CN109111913B - A kind of pair of transmitting cellulose base fluorescent material and its preparation method and application - Google Patents

Abstract

The invention discloses a double-emission cellulose-based fluorescent material and its preparation method and application. The double-emission cellulose-based fluorescent material has good biocompatibility and processability. The dual-emission cellulose-based fluorescent material includes a type of fluorescent group as an indicator because of its responsiveness to biogenic amine; a type of fluorescent group as an internal standard because of its non-responsiveness to biogenic amine. The present invention also discloses a detection method for biogenic amines, wherein the above-mentioned double-emission cellulose-based fluorescent material is used, and the detection method is based on the change of the fluorescence intensity ratio of the two types of fluorescent groups and the change of the fluorescent color of the cellulose-based fluorescent material , to achieve the detection of biogenic amines. During the detection process, the fluorescence intensity ratio of the two types of fluorophores changes in color visible to the naked eye as the concentration of biogenic amine increases, which can realize the visual detection of biogenic amine.

Description

A kind of double emission cellulose-based fluorescent material and its preparation method and application

technical field

The invention relates to a double-emission cellulose-based fluorescent material and its preparation method and application, belonging to the technical field of biological detection.

Background technique

Biogenic amines refer to a class of organic amine compounds, including ammonia, dimethylamine, trimethylamine, etc., which are closely related to various metabolic processes and are produced in large quantities during the degradation of amino acids. An abnormal increase in the concentration of biogenic amines is often taken as a signal of food spoilage or disease. Therefore, the development of an effective method for the detection of biogenic amines is crucial for its practical application. Recently, due to its unique high sensitivity and good selectivity, fluorescent sensors have made some research progress in the fields of food quality monitoring and auxiliary disease diagnosis. Benzhong Tang's group used the selective responsiveness of aggregation-induced luminescent fluorescent molecules to biogenic amines to successfully detect the freshness of seafood (ACS Sensor 2016, 1, 179-184). The pyrene fluorescent molecular derivatives designed by Liu Kaiqiang's research group can detect aniline at a lower concentration, so as to realize the auxiliary diagnosis of lung cancer (Sensors and Actuators B 2017, 241, 1316–1323). However, most of these fluorescent sensors used a single fluorescent molecule for monitoring in the past. During use, it is very susceptible to interference from factors such as the concentration of fluorescent molecules, the external environment, and instrument parameter settings, resulting in low measurement accuracy. At the same time, although the change in the intensity of fluorescence produced by a single fluorescent molecule during the detection process can also be observed with the naked eye, it is impossible to establish a unified observation standard, because the ability of the naked eye to perceive light intensity is greatly affected by human factors. In addition, the fluorescent sensors used today are based on small molecular compounds and cannot be used as materials alone. At the same time, small molecular fluorescent compounds are easy to migrate with environmental changes, and have high toxicity, which limits their practical application.

Contents of the invention

In order to solve the deficiencies of the prior art, the object of the present invention is to provide a dual-emission cellulose-based fluorescent material, which uses cellulose and its derivatives as matrix materials, and the cellulose and Its derivatives have the advantages of good biocompatibility, excellent processing performance, wide range of sources, and low price, and are excellent carriers as skeleton materials. At the same time, the molecular chains of cellulose and its derivatives have multiple hydroxyl groups that can be derivatized, and use the hydroxyl groups to undergo esterification or etherification reactions with molecules containing fluorescent groups to bond at least two types of fluorescent groups; , one type of fluorescent group is used as an indicator of biogenic amine because of its responsiveness to biogenic amine, and the other type of fluorescent group is used as an internal standard of biogenic amine because of its non-responsiveness to biogenic amine; not only that, these two types of fluorescence The group also needs to have partially or completely overlapped excitation spectra and distinguishable emission spectra; accurate detection of biogenic amines can be achieved by observing the change in the ratio of the fluorescence intensity emitted by these two types of fluorescent groups. At the same time, after a type of fluorescent group as an indicator responds to biogenic amine, the fluorescence color of the entire material system changes due to the change in fluorescence intensity, resulting in an obvious signal change that can be recognized by the naked eye, thereby realizing the detection of biogenic amine. Visual inspection.

