CN109111913A - A kind of pair of transmitting cellulose base fluorescent material and its preparation method and application - Google Patents
A kind of pair of transmitting cellulose base fluorescent material and its preparation method and application Download PDFInfo
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- CN109111913A CN109111913A CN201710488800.6A CN201710488800A CN109111913A CN 109111913 A CN109111913 A CN 109111913A CN 201710488800 A CN201710488800 A CN 201710488800A CN 109111913 A CN109111913 A CN 109111913A
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- fluorescent
- cellulose
- biogenic amine
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Classifications
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- C—CHEMISTRY; METALLURGY
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
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- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
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- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/42—Applications of coated or impregnated materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B11/00—Preparation of cellulose ethers
- C08B11/02—Alkyl or cycloalkyl ethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B11/00—Preparation of cellulose ethers
- C08B11/02—Alkyl or cycloalkyl ethers
- C08B11/04—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals
- C08B11/10—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals substituted with acid radicals
- C08B11/12—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals substituted with acid radicals substituted with carboxylic radicals, e.g. carboxymethylcellulose [CMC]
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- C—CHEMISTRY; METALLURGY
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- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B3/00—Preparation of cellulose esters of organic acids
- C08B3/06—Cellulose acetate, e.g. mono-acetate, di-acetate or tri-acetate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B3/00—Preparation of cellulose esters of organic acids
- C08B3/16—Preparation of mixed organic cellulose esters, e.g. cellulose aceto-formate or cellulose aceto-propionate
- C08B3/18—Aceto-butyrates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B5/00—Preparation of cellulose esters of inorganic acids, e.g. phosphates
- C08B5/02—Cellulose nitrate, i.e. nitrocellulose
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Abstract
The invention discloses a kind of double transmitting cellulose base fluorescent materials and its preparation method and application, double transmitting cellulose base fluorescent materials have good biocompatibility and machinability.It include a kind of fluorophor in double transmitting cellulose base fluorescent material due to having a responsiveness to biogenic amine as indicator;A kind of fluorophor is due to biogenic amine non-responsiveness as internal standard compound.Invention additionally discloses a kind of detection methods of biogenic amine, wherein use above-mentioned double transmitting cellulose base fluorescent materials, the detection method is changed according to the fluorescence color of the variation of the fluorescence intensity ratio of two class fluorophors and cellulose base fluorescent material, realizes the detection to biogenic amine.In the detection process, as the concentration of biogenic amine increases macroscopic color change occurs for the fluorescence intensity ratio of two class fluorophors, it can be achieved that Visual retrieval to biogenic amine.
Description
Technical Field
The invention relates to a dual-emission cellulose-based fluorescent material and a preparation method and application thereof, belonging to the technical field of biological detection.
Background
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 largely produced in the degradation process of amino acids. An abnormal increase in biogenic amine concentration is often used as a signal for food spoilage or disease development. Therefore, it is important to develop an effective biogenic amine detection method for its practical application. Recently, fluorescent sensors have been studied in the fields of food quality monitoring and auxiliary disease diagnosis due to their unique high sensitivity and good selectivity. The Tang Benzhou problem group successfully realizes the freshness detection of seafood by utilizing the selective responsiveness of aggregation-induced emission fluorescent molecules to biogenic amine (ACS Sensor 2016,1, 179-184). The pyrene fluorescent molecule derivative designed by the Liukai Qiang project group can detect aniline at a lower concentration, thereby realizing the auxiliary diagnosis of lung cancer (Sensors and activators B2017, 241, 1316-1323). However, in many of these conventional fluorescence sensors, a single fluorescent molecule is used for monitoring. In the using process, the device is very easily interfered by the fluorescent molecule concentration, the external environment, the instrument parameter setting and other factors, so that the measurement accuracy is low. Meanwhile, although the change of the fluorescence intensity generated by a single fluorescent molecule in the detection process can be observed by naked eyes, a uniform observation standard cannot be established, because the sensitivity of the naked eyes to the light intensity is greatly influenced by human factors. In addition, the fluorescence sensors used today are based on small molecule compounds and cannot be used alone as materials. Meanwhile, the small molecular fluorescent compound is easy to migrate along with environmental changes, and has high toxicity, so that the practical application of the small molecular fluorescent compound is limited.