Bio-fluorescent intelligent membrane, preparation method and application thereof

Abstract

The application provides a bio-fluorescent intelligent membrane and a preparation method and application thereof, and the preparation method comprises the following steps: (1) adding isocyanate monomers and amino compounds into a first solvent and stirring to react; (2) adding a bio-fluorescent agent and a hydroxyl compound into the reaction system and stirring to react, so as to obtain a polyurea reactant; wherein the bio-fluorescent agent is obtained by addition polymerization reaction with the isocyanate monomers and the amino compounds as reaction raw materials; (3) printing into a film by using the polyurea reactant as a printing line by means of 4D printing, so as to obtain the bio-fluorescent intelligent membrane. In the application, the bio-fluorescent agent is self-prepared, and the bio-fluorescent agent and the hydroxyl compound are introduced into the polyurea material to perform polymerization reaction, so that the bio-fluorescent polyurea intelligent membrane has excellent bio-fluorescent performance; the bio-fluorescent intelligent membrane of the application has no toxic side effects on cells, has good biocompatibility, has good shape memory performance, and can realize intelligent regulation and control.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of functional materials, in particular to a bio-fluorescent intelligent membrane and a preparation method and application thereof. BACKGROUND

[0002] With the development of science and technology, the demand for materials with special functions is increasing. In biomedical research, materials capable of effectively labeling and detecting biomolecules and cells are needed; in the field of environmental science, there is an urgent need for sensor materials that can detect pollutants in real time and sensitively.

[0003] Traditional detection methods and materials often have some limitations, such as poor labeling specificity, low detection sensitivity, and insufficient sensor stability. At the same time, the development of intelligent materials provides a new way to solve these problems. Polyurea materials have attracted attention due to their good mechanical properties and chemical stability; however, the existing polyurea materials have poor biocompatibility, and the comprehensive performance in bio-fluorescence and intelligent response needs to be improved.

[0004] Therefore, there is an urgent need to provide a bio-fluorescent intelligent membrane and a preparation method and application thereof. SUMMARY

[0005] The present application provides a bio-fluorescent intelligent membrane and a preparation method and application thereof, which can solve the problems of poor biocompatibility and poor fluorescence stability of traditional polyurea materials in the application process.

[0006] In a first aspect, the present application provides a preparation method of a bio-fluorescent intelligent membrane, which comprises the following steps:

[0007] (1) stirring and reacting isocyanate monomers and amino compounds in a first solvent;

[0008] (2) adding bio-fluorescent agents and hydroxyl compounds to the reaction system, and stirring and reacting to obtain polyurea reactants; wherein the bio-fluorescent agents are obtained by addition polymerization reaction using isocyanate monomers and amino compounds as raw materials;

[0009] (3) printing into a film by using 4D printing with the polyurea reactants as a printing solution to obtain the bio-fluorescent intelligent membrane.

[0010] Preferably, in step (2), the bio-fluorescent agents are prepared by mixing and reacting isocyanate monomers and amino compounds in a second solvent to obtain the bio-fluorescent agents; wherein the second solvent is an aqueous acetone solution or a phosphate buffered saline solution.

[0011] Preferably, the content of the isocyanate monomer is 5-20 mmol, the content of the amino compound is 5-20 mmol, and the content of the second solvent is 85-95%.

[0012] Preferably, the reaction temperature is 28-32° C. and the reaction time is 3-5 h.

[0013] Preferably, the isocyanate monomer is toluene diisocyanate or isophorone diisocyanate; and the amino compound is polyetheramine D-400, polyetheramine D-2000, diethyltoluenediamine or tetramethylethylenediamine.

[0014] Preferably, in step (1), the molar ratio of the isocyanate monomer to the amino compound is 10:(3-7).

[0015] More preferably, the first solvent is N,N'-dimethylformamide, N,N'-dimethylacetamide or dichloromethane, and the content of the first solvent is 10-30 mL.

[0016] Preferably, in step (2), the hydroxy compound is polycaprolactone diol-2000 or polycaprolactone diol-4000, and the molar ratio of the total amount of the hydroxy compound and the amino compound to the isocyanate monomer is 1:1.

[0017] Preferably, in the reaction system, the content of the bioluminescent agent is 20-50 mg / mL.

[0018] Preferably, in step (1), the reaction temperature is 20-30° C. and the reaction time is 3-5 h.

[0019] Preferably, in step (2), the reaction temperature is 50-60° C. and the reaction time is 20-27 h.

[0020] Preferably, in step (3), the printing temperature is 80-120°C.