To achieve the above object, the present invention provides the following technical solutions:

A dual-emission cellulose-based fluorescent material, the fluorescent material uses cellulose and its derivatives as a base material, and the fluorescent material also includes at least two types of fluorescent groups bonded to the base material; the two Fluorophores have partially or completely overlapped excitation spectra and resolvable emission spectra; among the two types of fluorophores, one type of fluorophore is responsive to biogenic amines, and the other type of fluorophore is responsive to biogenic amines. Amines are unresponsive.

According to the present invention, the two types of fluorescent groups are bonded to the same cellulose chain, or the two types of fluorescent groups are respectively bonded to two cellulose chains.

According to the invention, the structural formulas of the two cellulose chains are the same or different.

According to the present invention, the cellulose is selected from at least one of microcrystalline cellulose, cotton pulp, wood pulp, bamboo pulp, degreased cotton, bagasse, wood and cellulose prepared from plant straws.

According to the present invention, the cellulose derivative is at least one selected from cellulose ethers and cellulose esters.

Preferably, the cellulose ester is selected from cellulose acetate, cellulose acetate butyrate, cellulose propionate, cellulose acetate propionate, cellulose butyrate, cellulose nitrate, cellulose benzoate, cellulose At least one of cinnamate esters.

Preferably, the cellulose ether is at least one selected from methylcellulose, ethylcellulose, carboxymethylcellulose, hydroxyethylcellulose, and hydroxymethylcellulose.

In the present invention, the two types of fluorophores should meet the requirements of partially overlapping or completely overlapping excitation spectra and resolvable emission spectra. The reason is that the two types of fluorophores meeting the above conditions can be observed with naked eyes The fluorescence intensity changes of these two types of fluorophores are detected and distinguished according to different colors, so as to realize the visual detection of biogenic amines.

According to the present invention, the fluorescent group responsive to biogenic amine is from at least one of fluorescein-based fluorescent molecules, rhodamine-based fluorescent molecules, and aggregation-induced emission (AIE) fluorescent molecules.

Preferably, the fluorescein-based fluorescent molecules are selected from the group consisting of fluorescein and its isomers, fluorescein isothiocyanate and its isomers, fluorescein isocyanate and its isomers, aminofluorescein and its isomers , at least one of carboxyfluorescein and its isomers, 5-bromomethylfluorescein and its isomers.

Preferably, the rhodamine-based fluorescent molecules are selected from at least one of rhodamine B, rhodamine 110, rhodamine 123, rhodamine 6G, carboxytetramethylrhodamine, and tetramethylrhodamine ethyl ester.

Preferably, the aggregation-induced emission (AIE) fluorescent molecule is at least one selected from tetraphenylethylene and its derivatives, tetraphenylsilole and its derivatives.

According to the present invention, the fluorescent group non-responsive to biogenic amine is from at least one of porphyrin-based fluorescent molecules, spirocyclic fluorescent molecules, and fluoroboron-based fluorescent molecules.

Preferably, the porphyrin-based fluorescent molecule is selected from at least one of protoporphyrin, tetraphenylporphyrin, tetramethoxyporphyrin, and tetrapyridylporphyrin.

Preferably, the spirocyclic fluorescent molecule is selected from at least one of spiropyran and spirooxazine.

Preferably, the fluoroboron-based fluorescent molecules are selected from at least one of BODIPY FL, BODIPY R6G, BODIPY TR, and BODIPYTMR.

According to the present invention, the degree of substitution of the fluorescent group responsive to biogenic amines on the molecular chain of cellulose and its derivatives is 0.0001-1.5, preferably 0.0001-0.5; The substitution degree of the group on the molecular chain of cellulose and its derivatives is 0.0001-2.0, preferably 0.0001-0.8.

According to the present invention, the molar ratio of the fluorescent group non-responsive to biogenic amine to the fluorescent group responsive to biogenic amine is greater than 0 and less than 100%, preferably 2-80%, more preferably 10-60%.