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide a dual-emission cellulose-based fluorescent material, which takes cellulose and derivatives thereof as a base material, has the advantages of good biocompatibility, excellent processing performance, wide sources, low price and the like, and is an excellent carrier used as a framework material. Meanwhile, the molecular chain of the cellulose and the derivative thereof is provided with a plurality of hydroxyl groups capable of undergoing derivatization reaction, and the hydroxyl groups and molecules containing fluorescent groups are utilized to perform esterification or etherification reaction to bond at least two types of fluorescent groups; wherein one type of fluorescent group is used as an indicator of the biogenic amine due to responsiveness to the biogenic amine, and the other type of fluorescent group is used as an internal standard substance of the biogenic amine due to non-responsiveness to the biogenic amine; moreover, the two types of fluorescent groups also meet the requirements of excitation spectra with partial coincidence or complete coincidence and distinguishable emission spectra; accurate detection of the biogenic amine can be realized by observing the change of the ratio of the fluorescence intensities emitted by the two types of fluorophores. Meanwhile, after one type of fluorescent group serving as the indicator responds to biogenic amine, the fluorescence color of the whole material system is changed due to the change of the intensity of fluorescence, and obvious signal change which can be recognized by naked eyes is generated, so that the visual detection of biogenic amine is realized.
In order to achieve the purpose, the invention provides the following technical scheme:
a dual-emission cellulose-based fluorescent material takes cellulose and derivatives thereof as a base material, and also comprises at least two types of fluorescent groups bonded on the base material; the two types of fluorophores have partially or completely coincident excitation spectra and distinguishable emission spectra; in the two types of fluorescent groups, one type of fluorescent group is responsive to biogenic amine, and the other type of fluorescent group is not responsive to biogenic amine.
According to the invention, the two types of fluorophores are bonded on the same cellulose chain, or the two types of fluorophores are bonded on the two cellulose chains respectively.
According to the invention, the two cellulose chains have the same or different structural formula.
According to the present invention, the cellulose is selected from at least one of microcrystalline cellulose, cotton pulp, wood pulp, bamboo pulp, absorbent cotton, bagasse, wood, and cellulose prepared from plant straw.
According to the present invention, the derivative of cellulose is at least one selected from cellulose ethers and cellulose esters.
Preferably, the cellulose ester is selected from at least one of cellulose acetate, cellulose acetate butyrate, cellulose propionate, cellulose acetate propionate, cellulose butyrate, cellulose nitrate, cellulose benzoate, cellulose cinnamate.
Preferably, the cellulose ether is selected from at least one of methyl cellulose, ethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxymethyl cellulose.
In the invention, the two types of fluorescent groups need to have excitation spectra which are partially or completely overlapped and distinguishable emission spectra, and the reason is that the two types of fluorescent groups which meet the conditions can be observed by naked eyes when in detection, and the change of the fluorescence intensity of the two types of fluorescent groups can be distinguished according to different colors, so that the visual detection of the biogenic amine is realized.
According to the present invention, the fluorescent group responsive to biogenic amine is derived from at least one of a fluorescein-based fluorescent molecule, a rhodamine-based fluorescent molecule, and an aggregation-induced emission (AIE) -based fluorescent molecule.
Preferably, the fluorescein-based fluorescent molecule is at least one selected from fluorescein and its isomers, fluorescein isothiocyanate and its isomers, fluorescein isocyanate and its isomers, fluorescein amino and its isomers, fluorescein carboxyfluorescein and its isomers, and 5-bromomethyl fluorescein and its isomers.