[0021] In a second aspect, the present invention further provides a bioluminescent smart membrane, which is prepared using any preparation method described in the first aspect above.

[0022] In a third aspect, the present invention further provides an application of the bioluminescent smart film described in the second aspect in biomedical materials.

[0023] Compared with the prior art, the present invention has at least the following beneficial effects:

[0024] In the present invention, a low-molecular-weight bioluminescent agent is first prepared using an isocyanate monomer and an amino compound as reaction raw materials. Then, the bioluminescent agent and a hydroxyl compound are introduced into a polymerization reaction during the synthesis of a polyurea material to form a polyurea reactant. Finally, the polyurea reactant is printed into a film using 4D printing to obtain a bioluminescent smart membrane. In the present invention, a low-molecular-weight bioluminescent agent is prepared by itself and introduced into a polyurea material with a hydroxyl compound for polymerization reaction, so that the bioluminescent polyurea smart membrane of the present invention has excellent bioluminescent properties and can efficiently emit fluorescence when excited by light of a specific wavelength. In addition, the bioluminescent smart membrane of the present invention has no toxic side effects on cells, has good biocompatibility, and has good shape memory properties, and can achieve intelligent regulation. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] In order 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 some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0026] Figure 1 This is a luminescence image of a bioluminescent agent particle provided by an embodiment of the present invention;

[0027] Figure 2 is a particle size distribution diagram of the bioluminescent agent particles provided in Example 1 of the present invention;

[0028] Figure 3 This is the ultraviolet absorption spectrum of the bioluminescent agent particles provided in Example 1 of the present invention. DETAILED DESCRIPTION

[0029] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0030] An embodiment of the present invention provides a method for preparing a bioluminescent smart film, the method comprising the following steps:

[0031] (1) adding an isocyanate monomer and an amino compound into a first solvent and stirring for reaction;

[0032] (2) adding a bioluminescent agent and a hydroxyl compound to a reaction system, stirring and reacting the mixture to obtain a polyurea reactant; wherein the bioluminescent agent is obtained by an addition polymerization reaction using an isocyanate monomer and an amino compound as reaction raw materials;

[0033] (3) Using the polyurea reactant as a printing line, a 4D printing method is used to print a film to obtain the bioluminescent smart film.

[0034] In an embodiment of the present invention, a bioluminescent agent with a small particle size is first prepared using an isocyanate monomer and an amino compound as reaction raw materials. Then, during the synthesis process of a polyurea material, the bioluminescent agent and a hydroxyl compound are introduced into a polymerization reaction to form a polyurea reactant. Finally, the polyurea reactant is printed into a film using 4D printing to obtain a bioluminescent smart membrane. In the present invention, a bioluminescent agent with a small molecular weight is prepared and introduced into a polyurea material with a hydroxyl compound for polymerization reaction, so that the bioluminescent polyurea smart membrane of the present invention has excellent bioluminescent properties. When excited by light of a specific wavelength, it can efficiently emit fluorescence. In addition, the bioluminescent smart membrane of the present invention has no toxic side effects on cells, has good biocompatibility, and has good shape memory properties, and can achieve intelligent regulation.

[0035] According to some preferred embodiments, in step (2), the bioluminescent agent is prepared by the following method: adding the isocyanate monomer and the amino compound to a second solvent for mixed reaction to obtain the bioluminescent agent; wherein the second solvent is an acetone aqueous solution or a phosphate buffered saline solution.

[0036] In an embodiment of the present invention, an addition polymerization reaction is carried out using isocyanate and an amino compound as raw materials in a second solvent system to form a bioluminescent agent with a high fluorescence quantum yield and excellent fluorescence performance. The bioluminescent agent particles have a small particle size (100-300 nm), which allows the particle size of the prepared solution to be even smaller. The bioluminescent agent can be evenly dispersed in the bioluminescent smart film. The bioluminescent agent is also very sensitive to changes in environmental polarity and can exhibit different fluorescence intensities and wavelengths in different environments. At the same time, it will not be quenched during application.

[0037] According to some preferred embodiments, the content of the isocyanate monomer is 5-20 mmol (for example, it can be 5 mmol, 8 mmol, 10 mmol, 12 mmol, 15 mmol, 18 mmol or 20 mmol), the content of the amino compound is 5-20 mmol (for example, it can be 5 mmol, 8 mmol, 10 mmol, 12 mmol, 15 mmol, 18 mmol or 20 mmol), and the content of the second solvent is 85-95% (for example, it can be 85%, 88%, 90%, 92% or 95%).