The present invention also provides the following technical solutions:

A preparation method of the above-mentioned dual-emission cellulose-based fluorescent material, comprising the steps of:

1) Simultaneously reacting cellulose and its derivatives with two types of fluorescent molecules containing different fluorescent groups; or,

1') reacting cellulose and its derivatives with a class of fluorescent molecules containing a fluorescent group first, and then reacting with another class of fluorescent molecules containing another fluorescent group; or,

1") Respectively react cellulose and its derivatives with a class of fluorescent molecules containing fluorescent groups to obtain two types of cellulose-based fluorescent materials, and the fluorescent groups contained in the two types of fluorescent cellulose-based fluorescent materials are different, and then take Mixing the two types of cellulose-based fluorescent materials by means of solution blending or solid blending;

The two different fluorophores in steps 1), 1') and 1") have partially or completely overlapping excitation spectra and resolvable emission spectra; meanwhile, among the two different fluorophores, One class of fluorophores is responsive to biogenic amines and the other class of fluorophores is not responsive to biogenic amines.

According to the present invention, in steps 1), 1') and 1"), the reaction is an esterification reaction or an etherification reaction; the reaction temperature is 40-120°C; the reaction time is 2-72h.

The present invention also provides the following technical solutions:

The application of the above-mentioned double-emission cellulose-based fluorescent material can be applied to the fields of food quality monitoring and the like.

The present invention also provides the following technical solutions:

A method for detecting biogenic amines, wherein the above-mentioned dual-emission cellulose-based fluorescent material is used, and the detection method is based on the change of the fluorescence intensity ratio of the two types of fluorescent groups and the change in the fluorescent color of the cellulose-based fluorescent material. detection.

In the present invention, the emission spectrum of the dual-emission cellulose-based fluorescent material has two clearly distinguishable emission peaks, and each emission peak represents a color, and the color can be any two of the three primary colors , such as "red" and "green", "red" and "blue", "blue" and "green".

The present invention also provides the following technical solutions:

A film comprising the above-mentioned dual emission cellulose-based fluorescent material.

The preparation method of above-mentioned film, comprises the steps:

Prepared by dissolving the above-mentioned dual-emission cellulose-based fluorescent material in N,N-dimethylformamide, ethyl acetate, chloroform, pyridine, N,N-dimethylacetamide, acetone and other solvents, and volatilizing the solvent .

A nanofiber comprising the above-mentioned dual-emission cellulose-based fluorescent material.

The preparation method of the above-mentioned nanofibers is prepared by an electrospinning method, and specifically includes the following steps:

The above-mentioned double emission cellulose-based fluorescent material is dissolved in a mixed solvent of N,N-dimethylformamide and acetone at a concentration of 10-25wt%, and is sprayed from a syringe needle under a high pressure condition of 10-30kV. It is collected to obtain nanofibers.

A coating composition comprising the above-mentioned double emission cellulose-based fluorescent material.

The preparation method of above-mentioned coating composition, comprises the steps:

The above-mentioned dual-emission cellulose-based fluorescent material is dissolved in solvents such as N,N-dimethylformamide, ethyl acetate, chloroform, pyridine, N,N-dimethylacetamide, acetone, etc., and then stirred.

A coating comprising the above-mentioned dual-emission cellulose-based fluorescent material.

The preparation method of described coating comprises the steps:

The above coating composition is directly coated on the surface of the substrate to prepare the coating.

The coating can be spin coating, blade coating, spray coating, dripping, printing, rolling, etc.; the substrate can be plastic, glass, steel, paper, etc.

A printing ink comprising the above-mentioned double emission cellulose-based fluorescent material.

The preparation method of above-mentioned printing ink, comprises the steps:

Dissolve the above-mentioned dual-emission cellulose-based fluorescent material in solvents such as N,N-dimethylformamide, ethyl acetate, chloroform, pyridine, N,N-dimethylacetamide, acetone, etc., and then add a surfactant ( Such as Span-type surfactants, such as Span 80, etc.), the obtained solution is vigorously stirred at room temperature to obtain a homogeneous transparent solution.