Preferably, the rhodamine fluorescent molecule is at least one selected from rhodamine B, rhodamine 110, rhodamine 123, rhodamine 6G, carboxytetramethylrhodamine and tetramethylrhodamine ethyl ester.
Preferably, the aggregation-induced emission-based (AIE) fluorescent molecule is selected from at least one of tetraphenylethylene and its derivatives, tetraphenylsilole and its derivatives.
According to the invention, the fluorescent group nonresponsive to biogenic amine is at least one of porphyrin fluorescent molecules, spiro fluorescent molecules and boron fluoride 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 fluoboron fluorescent molecule is at least one selected from BODIPY FL, BODIPY R6G, BODIPY TR and BODIPYTMR.
According to the invention, the degree of substitution of the biological amine-responsive fluorescent group on the molecular chain of the cellulose and the derivative thereof is 0.0001-1.5, preferably 0.0001-0.5; the substitution degree of the fluorescent group which is not responsive to biogenic amine on the molecular chain of the cellulose and the derivative thereof is 0.0001-2.0, preferably 0.0001-0.8.
According to the invention, the molar ratio of the non-biological amine-responsive fluorophore to the biological amine-responsive fluorophore is greater than 0 and less than 100%, preferably 2 to 80%, more preferably 10 to 60%.
The invention also provides the following technical scheme:
a preparation method of the dual-emission cellulose-based fluorescent material comprises the following steps:
1) cellulose and derivatives thereof react with two types of fluorescent molecules containing different fluorescent groups simultaneously; or,
1') reacting cellulose and derivatives thereof with one type of fluorescent molecule containing one fluorescent group, and then reacting with another type of fluorescent molecule containing another fluorescent group; or,
1') respectively reacting cellulose and derivatives thereof with a fluorescent molecule containing a fluorescent group to obtain two types of cellulose-based fluorescent materials, wherein the fluorescent groups contained in the two types of fluorescent cellulose-based fluorescent materials are different, and then mixing the two types of cellulose-based fluorescent materials by adopting a solution blending or solid blending mode;
the two different types of fluorophores in steps 1), 1 ') and 1') have partially or completely coincident excitation spectra and distinguishable emission spectra; meanwhile, one type of the two different types of fluorescent groups is responsive to biogenic amine, and the other type of the two different types of fluorescent groups is not responsive to biogenic amine.
According to the invention, in steps 1), 1') and 1 "), the reaction is an esterification reaction or an etherification reaction; the reaction temperature is 40-120 ℃; the reaction time is 2-72 h.
The invention also provides the following technical scheme:
the application of the dual-emission cellulose-based fluorescent material can be applied to the fields of food quality monitoring and the like.
The invention also provides the following technical scheme:
the method for detecting the biogenic amine adopts the dual-emission cellulose-based fluorescent material, and is characterized in that the biogenic amine is detected according to the change of the ratio of the fluorescence intensity of the two types of fluorescent groups and the change of the fluorescence color of the cellulose-based fluorescent material.
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, which can be any two of three primary colors, such as "red" and "green", "red" and "blue", and "blue" and "green".
The invention also provides the following technical scheme:
a film comprising the dual emission cellulose-based fluorescent material described above.
The preparation method of the film comprises the following steps:
the dual-emission cellulose-based fluorescent material is prepared by dissolving the dual-emission cellulose-based fluorescent material in solvents such as N, N-dimethylformamide, ethyl acetate, chloroform, pyridine, N-dimethylacetamide and acetone, and volatilizing the solvents.
A nanofiber comprising the dual emission cellulose-based fluorescent material described above.
The preparation method of the nanofiber adopts an electrostatic spinning method, and specifically comprises the following steps:
dissolving the dual-emission cellulose-based fluorescent material in a mixed solvent of N, N-dimethylformamide and acetone at a concentration of 10-25 wt%, spraying from a syringe needle under a high pressure condition of 10-30kV, and collecting to obtain the nanofiber.
A coating composition comprising the dual emission cellulose-based fluorescent material.