[0038] According to some preferred embodiments, the reaction temperature is 28-32°C (for example, 28°C, 29°C, 30°C, 31°C or 32°C), and the reaction time is 3-5h (for example, 3h, 4h or 5h).

[0039] In the embodiments of the present invention, rational control of the types and contents of the isocyanate monomer, amino compound, and second solvent, as well as reaction conditions, during the reaction process facilitates the preparation of a bioluminescent agent with good solubility, good biocompatibility, and excellent bioluminescent properties, thereby facilitating the preparation of a bioluminescent smart membrane with stable fluorescent properties. The molar ratio of the isocyanate monomer to the amino compound is preferably 1:1. For example, if the isocyanate monomer content is too low, some amino groups may fail to fully react, forming incomplete intermediates or byproducts, ultimately adversely affecting the purity and fluorescent properties of the bioluminescent agent. On the other hand, if the isocyanate monomer content is too high, more cross-linked structures may form, thereby affecting the molecular weight distribution and solubility of the bioluminescent agent.

[0040] It should be noted that, in the embodiment of the present invention, the second solvent is preferably an acetone aqueous solution, wherein the mass ratio of acetone to water is 3:7.

[0041] According to some preferred embodiments, the isocyanate monomer is toluene diisocyanate or isophorone diisocyanate; and the amino compound is polyetheramine D-400, polyetheramine D-2000, diethyltoluenediamine or tetramethylethylenediamine.

[0042] In the embodiments of the present invention, by using the aforementioned isocyanate monomers and amino compounds, toluene diisocyanate and isophorone diisocyanate can form a stable cyclic structure with diethyltoluenediamine or tetramethylethylenediamine, which not only improves the stability of the molecule but also helps ensure good fluorescence properties of the bioluminescent agent.

[0043] At the same time, in an embodiment of the present invention, the polyurea material is prepared using the above-mentioned types of isocyanate monomers and amino compounds, and the raw materials for synthesizing the bioluminescent agent are preferably the same as the raw materials for synthesizing the polyurea matrix material. In this way, the bioluminescent agent can be fully dissolved and evenly dispersed in the polyurea material, thereby facilitating the stable and uniform fluorescence performance of the bio-smart membrane. Furthermore, the above-mentioned types of isocyanate monomers have high reactivity and can rapidly undergo addition reactions with amino compounds to form stable polyurea segments. At the same time, compared with other types of isocyanates, toluene diisocyanate and isophorone diisocyanate have lower toxicity under appropriate reaction conditions. Moreover, by selecting the above-mentioned types of amino compounds to react with them, the distribution and metabolic behavior of the polymer reactants in the organism can be optimized, so that the bio-smart membrane has excellent biocompatibility.

[0044] According to some preferred embodiments, in step (1), the molar ratio of the isocyanate monomer to the amino compound is 10:(3-7) (for example, it can be 10:3, 10:4, 10:5, 10:6 or 10:7); the first solvent is N,N'-dimethylformamide, N,N'-dimethylacetamide or dichloromethane, and the content of the first solvent is 10-30 mL (for example, it can be 10 mL, 20 mL or 30 mL).

[0045] In the embodiment of the present invention, in the process of synthesizing the polyurea reactant using isocyanate monomer and amino compound as raw materials in the above-mentioned first solvent, by reasonably controlling the ratio of isocyanate monomer and amino compound, it is beneficial to prepare a polyurea reactant with an appropriate degree of cross-linking and high purity. If the content of isocyanate monomer is too high or too low, unreacted reactants will exist in the reaction system, thereby affecting the molecular weight of the polyurea reactant.

[0046] According to some preferred embodiments, in step (2), the hydroxy compound is polycaprolactone diol-2000 or polycaprolactone diol-4000; and the molar ratio of the total amount of the hydroxy compound and the amino compound to the isocyanate monomer is 1:1.

[0047] In the embodiment of the present invention, during the reaction of the isocyanate monomer and the amino compound, the isocyanate group compound containing a benzene ring structure can serve as the hard segment of the polymer, and the amino compound can serve as the soft segment of the polymer. By further introducing a certain amount of hydroxyl compound, the hydroxyl compound can serve as a chain extender to control the ratio of the soft and hard segments during the reaction, thereby regulating the thermodynamic properties and toughness of the polyurea reactant, so that the polyurea reactant has excellent shape memory properties.