A kind of intelligent packaging material, described intelligent packaging material comprises base film, and optionally one or more in following (a) or (b):

(a) a coating on at least one surface of the basement membrane,

(b) Text and/or patterns on the surface of the material;

Wherein, the smart packaging material includes the above-mentioned double emission cellulose-based fluorescent material.

According to the present invention, the dual-emission cellulose-based fluorescent material is added to at least one structure of the base film, coating, characters and/or patterns.

A packaging body, the packaging body is prepared from the above-mentioned intelligent packaging material.

According to the present invention, the package includes a disposable plastic bag, a plastic bottle, a fresh-keeping film, a ziplock bag, and the like.

The present invention also provides the use of the above intelligent packaging material, which is used for food packaging.

Preferably, the intelligent packaging material is used for packaging seafood and meat.

A detection material applied in the biological field, the detection material includes a basement membrane, and optionally one or more of the following (c) or (d):

(c) a coating on at least one surface of the basement membrane,

(d) Text and/or patterns on the surface of the material;

Wherein, the detection material applied in the biological field includes the above-mentioned dual-emission cellulose-based fluorescent material.

According to the present invention, the dual-emission cellulose-based fluorescent material is added to at least one structure of the base film, coating, characters and/or patterns.

A detection product applied to the biological field, the detection product applied to the biological field is prepared from the above-mentioned detection material applied to the biological field.

According to the present invention, the detection products applied in the biological field include disposable test paper, label paper, reagent kit and the like.

Beneficial effects of the present invention:

1. The present invention provides a dual-emission cellulose-based fluorescent material and its preparation method and application. The dual-emission cellulose-based fluorescent material has good biocompatibility and processability. Utilizing the dual-emission cellulose-based fluorescent material and through traditional processing methods, it can be prepared into a variety of material forms that are easy to use directly, such as films, coatings, printing inks, and the like. At the same time, a class of fluorescent groups introduced into the cellulose molecular chain has responsiveness to biogenic amines; a class of fluorescent groups has no response to biogenic amines and is used as an internal standard.

2. The present invention also provides a detection method for biogenic amines, wherein the above-mentioned double-emission cellulose fluorescent material is used, and the detection method is based on the change in the fluorescence intensity ratio of the two types of fluorescent groups and the change in the fluorescent color of the cellulose fluorescent material , to achieve the detection of biogenic amines. During the detection process, as the concentration of biogenic amine increases, the fluorescence intensity ratio of the two types of fluorophores changes, and a color change visible to the naked eye occurs.

3. Compared with the existing fluorescent materials, the biogenic amine-responsive double-emission cellulose-based fluorescent material of the present invention can effectively avoid the influence of external environment, instrument settings and other factors on the measurement results, so that it has excellent detection accuracy and resolution. At the same time, the fluorescence color change produced during the detection process has a higher degree of recognition than the previous fluorescence intensity change, which largely eliminates possible misjudgments due to human factors. In addition, the use of cellulose and its derivatives as a carrier also makes the obtained material have good safety and biocompatibility, and its excellent processing performance can be widely used in food quality monitoring and auxiliary disease diagnosis and other fields.

Description of drawings

FIG. 1 is a ¹ H-NMR chart of cellulose acetate bonded with fluorescein isothiocyanate in Example 2. FIG.

2 is a ¹ H-NMR chart of protoporphyrin-bonded cellulose acetate in Example 2. FIG.

Fig. 3 is the fluorescence emission spectrum of the fluorescent material in Example 3 after reacting with different concentrations of ammonia.

Fig. 4 is a fluorescent photo of the above-mentioned fluorescent material product in Example 3 under a 365nm ultraviolet lamp. From left to right, it is a printing material, a coating, a transparent flexible film, and an electrospun film.

Fig. 5 is a graph showing the change in fluorescence color after the fluorescent material in Example 4 reacts with different concentrations of ammonia.

Fig. 6 is a photo of the above-mentioned fluorescent material in Example 5 used as a smart label for seafood freshness detection.

Detailed ways

As mentioned above, the present invention provides a dual-emission cellulose-based fluorescent material, the fluorescent material uses cellulose and its derivatives as a base material, and the fluorescent material also includes at least two A class of fluorescent groups; the two types of fluorescent groups have partially or completely overlapping excitation spectra and resolvable emission spectra; among the two types of fluorescent groups, one type of fluorescent groups is responsive to biogenic amines, Another class of fluorophores is not responsive to biogenic amines.

