CN111072850B - Fluorescent molecular monomer and preparation method thereof, aggregation-induced emission hydrogel and preparation method and application thereof - Google Patents

Fluorescent molecular monomer and preparation method thereof, aggregation-induced emission hydrogel and preparation method and application thereof Download PDF

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CN111072850B
CN111072850B CN201911309123.2A CN201911309123A CN111072850B CN 111072850 B CN111072850 B CN 111072850B CN 201911309123 A CN201911309123 A CN 201911309123A CN 111072850 B CN111072850 B CN 111072850B
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刘晓光
骆蕲
李玲
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Abstract

The invention belongs to the technical field of high-molecular luminous hydrogel, and particularly relates to a fluorescent molecular monomer and a preparation method thereof, an aggregation-induced luminous hydrogel and a preparation method and application thereof. The aggregation-induced emission hydrogel provided by the invention has a structure formed by modifying double bonds on aggregation-induced fluorescence molecules and further copolymerizing and crosslinking the aggregation-induced fluorescence molecules with monomers. The synthesis method is simple, has low cost, and is an effective new method for preparing the luminescent hydrogel. The luminescent hydrogel has good and stable fluorescence performance and biocompatibility, and has wide application prospect in the fields of photoelectricity, sensors and biological fluorescent probes.

Description

Fluorescent molecular monomer and preparation method thereof, aggregation-induced emission hydrogel and preparation method and application thereof
Technical Field
The invention belongs to the technical field of high-molecular luminous hydrogel, and particularly relates to a fluorescent molecular monomer and a preparation method thereof, an aggregation-induced luminous hydrogel and a preparation method and application thereof.
Background
The polymer hydrogel is a flexible material which is formed by crosslinking hydrophilic polymer chains through physical action (such as hydrogen bonds, electrostatic action, hydrophile and lyophobicity, ionic bonds, crystallization and the like) or chemical action (covalent bonds or dynamic covalent bonds, such as acylhydrazone bonds, imine bonds, boron ester bonds and the like) to form a three-dimensional network structure, and swells to absorb a large amount of water to fill the network structure. Hydrogels are capable of absorbing large amounts of water in their three-dimensional network structure, swell but do not dissolve, and have received much attention for their unique physicochemical properties (e.g., viscoelasticity, biocompatibility, moisture retention, etc.) and broad functional plasticity.
At present, a polymer material having a light-emitting property may be used as it is, or a light-emitting substance may be stably immobilized in a polymer network of a gel to impart a light-emitting property to the gel. Currently, photoluminescent hydrogels are obtained by incorporating various photoluminescent species (such as organic dye molecules, quantum dots, and rare earth metal complexes) into the polymer network of the hydrogel. However, the synthesized luminescent hydrogel has poor luminescence property, difficult spectrum regulation, brittle and fragile quality and poor mechanical property, and the application range of the luminescent hydrogel is severely limited.
Disclosure of Invention
The invention aims to provide a fluorescent molecular monomer and a preparation method thereof, an aggregation-induced emission hydrogel and a preparation method and application thereof, aiming at the problems of the existing emission hydrogel.
The technical scheme provided by the invention is as follows:
a fluorescent molecular monomer has the following structural general formula:
Figure BDA0002324021860000021
wherein R is1、R2、R3Each independently selected from any one of hydrogen, hydroxyl, amino, alkyl with 1 to 3 carbon atoms or carboxyl, R1、R2、R3The same or different.
According to the fluorescent molecular monomer provided by the technical scheme, the vinyl can be used as a copolymerization point to form high-molecular hydrogel with other monomers, and meanwhile, intermolecular hydrogen bonds can be formed with other monomers, so that certain mechanical strength can be enhanced.
The invention also provides a preparation method of the fluorescent molecular monomer, which comprises the following steps:
1) dissolving 5-10 parts by weight of a raw material nitrile styrene derivative in dimethyl sulfoxide (DMSO) as a solvent, adding 2-5 parts by weight of N, N' -carbonyldiimidazole as an activating agent, adjusting the pH value to acidity, refluxing at 85-95 ℃ for reaction, and separating and purifying to obtain an intermediate amidated styrene derivative;
2) dissolving the intermediate amidated styrene derivative obtained in the step 1), namely dissolving the mixed product obtained in the step 1) in 18-22 parts of dichloromethane, adding 4-6 parts of pyridine, uniformly stirring, adding 8-15 parts of acryloyl chloride, carrying out an ice water bath reflux reaction, separating, purifying, drying and removing a solvent to obtain the vinyl-modified styrene derivative, namely the fluorescent molecular monomer.
Specifically, in step 1): adjusting the pH value to 4-5; the reflux time is 6-10 h.
Specifically, in step 1): the separation comprises the following specific steps: adding a small amount of dilute hydrochloric acid into the reaction solution, shaking uniformly until solid is separated out, then carrying out reduced pressure filtration to remove the separated imidazole salt, and repeating for several times to obtain filtrate without the imidazole salt; the purification comprises the following specific steps: and (3) adding a proper amount of n-butane into the filtrate as an extracting agent to extract the dimethyl sulfoxide because the intermediate product is insoluble in n-butane, removing a large amount of dimethyl sulfoxide through liquid separation, repeating for multiple times to obtain a water-phase product, and finally performing freeze drying on the water-phase product to obtain a dried purified intermediate.