The preparation method of the coating composition comprises the following steps:
dissolving the dual-emission cellulose-based fluorescent material in solvents such as N, N-dimethylformamide, ethyl acetate, chloroform, pyridine, N-dimethylacetamide and acetone, and stirring.
A coating comprising the dual emission cellulose-based fluorescent material described above.
The preparation method of the coating comprises the following steps:
the coating is prepared by directly coating the coating composition on the surface of a substrate.
The coating can be spin coating, blade coating, spray coating, dripping, printing, rolling and the like; the substrate may be plastic, glass, steel, paper, and the like.
A printing ink comprising the dual emission cellulose-based fluorescent material described above.
The preparation method of the printing ink comprises the following steps:
dissolving the dual-emission cellulose-based fluorescent material in solvents such as N, N-dimethylformamide, ethyl acetate, chloroform, pyridine, N-dimethylacetamide and acetone, adding a surfactant (such as a span surfactant, specifically span 80) and the like, and violently stirring the obtained solution at normal temperature to obtain a homogeneous transparent solution.
A smart packaging material comprising a base film, and optionally one or more of the following (a) or (b):
(a) a coating on at least one surface of the substrate film,
(b) characters and/or patterns on the surface of the material;
wherein the intelligent packaging material comprises the 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, the coating, the text and/or the pattern.
The packaging body is prepared from the intelligent packaging material.
According to the invention, the packaging body comprises a disposable plastic bag, a plastic bottle, a preservative film, a self-sealing bag and the like.
The invention also provides application of the intelligent packaging material, which is used for food packaging.
Preferably, the intelligent packaging material is used for packaging seafood and meat.
A detection material for use in the biological field, the detection material comprising a basement membrane, and optionally one or more of the following (c) or (d):
(c) a coating on at least one surface of the substrate film,
(d) characters and/or patterns on the surface of the material;
wherein, the detection material applied to the biological field comprises the 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, the coating, the text and/or the pattern.
The detection product applied to the biological field is prepared from the detection material applied to the biological field.
According to the present invention, the detection article applied to the biological field includes disposable test paper, label paper, a kit, and the like.
The invention has the beneficial effects that:
1. the invention provides a dual-emission cellulose-based fluorescent material, and a preparation method and application thereof. The dual-emission cellulose-based fluorescent material can be prepared into various material forms which are easy to directly use, such as films, coatings, printing ink and the like, by using a traditional processing mode. Meanwhile, one type of fluorescent group introduced into a cellulose molecular chain has responsiveness to biogenic amine; one type of fluorophore is non-responsive to biogenic amines and is used as an internal standard.
2. The invention also provides a method for detecting biogenic amine, wherein the dual-emission cellulose fluorescent material is adopted, and the detection method realizes the detection of biogenic amine according to the change of the fluorescence intensity ratio of the two types of fluorescent groups and the change of the fluorescence color of the cellulose fluorescent material. During the detection process, as the concentration of the biogenic amine increases, the ratio of the fluorescence intensity of the two types of fluorescent groups changes, and a color change which can be seen by naked eyes is generated.
3. Compared with the existing fluorescent material, the biogenic amine response type dual-emission cellulose-based fluorescent material can effectively avoid the influence of factors such as external environment, instrument setting and the like on the measurement result, so that the biogenic amine response type dual-emission cellulose-based fluorescent material has excellent detection accuracy and resolution. Meanwhile, the fluorescence color change generated in the detection process has higher identification degree compared with the previous fluorescence intensity change, and the misjudgment possibly generated due to human factors is eliminated to a great extent. In addition, the cellulose and the derivatives thereof are used as carriers, so that the obtained material has good safety and biocompatibility, and can be widely applied to the fields of food quality monitoring, auxiliary disease diagnosis and the like by utilizing the excellent processing performance of the material.
Drawings
FIG. 1 is a drawing showing fluorescein isothiocyanate-bonded cellulose acetate in example 21H-NMR chart.