Taking an amine-responsive cellulose acetate with red and green dual emission peaks as an example, its structure is as follows:

Below in conjunction with specific embodiment, further illustrate the present invention. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the contents of the present invention, those skilled in the art may make various changes or modifications to the present invention, and these equivalent forms also fall within the scope of the present invention.

The raw materials can be obtained from open commercial channels unless otherwise specified.

Example 1

Preparation of Dual Emission Cellulose-Based Fluorescent Materials by Twice Esterification

Weigh 1.9g cellulose acetate butyrate and 0.016g fluorescein isothiocyanate to carry out esterification reaction under the catalytic conditions of dibutyltin dilaurate (esterification reaction temperature is 100°C; esterification reaction time is 4h) , the obtained product was precipitated, washed and dried, then dissolved again, and subjected to an esterification reaction with 0.11 g of protoporphyrin under the catalysis of carbonyldiimidazole (the esterification reaction temperature was 80° C.; the esterification reaction time was 20 h).

The fluorescent group of fluorescein isothiocyanate and the fluorescent group of protoporphyrin in the double-emission cellulose-based fluorescent material are bonded on the same cellulose, wherein the fluorescent group of fluorescein isothiocyanate is bound to the biogenic amine Responsive, protoporphyrin fluorophore is not responsive to biogenic amines.

The degree of substitution of the isothiocyanate fluorescein fluorescent group responsive to biogenic amines on the molecular chain of cellulose and its derivatives is 0.0024; the protoporphyrin fluorescent group non-responsive to biogenic amines The degree of substitution on the molecular chain of cellulose and its derivatives is 0.002.

Example 2

Preparation of dual-emission cellulose-based fluorescent materials by solid blending method

Weigh 0.9478g cellulose acetate and 0.0389g fluorescein isothiocyanate to carry out esterification reaction under the catalytic condition of dibutyltin dilaurate (esterification reaction temperature is 100 ℃; esterification reaction time is 4h), will The obtained product is precipitated, washed and dried for later use.

Weigh 0.9478g cellulose acetate and 0.0563g protoporphyrin to carry out esterification reaction under the catalysis of carbonyldiimidazole (esterification reaction temperature is 80°C; esterification reaction time is 20h), the obtained product is precipitated, washed and dried for backup use.

Mix the cellulose and its derivatives bonded to the isothiocyanate fluorescein fluorescent group and the cellulose and its derivatives bonded to the protoporphyrin fluorescent group with a mass ratio of 1:5 , and ground in a mortar to prepare a double-emission cellulose-based fluorescent material.

The fluorescein isothiocyanate fluorescent group and the protoporphyrin fluorescent group in the dual-emission cellulose-based fluorescent material are bonded to different celluloses, wherein the fluorescein isothiocyanate fluorescent group is Responsive, protoporphyrin fluorophore is not responsive to biogenic amines.

The degree of substitution of the isothiocyanate fluorescein fluorescent group responsive to biogenic amines on the molecular chain of the cellulose derivative is 0.010; the protoporphyrin fluorescent group non-responsive to biogenic amines is The degree of substitution on the molecular chain of the prime derivative is 0.0015.

FIG. 1 is a ¹ H-NMR chart of cellulose acetate bonded with an isothiocyanate fluorescent group in Example 2. FIG. It can be seen from the figure that the fluorescent group of fluorescein isothiocyanate has been successfully bonded to the molecular chain of cellulose acetate.

FIG. 2 is a ¹ H-NMR chart of cellulose acetate bonded with a protoporphyrin fluorescent group in Example 2. FIG. It can be seen from the figure that the protoporphyrin fluorescent group has been successfully bonded to the cellulose acetate molecular chain.

Example 3

Preparation of Dual Emission Cellulose-Based Fluorescent Materials by Solution Blending

Weigh 0.9478g of cellulose nitrate and 0.0389g of fluorescein isocyanate to carry out esterification reaction under the catalytic conditions of dibutyltin dilaurate (esterification reaction temperature is 100°C; esterification reaction time is 4h), and the resulting product is precipitated , Wash and dry for later use.