[0048] According to some preferred embodiments, in the reaction system, the content of the bioluminescent agent is 20-50 mg / mL (for example, 20 mg / mL, 30 mg / mL, 40 mg / mL or 50 mg / mL).

[0049] In the embodiment of the present invention, during the synthesis of the polyurea reactant, by introducing the bioluminescent agent prepared as described above and rationally controlling the content of the bioluminescent agent, the bioluminescent agent can interact with the polyurea molecular chain through chemical bonding between the isocyanate component and the amino compound component. This allows the bioluminescent agent to be uniformly dispersed in the polyurea reactant matrix without affecting the curing performance and shape memory properties of the polyurea reactant, thereby enabling the bioluminescent smart film to have excellent bioluminescent properties. For example, in the reaction system for polyurea synthesis, if the content of the bioluminescent agent is too low, it is not conducive to significantly enhancing the fluorescence properties of the bioluminescent smart film. On the other hand, if the content of the bioluminescent agent is too high, not only will the amount of printable polyurea reactant material be reduced, but the subsequent curing effect will also be affected.

[0050] According to some preferred embodiments, in step (1), the reaction temperature is 20-30°C (for example, 20°C, 22°C, 25°C, 28°C or 30°C), and the reaction time is 3-5h (for example, 3h, 4h or 5h); in step (2), the reaction temperature is 50-60°C (for example, 50°C, 52°C, 55°C, 58°C or 60°C), and the reaction time is 20-27h (for example, 20h, 22h, 24h or 27h).

[0051] In an embodiment of the present invention, during the synthesis of the polyurea reactant, the reactant is first reacted at 20-30°C for 3-5 hours, and then the temperature of the reaction system is raised to 50-60°C. A bioluminescent agent and a hydroxyl compound are sequentially added and stirred to obtain a polyurea reactant having fluorescent properties and shape memory properties (glass transition temperature of 40-45°C).

[0052] According to some preferred embodiments, in step (3), the printing temperature is 80-120°C (for example, 80°C, 90°C, 100°C, 110°C or 120°C).

[0053] In an embodiment of the present invention, the polyurea reactant obtained by the reaction is used as a printing solution, and a film with certain gaps is designed and printed on a suitable substrate (such as a glass sheet, plastic sheet or metal sheet, etc., selected according to the application scenario) using a 4D printing method. During the printing process, the printing temperature is controlled to 80-120°C and the bottom temperature of the printing is controlled to 55°C, thereby forming a bioluminescent smart membrane with a certain porosity. In this way, the bioluminescent smart membrane can be permeable and exchange substances during the application process, allowing cells to exchange necessary substances with the external environment, such as the entry and exit of oxygen, carbon dioxide, nutrients and metabolic waste.

[0054] It should be noted that, in the embodiment of the present invention, after printing is completed, the printed bio-intelligent membrane needs to be dried, cured and other processing steps. Specifically, the drying temperature can be 60-80°C and the time can be more than 48 hours, and the curing temperature can be 55-65°C and the time can be 40 hours.

[0055] An embodiment of the present invention further provides a bioluminescent smart film, which is prepared using any of the preparation methods described above.

[0056] The bioluminescent smart film in the embodiment of the present invention has excellent fluorescence performance and biocompatibility, and has shape memory performance and thermal degradation performance, and can realize intelligent control of the bioluminescent film by regulating temperature.

[0057] The embodiments of the present invention also provide applications of the above-mentioned bioluminescent smart film in biomedical materials.

[0058] The bioluminescent smart film in the embodiment of the present invention can efficiently emit fluorescence (such as Figure 1 The fluorescence emission wavelength range is broad and can be controlled, from ultraviolet to visible light, depending on the selected fluorescent substance. Its high fluorescence intensity and excellent photostability maintain a stable fluorescence signal over time, facilitating long-term detection and observation. This bioluminescent smart membrane can be used to label and observe specific structures or molecules within living cells.

[0059] In order to more clearly illustrate the technical solutions and advantages of the present invention, the preparation method and application of a bioluminescent smart film are described in detail below through several embodiments.

[0060] Example 1:

[0061] Preparation of a bioluminescent agent: 5 mmol of an isocyanate monomer (toluene diisocyanate) and 5 mmol of an amino compound (diethyltoluenediamine) were added to 20 mL of a first solvent (acetone and deionized water in a mass ratio of 3:7) and reacted at 30°C for 5 h. The bioluminescent agent was obtained after centrifugation.