FIG. 2 shows the preparation of protoporphyrin-bonded cellulose acetate in example 21H-NMR chart.
FIG. 3 shows fluorescence emission spectra of the fluorescent material of example 3 after reacting with different concentrations of ammonia.
Fig. 4 is a real fluorescent photograph of the fluorescent material product in example 3 under a 365nm ultraviolet lamp, which sequentially comprises a printing material, a coating, a transparent flexible film and an electrostatic spinning film from left to right.
FIG. 5 is a graph showing the change in fluorescence color of the fluorescent material of example 4 after reacting with different concentrations of ammonia.
Fig. 6 is a photo of the fluorescent material used as a smart tag for detecting freshness of seafood in example 5.
Detailed Description
As described above, the present invention provides a dual emission cellulose-based fluorescent material, wherein the fluorescent material comprises a base material of cellulose and derivatives thereof, and at least two types of fluorescent groups bonded to the base material; the two types of fluorophores have partially or completely coincident excitation spectra and distinguishable emission spectra; in the two types of fluorescent groups, one type of fluorescent group is responsive to biogenic amine, and the other type of fluorescent group is not responsive to biogenic amine.
Taking an amine-responsive cellulose acetate with red-green dual emission peaks as an example, the structure is shown as follows:
the invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Furthermore, it should be understood that various changes or modifications can be made by those skilled in the art after reading the description of the present invention, and such equivalents also fall within the scope of the invention.
The starting materials are commercially available from the open literature unless otherwise specified.
Example 1
Double-emission cellulose-based fluorescent material prepared by two-time esterification method
1.9g of cellulose acetate butyrate and 0.016g of fluorescein isothiocyanate were weighed and subjected to esterification reaction under the catalysis of dibutyltin dilaurate (the esterification reaction temperature is 100 ℃, the esterification reaction time is 4 hours), the obtained product was precipitated, washed, dried, dissolved again, and subjected to esterification reaction again with 0.11g of protoporphyrin under the catalysis of carbonyl diimidazole (the esterification reaction temperature is 80 ℃, the esterification reaction time is 20 hours).
In the dual-emission cellulose-based fluorescent material, an isothiocyanate fluorescein fluorescent group and a protoporphyrin fluorescent group are bonded on the same cellulose, wherein the isothiocyanate fluorescein fluorescent group has responsiveness to biogenic amine, and the protoporphyrin fluorescent group has no responsiveness to biogenic amine.
The substitution degree of the isothiocyanate fluorescein fluorophore responsive to biogenic amine on molecular chains of cellulose and derivatives thereof is 0.0024; the substitution degree of the protoporphyrin fluorescent group which is not responsive to biogenic amine on the molecular chain of the cellulose and the derivative thereof is 0.002.
Example 2
Preparation of dual-emission cellulose-based fluorescent material by solid blending method
0.9478g of cellulose acetate and 0.0389g of fluorescein isothiocyanate are weighed to carry out esterification reaction under the catalysis of dibutyltin dilaurate (the esterification reaction temperature is 100 ℃, the esterification reaction time is 4 hours), and the obtained product is precipitated, washed and dried for later use.
0.9478g of cellulose acetate and 0.0563g of protoporphyrin are weighed and subjected to esterification reaction under the catalysis of carbonyl diimidazole (the esterification reaction temperature is 80 ℃, the esterification reaction time is 20 hours), and the obtained product is precipitated, washed and dried for later use.
Mixing the synthesized cellulose bonded with the fluorescein isothiocyanate and the derivative thereof with the cellulose bonded with the protoporphyrin fluorophore and the derivative thereof according to the mass ratio of 1:5, and grinding in a mortar to prepare the dual-emission cellulose-based fluorescent material.
In the dual-emission cellulose-based fluorescent material, an isothiocyanate fluorescein fluorescent group and a protoporphyrin fluorescent group are bonded on different celluloses, wherein the isothiocyanate fluorescein fluorescent group has responsiveness to biogenic amine, and the protoporphyrin fluorescent group has no responsiveness to biogenic amine.