Weigh 0.9478g of methylcellulose and 0.0563g of protoporphyrin to carry out esterification reaction under the catalysis of carbonyldiimidazole (esterification reaction temperature is 80°C; esterification reaction time is 20h), and the resulting product is precipitated, washed and dried Backup.

Dissolve the cellulose derivatives bonded to the isocyanate fluorescein fluorescent group and the cellulose derivatives bonded to the protoporphyrin fluorescent group that were synthesized respectively in N,N-dimethylformamide, and then the above two The solutions are mixed at a volume-to-mass ratio of 1:5, and then electrospinning, film laying, printing, etc. are performed to obtain a dual-emission cellulose-based fluorescent material.

The isocyanate fluorescein fluorescent group and the protoporphyrin fluorescent group in the dual-emission cellulose-based fluorescent material are bonded to different celluloses, wherein the isocyanate fluorescein fluorescent group is responsive to biogenic amines, and the protoporphyrin fluorescent group is responsive to biogenic amines. The group is not responsive to biogenic amines.

The degree of substitution of the isocyanate fluorescein fluorescent group responsive to biogenic amines on the molecular chain of cellulose derivatives is 0.020; The degree of substitution on the molecular chain of the compound is 0.010.

Fig. 3 is the fluorescence emission spectrum of the fluorescent material in Example 3 after reacting with different concentrations of ammonia. It can be seen from the figure that before the interaction with ammonia, the material exhibits double emission peaks, which are the emission peak of isocyanate fluorescein at 525nm and the emission peak of protoporphyrin fluorescein at 670nm, indicating the successful construction of dual emission cellulose-based fluorescent materials . After reacting with ammonia water, the fluorescence intensity of fluorescein isocyanate increases with the increase of ammonia water concentration.

Fig. 4 is a fluorescent photo of the fluorescent material product in Example 3 under a 365nm ultraviolet lamp. From left to right, it is a printing material, a coating, a transparent flexible film, and an electrospun film. It can be seen from the figure that the prepared dual-emission cellulose-based fluorescent material has excellent processing performance.

Example 4

Preparation of Dual Emission Cellulose-Based Fluorescent Materials by Secondary Etherification

Weigh 3g of carboxymethyl cellulose and 0.05g of 5-bromomethyl fluorescein under the catalytic conditions of pyridine, carry out the etherification reaction (the etherification reaction temperature is 80°C; the etherification reaction time is 4h), and the resulting product is precipitated , washing, drying, redissolving, and 0.3g bromophenylporphyrin under the catalysis of picoline for etherification reaction again (etherification reaction temperature is 80°C; etherification reaction time is 20h).

The 5-bromomethylfluorescein fluorescent group and the bromophenylporphyrin fluorescent group in the double-emission cellulose-based fluorescent material are bonded to the same cellulose, wherein the 5-bromomethylfluorescein fluorescent group is Biogenic amines are responsive, and bromophenylporphyrin fluorescent groups are not responsive to biogenic amines.

The degree of substitution of the 5-bromomethylfluorescein fluorescent group responsive to biogenic amines on the cellulose derivative molecular chain is 0.006; the bromophenylporphyrin fluorescent group non-responsive to biogenic amines The degree of substitution on the molecular chain of the cellulose derivative is 0.004.

Fig. 5 is a graph showing the change in fluorescence color after the fluorescent material in Example 4 reacts with different concentrations of ammonia. It can be seen from the figure that the material is initially red fluorescent, and then as the concentration of ammonia water interacting with it increases, the material produces a series of fluorescent color changes, from red to orange, yellow, green, etc.

Example 5

Preparation of dual-emission cellulose-based fluorescent materials by one-time etherification

Weigh 3g of methylcellulose, 0.08g of dichlorofluorescein and 0.07g of bromophenylporphyrin under the catalytic conditions of pyridine, and carry out the etherification reaction simultaneously (the etherification reaction temperature is 80°C; the etherification reaction time is 4h) , the resulting product was precipitated, washed and dried.

