mL layered zirconium phosphate nanosheet dispersion were added sequentially to the grafted phosphorescent collagen solution. The mixture was stirred for another 2 h to obtain a film-forming solution. Finally, the film-forming solution was poured into a polytetrafluoroethylene mold and dried at room temperature for 24 h to obtain a room-temperature phosphorescent collagen composite film based on network synergistic enhancement.

[0027] Example 2

[0028] First, 4-aminobiphenyl was dissolved in N,N-dimethylformamide to obtain a phosphorescent molecular solution with a concentration of 10 mg / mL. Next, 0.5 mL of 16 mg / mL 1-ethyl-(3-dimethylaminopropyl)carbodiimide aqueous solution, 0.5 mL of 16 mg / mL N-hydroxysuccinimide aqueous solution, and the aforementioned 0.5 mL 4-aminobiphenyl molecular solution were added sequentially to 5 mL of 10 mg / mL collagen acetate solution. The mixture was stirred at room temperature for 6 h to obtain a grafted phosphorescent collagen solution. Then, 3 mL of 10 mg / mL polyvinyl alcohol aqueous solution and 4 mL of deionized water were added sequentially to the grafted phosphorescent collagen solution. The mixture was stirred for another 2 h to obtain a film-forming solution. Finally, the film-forming solution was poured into a polytetrafluoroethylene mold and dried at room temperature for 24 h to obtain a room-temperature phosphorescent collagen composite film based on network synergistic enhancement.

[0029] Example 3

[0030] First, 1-naphthylamine was dissolved in N,N-dimethylformamide to obtain a phosphorescent molecular solution with a concentration of 10 mg / mL. Next, 0.5 mL of 16 mg / mL 1-ethyl-(3-dimethylaminopropyl)carbodiimide aqueous solution, 0.5 mL of 16 mg / mL N-hydroxysuccinimide aqueous solution, and the aforementioned 0.5 mL 1-naphthylamine molecular solution were added sequentially to 5 mL of 10 mg / mL collagen acetate solution. The mixture was stirred at room temperature for 6 h to obtain a grafted phosphorescent collagen solution. Then, 3 mL of 10 mg / mL polyvinyl alcohol aqueous solution and 4 mL of 8 mg / mL layered zirconium phosphate nanosheet dispersion were added sequentially to the grafted phosphorescent collagen solution. The mixture was stirred for another 2 h to obtain a film-forming solution. Finally, the film-forming solution was poured into a polytetrafluoroethylene mold and dried at room temperature for 24 h to obtain a room-temperature phosphorescent collagen composite film based on network synergistic enhancement.

[0031] Example 4

[0032] First, 1-naphthylamine was dissolved in N,N-dimethylformamide to obtain a phosphorescent molecular solution with a concentration of 10 mg / mL. Next, 0.5 mL of 16 mg / mL 1-ethyl-(3-dimethylaminopropyl)carbodiimide aqueous solution, 0.5 mL of 16 mg / mL N-hydroxysuccinimide aqueous solution, and the aforementioned 0.5 mL 1-naphthylamine molecular solution were added sequentially to 5 mL of 10 mg / mL collagen acetate solution. The mixture was stirred at room temperature for 6 h to obtain a grafted phosphorescent collagen solution. Then, 3 mL of 10 mg / mL polyvinyl alcohol aqueous solution and 4 mL of deionized water were added sequentially to the grafted phosphorescent collagen solution. The mixture was stirred for another 2 h to obtain a film-forming solution. Finally, the film-forming solution was poured into a polytetrafluoroethylene mold and dried at room temperature for 24 h to obtain a room-temperature phosphorescent collagen composite film based on network synergistic enhancement.

[0033] Example 5

[0034] First, 3-amino-N-ethylcarbazole was dissolved in N,N-dimethylformamide to obtain a phosphorescent molecular solution with a concentration of 10 mg / mL. Next, 0.5 mL of 16 mg / mL 1-ethyl-(3-dimethylaminopropyl)carbodiimide aqueous solution, 0.5 mL of 16 mg / mL N-hydroxysuccinimide aqueous solution, and the aforementioned 0.5 mL 3-amino-N-ethylcarbazole molecular solution were added sequentially to 5 mL of 10 mg / mL collagen acetate solution. The mixture was stirred at room temperature for 6 h to obtain a grafted phosphorescent collagen solution. Then, 3 mL of 10 mg / mL polyvinyl alcohol aqueous solution and 4 mL of 8 mg / mL layered zirconium phosphate nanosheet dispersion were added sequentially to the grafted phosphorescent collagen solution. The mixture was stirred for another 2 h to obtain a film-forming solution. Finally, the film-forming solution was poured into a polytetrafluoroethylene mold and dried at room temperature for 24 h to obtain a room-temperature phosphorescent collagen composite film based on network synergistic enhancement.