The substitution degree of the isothiocyanate fluorescein fluorophore with response to biogenic amine on the molecular chain of the cellulose derivative is 0.010; the substitution degree of the protoporphyrin fluorescent group which is not responsive to biogenic amine on the molecular chain of the cellulose derivative is 0.0015.
FIG. 1 shows the preparation of cellulose acetate with isothiocyanate fluorophores bonded in example 21H-NMR chart. As can be seen from the figure, the fluorescein isothiocyanate fluorescent group is successfully bonded on the molecular chain of the cellulose acetate.
FIG. 2 shows cellulose acetate with protoporphyrin fluorophore bonded in example 21H-NMR chart. From the figureIt is known that protoporphyrin fluorophores have been successfully bonded to cellulose acetate molecular chains.
Example 3
Method for preparing dual-emission cellulose-based fluorescent material by solution blending method
0.9478g of cellulose nitrate and 0.0389g of isocyanate fluorescein are weighed to carry out esterification reaction under the catalysis of dibutyltin dilaurate (the esterification reaction temperature is 100 ℃, the esterification reaction time is 4 hours), and the obtained product is precipitated, washed and dried for later use.
0.9478g of methylcellulose and 0.0563g of protoporphyrin are weighed and subjected to esterification reaction under the catalysis of carbonyl diimidazole (the esterification reaction temperature is 80 ℃, the esterification reaction time is 20 hours), and the obtained product is precipitated, washed and dried for later use.
Respectively dissolving the synthesized cellulose derivative bonded with the isocyanate fluorescein fluorophore and the synthesized cellulose derivative bonded with the protoporphyrin fluorophore in N, N-dimethylformamide, mixing the two solutions in a volume-mass ratio of 1:5, and then performing electrostatic spinning, film paving, printing and the like to obtain the 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 on different celluloses, wherein the isocyanate fluorescein fluorescent group has responsiveness to biogenic amine, and the protoporphyrin fluorescent group has no responsiveness to biogenic amine.
The substitution degree of the isocyanate fluorescein fluorescent group responsive to biogenic amine on the molecular chain of the cellulose derivative is 0.020; the substitution degree of the protoporphyrin fluorescent group which is not responsive to biogenic amine on the molecular chain of the cellulose and the derivative thereof is 0.010.
FIG. 3 shows fluorescence emission spectra of the fluorescent material of example 3 after reacting with different concentrations of ammonia. As can be seen from the figure, before the material reacts with ammonia, the material shows double emission peaks, namely an emission peak of isocyanate fluorescein at 525nm and an emission peak of protoporphyrin fluorescein at 670nm, which indicates the successful construction of the double-emission cellulose-based fluorescent material. After the reaction with ammonia water, the fluorescence intensity of isocyanate fluorescein is increased along with the increase of the concentration of the ammonia water.
Fig. 4 is a real fluorescent photograph of the fluorescent material product in example 3 under a 365nm ultraviolet lamp, which sequentially comprises a printing material, a coating, a transparent flexible film and an electrostatic spinning film from left to right. As can be seen from the figure, the prepared dual-emission cellulose-based fluorescent material has excellent processability.
Example 4
Double-emission cellulose-based fluorescent material prepared by secondary etherification method
3g of carboxymethyl cellulose and 0.05g of 5-bromomethyl fluorescein are weighed and subjected to etherification reaction under the catalysis of pyridine (the etherification reaction temperature is 80 ℃, the etherification reaction time is 4 hours), the obtained product is precipitated, washed, dried and dissolved again, and the obtained product and 0.3g of bromophenyl porphyrin are subjected to etherification reaction again under the catalysis of picoline (the etherification reaction temperature is 80 ℃, the etherification reaction time is 20 hours).