The dichlorofluorescein fluorescent group and the bromophenylporphyrin fluorescent group in the dual-emission cellulose-based fluorescent material are bonded to the same cellulose, wherein the dichlorofluorescein fluorescent group is responsive to biogenic amines, The bromophenylporphyrin fluorophore is not responsive to biogenic amines.

The degree of substitution of the dichlorofluorescein fluorescent group responsive to biogenic amines on the cellulose derivative molecular chain is 0.0045; the bromophenylporphyrin fluorescent group non-responsive to biogenic amines is The degree of substitution on the molecular chain of the derivative is 0.0035.

Figure 6 is a photo of the fluorescent material used as a smart label in seafood freshness detection in Example 5. It can be seen from the figure that the initial fluorescence of the material is red, indicating that the food is in a fresh state, and then with the slow release of biogenic amine, the fluorescent color of the material Changes to yellow or green, proving the practicality of using the above materials in the field of food testing.

The embodiments of the present invention have been described above. However, the present invention is not limited to the above-mentioned embodiments. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

Claims (28)

1. A double-emission cellulose-based fluorescent material, characterized in that, the fluorescent material uses cellulose and derivatives thereof as a base material, and the fluorescent material also includes at least two types of fluorescent materials bonded to the base material. group; the two types of fluorophores have partially or completely overlapped excitation spectra, and resolvable emission spectra; among the two types of fluorophores, one type of fluorophore is responsive to biogenic amines, and the other Fluorophores are not responsive to biogenic amines. 2. The fluorescent material according to claim 1, wherein the two types of fluorescent groups are bonded to the same cellulose chain, or the two types of fluorescent groups are respectively bonded to two cellulose chains. 3. The fluorescent material according to claim 2, characterized in that, the structural formulas of the two cellulose chains are the same or different. 4. The fluorescent material according to claim 1, wherein the fluorescent group responsive to biogenic amines is from at least one of fluorescein-based fluorescent molecules, rhodamine-based fluorescent molecules, and aggregation-induced luminescent fluorescent molecules ; The fluorescent group that has no response to biogenic amine is from at least one of porphyrin fluorescent molecules, spirocyclic fluorescent molecules and fluoroboron fluorescent molecules. 5. The fluorescent material according to claim 4, wherein the fluorescein fluorescent molecules are selected from the group consisting of fluorescein and isomers thereof, fluorescein isothiocyanate and isomers thereof, fluorescein isocyanate and At least one of its isomers, aminofluorescein and its isomers, carboxyfluorescein and its isomers, and 5-bromomethylfluorescein and its isomers. 6. The fluorescent material according to claim 4, wherein the rhodamine fluorescent molecules are selected from rhodamine B, rhodamine 110, rhodamine 123, rhodamine 6G, carboxytetramethylrhodamine and tetramethylrhodamine At least one of rhodamine ethyl esters. 7 . The fluorescent material according to claim 4 , wherein the aggregation-induced luminescent fluorescent molecules are selected from at least one of tetraphenylethylene and its derivatives, and tetraphenylsilole and its derivatives. 8. The fluorescent material according to claim 4, wherein the porphyrin fluorescent molecule is selected from at least one of protoporphyrin, tetraphenylporphyrin, tetramethoxyporphyrin and tetrapyridyl porphyrin. A sort of. 9. The fluorescent material according to claim 4, wherein the spiro fluorescent molecule is selected from at least one of spiropyran and spirooxazine. 10 . The fluorescent material according to claim 4 , wherein the fluorine-boron fluorescent molecule is selected from at least one of BODIPYFL, BODIPY R6G, BODIPY TR and BODIPY TMR. 11. The fluorescent material according to claim 1, characterized in that the degree of substitution of the fluorescent group responsive to biogenic amines on the molecular chain of cellulose and its derivatives is 0.0001-1.5; non-responsive to biogenic amines The degree of substitution of the fluorescent group on the molecular chain of cellulose and its derivatives is 0.0001-2.0. 12. The fluorescent material according to claim 11, characterized in that the molar ratio of the fluorescent group non-responsive to biogenic amine to the fluorescent group responsive to biogenic amine is greater than 0 and less than 100 %. 13 . The fluorescent material according to claim 12 , wherein the molar ratio of the fluorescent group non-responsive to biogenic amine to the fluorescent group responsive to biogenic amine is 2-80%. 