[0062] (1) 10 mmol of isocyanate monomer (toluene diisocyanate) and 5 mmol of amino compound (polyetheramine D-400) were added to 30 mL of the first solvent (N,N'-dimethylformamide) and reacted at 30°C for 5 h;

[0063] (2) Then, 30 mg / mL of the bioluminescent agent prepared above and 5 mmol of the hydroxy compound (polycaprolactone diol-2000) were added to the reaction system of step (1) in sequence and stirred to mix evenly. The temperature of the reaction system was raised to 60° C. and the reaction was carried out for 25 hours to obtain a polyurea reactant.

[0064] (3) Polyurea reactants were used as printing materials to form a film on a glass sheet using a 4D printing method. The printing temperature was controlled at 180°C during the printing process to obtain a bioluminescent smart film.

[0065] Example 2:

[0066] Preparation of a bioluminescent agent: 20 mmol of an isocyanate monomer (isophorone diisocyanate) and 20 mmol of an amino compound (tetramethylethylenediamine) were added to 80 mL of a first solvent (acetone and deionized water in a mass ratio of 3:7) and reacted at 30°C for 5 h. The bioluminescent agent was obtained after centrifugation.

[0067] (1) 10 mmol of isocyanate monomer (isophorone diisocyanate) and 3 mmol of amino compound (polyetheramine D-2000) were added to 30 mL of the first solvent (N,N'-dimethylformamide) and reacted at 30°C for 4 h;

[0068] (2) Then, 50 mg / mL of the bioluminescent agent prepared above and 7 mmol of the hydroxy compound (polycaprolactone diol-4000) were added to the reaction system of step (1) in sequence and stirred to mix evenly. The temperature of the reaction system was raised to 55° C. and the reaction was carried out for 26 hours to obtain a polyurea reactant.

[0069] (3) Using polyurea reactants as printing lines, a film was printed on a glass sheet using a 4D printing method. During the printing process, the printing temperature was controlled at 180°C to obtain a bioluminescent smart film.

[0070] Example 3:

[0071] Preparation of a bioluminescent agent: 15 mmol of an isocyanate monomer (toluene diisocyanate) and 15 mmol of an amino compound (diethyltoluenediamine) were added to 60 mL of a first solvent (acetone and deionized water in a mass ratio of 3:7) and reacted at 30°C for 5 h. The bioluminescent agent was obtained after centrifugation.

[0072] (1) 10 mmol of isocyanate monomer (toluene diisocyanate) and 7 mmol of amino compound (tetramethyl ethylenediamine) were added to 30 mL of the first solvent (dichloromethane) to react at 25 °C for 5 h;

[0073] (2) 20 mg / mL of the above-prepared biofluorescent agent and 3 mmol of hydroxyl compound (polycaprolactone diol-2000) were then sequentially added to the reaction system of step (1) to stir and mix, and the temperature of the reaction system was increased to 60 °C, and the reaction was carried out for 25 h to obtain a polyurea reactant;

[0074] (3) The polyurea reactant was used as a printing line to perform printing and film formation on a glass sheet by 4D printing, and the printing temperature was controlled at 180 °C during the printing process to obtain a biofluorescent intelligent film.

[0075] Example 4:

[0076] Example 4 is basically the same as Example 1, except that in step (1), the content of isocyanate monomer is 15 mmol.

[0077] Example 5:

[0078] Example 5 is basically the same as Example 1, except that in step (2), the content of hydroxyl compound is 15 mmol.

[0079] Example 6:

[0080] Example 6 is basically the same as Example 1, except that in step (2), the hydroxyl compound is replaced by polyetheramine-400 of the same content.

[0081] Example 7:

[0082] Example 7 is basically the same as Example 1, except that in step (1), the isocyanate monomer (isophorone diisocyanate) is replaced by hexamethylene diisocyanate trimer of the same content, and the amino compound (diethyl toluene diamine) is replaced by tris (2-aminoethyl) amine of the same content.

[0083] Example 8:

[0084] Example 8 is basically the same as Example 1, except that when preparing the biofluorescent agent, the content of isocyanate monomer is 10 mmol.

[0085] Example 9:

[0086] Example 9 is basically the same as Example 1, except that in step (2), the content of biofluorescent agent is 60 mg / mL.

[0087] Comparative Example 1:

[0088] Comparative Example 1 is substantially the same as Example 1, except that in step (2), the bioluminescent agent is replaced with the same content of rhodamine B.

[0089] Comparative Example 2:

[0090] Comparative Example 2 is substantially the same as Example 1, except that, in step (2), no hydroxy compound is added.