In the dual-emission cellulose-based fluorescent material, a 5-bromomethyl fluorescein fluorescent group and a bromophenyl porphyrin fluorescent group are bonded on the same cellulose, wherein the 5-bromomethyl fluorescein fluorescent group has responsiveness to biogenic amine, and the bromophenyl porphyrin fluorescent group has no responsiveness to biogenic amine.
The substitution degree of the 5-bromomethyl fluorescein fluorophore responsive to biogenic amine on the molecular chain of the cellulose derivative is 0.006; the substitution degree of the bromophenyl porphyrin fluorescent group nonresponsive to biogenic amine on the molecular chain of the cellulose derivative is 0.004.
FIG. 5 is a graph showing the change in fluorescence color of the fluorescent material of example 4 after reacting with different concentrations of ammonia. As can be seen from the figure, the material initially fluoresces red, and then as the concentration of ammonia water acting on the material increases, the material undergoes a series of fluorescent color changes from red to orange, yellow, green, and the like.
Example 5
One-time etherification method for preparing dual-emission cellulose-based fluorescent material
3g of methylcellulose, 0.08g of dichlorofluorescein and 0.07g of bromophenyl porphyrin are weighed and subjected to etherification reaction simultaneously under the catalysis of pyridine (the etherification reaction temperature is 80 ℃, the etherification reaction time is 4 hours), and the obtained product is precipitated, washed and dried.
The dichlorofluorescein fluorescent group and the bromophenyl porphyrin fluorescent group in the dual-emission cellulose-based fluorescent material are bonded on the same cellulose, wherein the dichlorofluorescein fluorescent group has responsiveness to biogenic amine, and the bromophenyl porphyrin fluorescent group has no responsiveness to biogenic amine.
The substitution degree of the dichlorofluorescein fluorescent group responsive to the biogenic amine on the molecular chain of the cellulose derivative is 0.0045; the substitution degree of the bromophenyl porphyrin fluorescent group nonresponsive to biogenic amine on the molecular chain of the cellulose derivative is 0.0035.
Fig. 6 is a photograph of the fluorescent material used as the smart tag for detecting freshness of seafood in example 5, and it can be seen from the figure that the initial fluorescence of the material is red, which indicates that the food is in a fresh state, and then the fluorescence color of the material changes to yellow or green with the slow release of biogenic amine, thus proving the practical operability of the material in the field of food detection.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The dual-emission cellulose-based fluorescent material is characterized in that cellulose and derivatives thereof are used as a base material, and the fluorescent material further comprises at least two types of fluorescent groups bonded on the base material; the two types of fluorophores have partially or completely coincident excitation spectra and distinguishable emission spectra; in the two types of fluorescent groups, one type of fluorescent group is responsive to biogenic amine, and the other type of fluorescent group is not responsive to biogenic amine.
2. The fluorescent material of claim 1, wherein the two types of fluorophores are bonded to the same cellulose chain, or the two types of fluorophores are bonded to two cellulose chains, respectively.
Preferably, the two cellulose chains have the same or different structural formula.
Preferably, the biological amine-responsive fluorescent group is derived from at least one of fluorescein fluorescent molecules, rhodamine fluorescent molecules and aggregation-induced emission (AIE) fluorescent molecules; the fluorescent group which is nonresponsive to biogenic amine is at least one of porphyrin fluorescent molecules, spiro fluorescent molecules and boron fluoride fluorescent molecules.
Preferably, the fluorescein-based fluorescent molecule is at least one selected from fluorescein and its isomers, fluorescein isothiocyanate and its isomers, fluorescein isocyanate and its isomers, fluorescein amino and its isomers, fluorescein carboxyfluorescein and its isomers, and 5-bromomethyl fluorescein and its isomers.
Preferably, the rhodamine fluorescent molecule is at least one selected from rhodamine B, rhodamine 110, rhodamine 123, rhodamine 6G, carboxytetramethylrhodamine and tetramethylrhodamine ethyl ester.
Preferably, the aggregation-induced emission-based (AIE) fluorescent molecule is selected from at least one of tetraphenylethylene and its derivatives, tetraphenylsilole and its derivatives.