[0035] Example 6

[0036] First, 3-amino-N-ethylcarbazole was dissolved in N,N-dimethylformamide to obtain a phosphorescent molecular solution with a concentration of 10 mg / mL. Next, 0.5 mL of 16 mg / mL 1-ethyl-(3-dimethylaminopropyl)carbodiimide aqueous solution, 0.5 mL of 16 mg / mL N-hydroxysuccinimide aqueous solution, and the aforementioned 0.5 mL 3-amino-N-ethylcarbazole molecular solution were added sequentially to 5 mL of 10 mg / mL collagen acetate solution. The mixture was stirred at room temperature for 6 h to obtain a grafted phosphorescent collagen solution. Then, 3 mL of 10 mg / mL polyvinyl alcohol aqueous solution and 4 mL of deionized water were added sequentially to the grafted phosphorescent collagen solution. The mixture was stirred for another 2 h to obtain a film-forming solution. Finally, the film-forming solution was poured into a polytetrafluoroethylene mold and dried at room temperature for 24 h to obtain a room-temperature phosphorescent collagen composite film based on network synergistic enhancement.

[0037] The room-temperature phosphorescent collagen composite films prepared in Examples 1-6 were photographed under 25°C and 8W UV light, as shown in Figure 1. Figure 1 shows photographs of the composite films of the examples under sunlight, 254nm UV light, and 365nm UV light. It can be seen from the figure that the products prepared in the examples possess room-temperature phosphorescence properties.

Claims

1. A method for preparing a room-temperature phosphorescent collagen composite film based on network synergistic enhancement, characterized in that, Specifically, the following steps are included: (1) The amino-containing phosphorescent molecules were dissolved in N,N-dimethylformamide to obtain a phosphorescent molecule solution with a concentration of 10 mg / mL; (2) 1-ethyl-(3-dimethylaminopropyl)carbodiimide, N-hydroxysuccinimide aqueous solution and the above phosphorescent molecule solution were added sequentially to a 10 mg / mL collagen acetic acid solution and stirred at room temperature for 6 h to obtain a grafted phosphorescent molecule collagen solution; (3) Hydroxyl-containing polymer aqueous solution and layered nanosheet dispersion were added sequentially to the above grafted phosphorescent molecule collagen solution and stirred for 2 h to obtain a film-forming solution. The film-forming solution was then poured into a polytetrafluoroethylene mold and dried at room temperature for 24 h to obtain a room temperature phosphorescent collagen composite film based on network synergistic enhancement.

2. The method for preparing a room-temperature phosphorescent collagen composite film based on network synergistic enhancement according to claim 1, characterized in that: The amino-containing phosphorescent molecule is any one of 3-amino-N-ethylcarbazole, 4-aminopyridine, 4-aminobenzophenone, 4-aminobiphenyl, and 1-naphthylamine.

3. The method for preparing a room-temperature phosphorescent collagen composite film based on network synergistic enhancement according to claim 1, characterized in that: The hydroxyl-containing polymer is any one of polyvinyl alcohol, cellulose, and chitosan.

4. The method for preparing a room-temperature phosphorescent collagen composite film based on network synergistic enhancement according to claim 1, characterized in that: The layered nanosheets are any one of layered zirconium phosphate, layered bimetallic hydroxide, and montmorillonite.

5. The method for preparing a room-temperature phosphorescent collagen composite film based on network synergistic enhancement according to claim 1, characterized in that: In step 2, the mass ratio of the collagen to the amino phosphorescent molecule, 1-ethyl-(3-dimethylaminopropyl)carbodiimide, and N-hydroxysuccinimide is 1:(0.01~0.1):(0.15~0.2):(0.15~0.2).

6. The method for preparing a room-temperature phosphorescent collagen composite film based on network synergistic enhancement according to claim 1, characterized in that: The mass ratio of the grafted phosphorescent collagen to the hydroxyl-containing polymer and layered nanosheets is 1:(0.5~1):(0.1~0.5).

7. A room-temperature phosphorescent collagen composite film based on network synergistic enhancement, prepared by any one of the preparation methods described in claims 1-6.

8. The application of the room-temperature phosphorescent collagen composite film based on network synergistic enhancement as described in claim 7 in the field of room-temperature phosphorescent materials.

9. The application of the room-temperature phosphorescent collagen composite film based on network synergistic enhancement according to claim 8, characterized in that: Used to manufacture anti-counterfeiting patterns, and applied in the fields of anti-counterfeiting, information encryption, flexible sensing, and smart labels.

Images