[0091] The bioluminescent smart membranes prepared in Examples 1 to 9 and Comparative Examples 1 to 2 (hereinafter referred to as samples) were subjected to performance tests. The test results are shown in FIG. Figure 1 and as shown in Table 1.

[0092] Fluorescence test: The fluorescence properties of the sample are detected by ultraviolet light irradiation; Biocompatibility test: Cells are cultured on the surface of each sample and the cell growth is observed after 7 days of cell culture to evaluate the biocompatibility of the sample.

[0093] Table 1

[0094]

[0095] From Table 1 and Figures 1 to 3 As can be seen from the figure, compared with the comparative example, the particle size of the bioluminescent agent in the embodiment of the present invention is smaller (particle size 100-300nm) and has excellent fluorescence performance. This makes the particle size of the prepared solution smaller, and the bioluminescent agent can be evenly dispersed in the bioluminescent smart film, so that the bioluminescent smart film prepared in the embodiment of the present invention has excellent fluorescence performance. In addition, the bioluminescent smart film has good biocompatibility and shape memory performance, and is easy to print and form. In Examples 4 and 5, if the content of the isocyanate monomer is too high or too low, the reactant will remain after the reaction and printing cannot be performed. In Example 6 If the hydroxyl compound uses materials from the prior art, the glass transition temperature of the biofilm will increase, making it difficult to maintain shape memory within the body temperature range. In Example 7, if the isocyanate monomer and the amino compound use compounds commonly used in the prior art, not only will the material be unable to be printed and formed, but it will also be difficult to prepare a non-biotoxic fluorescent smart film. In Example 8, if the amount of bioluminescent agent added is too much, it will not only be detrimental to enhancing the fluorescence performance, but will inhibit cell growth. Furthermore, in Comparative Example 1, if the bioluminescent agent used in the prior art is used, not only will the bioluminescent membrane be unable to emit light stably, but it will also have toxic side effects on cells.

[0096] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the various embodiments of the present invention.

Claims

1. A method for preparing a bioluminescent smart film, characterized in that: The preparation method comprises the following steps: (1) adding an isocyanate monomer and an amino compound into a first solvent and stirring to react; (2) adding a bioluminescent agent and a hydroxyl compound to a reaction system, stirring and reacting the mixture to obtain a polyurea reactant; wherein the bioluminescent agent is obtained by an addition polymerization reaction using an isocyanate monomer and an amino compound as reaction raw materials; The isocyanate monomer is toluene diisocyanate or isophorone diisocyanate; The amino compound in step (1) is polyetheramine D-400 or polyetheramine D-2000, and in step (2), the amino compound in preparing the bioluminescent agent is diethyltoluenediamine or tetramethylethylenediamine. The hydroxy compound is polycaprolactone diol-2000 or polycaprolactone diol-4000; (3) The polyurea reactant is used as a printing solution to print a film using a 4D printing method to obtain the bioluminescent smart film.

2. The preparation method according to claim 1, characterized in that In step (2), the bioluminescent agent is prepared by the following method: adding the isocyanate monomer and the amino compound into a second solvent for mixed reaction to obtain the bioluminescent agent; wherein the second solvent is an acetone aqueous solution or a phosphate buffered saline solution.

3. The preparation method according to claim 2, characterized in that The content of the isocyanate monomer is 5-20 mmol, the content of the amino compound is 5-20 mmol, and the content of the second solvent is 85-95 wt %.

4. The preparation method according to claim 2, characterized in that The reaction temperature is 28-32° C. and the reaction time is 3-5 h.

5. The preparation method according to claim 1, characterized in that In step (1), the molar ratio of the isocyanate monomer to the amino compound is 10:(3-7); and / or The first solvent is N,N'-dimethylformamide, N,N'-dimethylacetamide or dichloromethane, and the content of the first solvent is 10-30 mL.

6. The preparation method according to claim 1, characterized in that In step (2), the molar ratio of the total amount of the hydroxyl compound and the amino compound to the isocyanate monomer is 1:1; and / or In the reaction system, the content of the bioluminescent agent is 20-50 mg / mL.

7. The preparation method according to claim 1, characterized in that In step (1), the reaction temperature is 20-30°C and the reaction time is 3-5h; and / or In step (2), the reaction temperature is 50-60°C and the reaction time is 20-27 hours.

8. The preparation method according to claim 1, characterized in that In step (3), the printing temperature is 80-120°C.

9. A bioluminescent smart film, characterized in that: The preparation method according to any one of claims 1 to 8 is used.

10. Use of the bioluminescent smart film according to claim 9 in biomedical materials.

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