14 . The fluorescent material according to claim 13 , wherein the molar ratio of the fluorescent group non-responsive to biogenic amine to the fluorescent group responsive to biogenic amine is 10-60%. 15. The preparation method of the dual-emission cellulose-based fluorescent material according to any one of claims 1-14, characterized in that the preparation method comprises the steps of: 1) Simultaneously reacting cellulose and its derivatives with two types of fluorescent molecules containing different fluorescent groups; or, 1') reacting cellulose and its derivatives with a class of fluorescent molecules containing a fluorescent group first, and then reacting with another class of fluorescent molecules containing another fluorescent group; or, 1") Respectively react cellulose and its derivatives with a class of fluorescent molecules containing fluorescent groups to obtain two types of cellulose-based fluorescent materials, and the fluorescent groups contained in the two types of fluorescent cellulose-based fluorescent materials are different, and then take Mixing the two types of cellulose-based fluorescent materials by means of solution blending or solid blending; The two different fluorophores in steps 1), 1') and 1") have partially or completely overlapping excitation spectra and resolvable emission spectra; meanwhile, among the two different fluorophores, One class of fluorophores is responsive to biogenic amines and the other class of fluorophores is not responsive to biogenic amines. 16. The preparation method of double emission cellulose-based fluorescent material according to claim 15, characterized in that, in steps 1), 1') and 1"), the reaction is an esterification reaction or an etherification reaction; The reaction temperature is 40-120°C; the reaction time is 2-72h. 17. A detection method for biogenic amines, characterized in that the detection method adopts the dual-emission cellulose-based fluorescent material according to any one of claims 1-14, and the detection method is based on two types of fluorescent groups. Fluorescent intensity ratio changes and fluorescent color changes of cellulose-based fluorescent materials are used to detect biogenic amines. 18. A film, nanofiber, coating composition, coating or printing ink, characterized in that, the film, nanofiber, coating composition, coating or printing ink comprises any one of claims 1-14 The above-mentioned dual-emission cellulose-based fluorescent material. 19. An intelligent packaging material, characterized in that the intelligent packaging material comprises a base film, and optionally one or more of the following (a) or (b): (a) a coating on at least one surface of the basement membrane, (b) Text and/or patterns on the surface of the material; Wherein, the smart packaging material comprises the dual-emission cellulose-based fluorescent material according to any one of claims 1-14. 20 . The smart packaging material according to claim 19 , wherein the dual-emission cellulose-based fluorescent material is added to at least one structure of the base film, coating, characters and/or patterns. 21. A packaging body, characterized in that the packaging body is prepared from the intelligent packaging material according to claim 19 or 20. 22. The package according to claim 21, characterized in that the package is a disposable plastic bag, plastic bottle, plastic wrap or ziplock bag. 23. The application of the intelligent packaging material according to claim 19 or 20, characterized in that the intelligent packaging material is used for food packaging. 24. The application of the intelligent packaging material according to claim 23, characterized in that, the intelligent packaging material is used for packaging of seafood and meat. 25. A detection material applied to the biological field, characterized in that the detection material applied to the biological field includes a basement membrane, and optionally one or more of the following (c) or (d): (c) a coating on at least one surface of the basement membrane, (d) Text and/or patterns on the surface of the material; Wherein, the detection material applied in the biological field includes the dual-emission cellulose-based fluorescent material according to any one of claims 1-14. 26. The detection material applied in the biological field according to claim 25, characterized in that, the double emission cellulose-based fluorescent material is added to at least one of the base film, coating, characters and/or patterns in structure. 27. A detection product applied to the biological field, characterized in that the detection product applied to the biological field is prepared from the detection material applied to the biological field according to claim 25 or 26. 28. The detection product applied in the biological field according to claim 27, characterized in that, the detection product applied in the biological field is a disposable test paper, a label paper or a kit.