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 fluoroboric fluorescent molecule is at least one selected from the group consisting of BODIPY FL, BODIPY R6G, BODIPY TR and BODIPY TMR.
Preferably, the degree of substitution of the biological amine-responsive fluorescent group on the molecular chain of the cellulose and the derivative thereof is 0.0001-1.5, preferably 0.0001-0.5; the substitution degree of the fluorescent group which is not responsive to biogenic amine on the molecular chain of the cellulose and the derivative thereof is 0.0001-2.0, preferably 0.0001-0.8.
Preferably, the molar ratio of the non-biological amine-responsive fluorophore to the biological amine-responsive fluorophore is greater than 0 and less than 100%, preferably 2-80%, more preferably 10-60%.
3. The method of preparing the dual emission cellulose-based fluorescent material of claim 1 or 2, comprising the steps of:
1) cellulose and derivatives thereof react with two types of fluorescent molecules containing different fluorescent groups simultaneously; or,
1') reacting cellulose and derivatives thereof with one type of fluorescent molecule containing one fluorescent group, and then reacting with another type of fluorescent molecule containing another fluorescent group; or,
1') respectively reacting cellulose and derivatives thereof with a fluorescent molecule containing a fluorescent group to obtain two types of cellulose-based fluorescent materials, wherein the fluorescent groups contained in the two types of fluorescent cellulose-based fluorescent materials are different, and then mixing the two types of cellulose-based fluorescent materials by adopting a solution blending or solid blending mode;
the two different types of fluorophores in steps 1), 1 ') and 1') have partially or completely coincident excitation spectra and distinguishable emission spectra; meanwhile, one type of the two different types of fluorescent groups is responsive to biogenic amine, and the other type of the two different types of fluorescent groups is not responsive to biogenic amine.
Preferably, in steps 1), 1') and 1 "), the reaction is an esterification reaction or an etherification reaction; the reaction temperature is 40-120 ℃; the reaction time is 2-72 h.
4. The method for detecting the biogenic amine is characterized in that the birmissive cellulose-based fluorescent material as claimed in claim 1 or 2 is adopted, and the biogenic amine is detected according to the change of the ratio of the fluorescence intensity of the two types of fluorescent groups and the change of the fluorescence color of the cellulose-based fluorescent material.
5. A film, nanofiber, coating composition, coating or printing ink, characterized in that said film, nanofiber, coating composition, coating or printing ink comprises a dual emission cellulose based fluorescent material according to claim 1 or 2.
6. A smart packaging material comprising a base film, and optionally one or more of the following (a) or (b):
(a) a coating on at least one surface of the substrate film,
(b) characters and/or patterns on the surface of the material;
wherein the smart packaging material comprises the dual emission cellulose-based fluorescent material of claim 1 or 2.
Preferably, the dual emission cellulose-based fluorescent material is added to at least one of the structures of the substrate film, the coating, the letters and/or the patterns.
7. A package prepared from the smart packaging material of claim 6.
Preferably, the packaging body comprises a disposable plastic bag, a plastic bottle, a preservative film and a self-sealing bag.
8. Use of the smart packaging material of claim 7 wherein the smart packaging material is used for food packaging.
Preferably, the intelligent packaging material is used for packaging seafood and meat.
9. A detection material for biological applications, comprising a basement membrane, and optionally one or more of the following (c) or (d):
(c) a coating on at least one surface of the substrate film,
(d) characters and/or patterns on the surface of the material;
wherein the detection material applied to the biological field comprises the dual emission cellulose-based fluorescent material of claim 1 or 2.
Preferably, the dual emission cellulose-based fluorescent material is added to at least one of the structures of the substrate film, the coating, the letters and/or the patterns.
10. A detection product for biological applications, which is prepared from the detection material for biological applications according to claim 9.
Preferably, the detection article applied to the biological field includes disposable test paper, label paper, a kit, and the like.
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