Specifically, in the step 2): performing ice-water bath at 0 ℃; the reflux time is 10-14 h.
Specifically, in the step 2): the separation comprises the following specific steps: because the product is insoluble in toluene, and dichloromethane, pyridine and acryloyl chloride are all soluble in toluene, toluene is selected as an extracting agent, a proper amount of toluene is added into the reaction solution, the mixture is fully shaken up, and filtered under normal pressure to obtain a solid crude product, and the operation is repeated for a plurality of times; the purification comprises the following specific steps: adding a small amount of distilled water to dissolve the obtained crude product, and carrying out reduced pressure distillation at the temperature of 60 ℃ to obtain a purified product; the drying method comprises the following specific steps: and (3) drying the purified product in the previous step in a vacuum drying oven at 50 ℃ for 6 hours to obtain a dried product.
The fluorescent molecular monomer can be prepared based on the technical scheme.
The invention also provides an aggregation-induced emission hydrogel, which has the following structural general formula:
Figure BDA0002324021860000031
wherein a, b and d are mole fractions of monomer units, c is mole fraction of N, N-methylene bisacrylamide unit as a crosslinking agent, a is 0.0001-0.3, b is 0-0.99, c is 0.00001-0.03, d is 0-0.99, and b and d are not 0 at the same time; r 'and R' are independently selected from-NH2、-OH、
Figure BDA0002324021860000032
Any of (a), R 'is the same as or different from R'; r1、R2、R3Each independently selected from any one of hydrogen, hydroxyl, amino, alkyl with 1 to 3 carbon atoms or carboxyl, R1、R2、R3The same or different.
The aggregation-induced emission hydrogel provided by the technical scheme has an aggregation-induced fluorescence effect and can form hydrogel, so that the hydrogel has a wide application prospect in the fields of photoelectricity, sensors and biological fluorescent probes.
Specifically, the fluorescent material is obtained by polymerizing a fluorescent molecular monomer, a second monomer and a third monomer.
The invention also provides a preparation method of the aggregation-induced emission hydrogel, which comprises the following steps:
1) taking 0.001-10 parts by weight of the fluorescent molecular monomer as claimed in claim 1 as a first monomer, adding the first monomer into 75-85 parts by weight of deionized water, and fully stirring at 25-35 ℃ to obtain a uniform solution;
2) adding 10-20 parts of a second monomer and a third monomer into the uniform solution obtained in the step 1), and stirring for 1-3 hours to obtain a uniform monomer mixed solution;
3) adding 0.001-3 mol% of cross-linking agent N, N-methylene bisacrylamide based on the total amount of the monomers into the uniform monomer mixed solution obtained in the step 2), uniformly stirring, then adding 0.001-5 mol% of initiator ammonium persulfate based on the total amount of the monomers, stirring at room temperature for 8-12 min, then adding 0.0001-0.0005 mol% of accelerator tetramethylethylenediamine based on the total amount of the monomers, and continuously stirring for 1-3 min for reaction to obtain a precursor solution;
4) injecting the precursor solution obtained in the step 3) into a mold, and reacting for 2-4 hours in a water bath at the temperature of 60-70 ℃ to obtain the aggregation-induced emission hydrogel;
wherein:
the structural formula of the second monomer is
Figure BDA0002324021860000041
；
The structural formula of the third monomer is
Figure BDA0002324021860000042
；
R 'and R' are independently selected from-NH2、-OH、
Figure BDA0002324021860000051
Figure BDA0002324021860000052
R 'is the same as or different from R'.
Specifically, in the step 2), the stirring time is 1-3 h;
specifically, in the step 3); stirring at room temperature for 8-12 min; the time for continuing stirring is 1-3 min.
According to the invention, double bonds are modified on aggregation-induced fluorescent molecules, and then the double bonds are copolymerized and crosslinked with monomers to form the fluorescent hydrogel. The synthesis method is simple and low in cost, and is an effective novel method for preparing the luminescent hydrogel.
The invention also provides the aggregation-induced emission hydrogel prepared by the preparation method.
Further, the hydrogel is a blue-blue fluorescent hydrogel.
The invention also provides application of the aggregation-induced emission hydrogel as a fluorescent luminescent material.
In general, the advantages of the present invention are as follows:
for the preparation of the luminescent hydrogel, in the prior art, physical doping or rare earth ion coordination is mostly selected to realize the luminescence of the hydrogel, but the hydrogel prepared by the two methods has poor mechanical property, luminescence stability and biocompatibility. According to the invention, double bonds are modified on aggregation-induced fluorescent molecules, and then the double bonds are copolymerized and crosslinked with monomers to form the fluorescent hydrogel. The synthesis method is simple and low in cost, and is an effective novel method for preparing the luminescent hydrogel. The synthesized luminescent hydrogel has high luminescent efficiency, good mechanical property and excellent flexibility, can overcome the defects of small molecular materials in functional compounding, and meets diversified application requirements. The luminescent hydrogel has good and stable fluorescence performance and biocompatibility, and has wide application prospect in the fields of photoelectricity, sensors and biological fluorescent probes.
Drawings
FIG. 1 is a picture of the fluorescent hydrogel prepared in example 1 under natural light and ultraviolet light at 365nm, respectively. The hydrogel is yellowish under natural light, and blue fluorescence appears under ultraviolet light.
FIG. 2 is a stress-strain plot of the fluorescent hydrogel prepared in example 1 under tension and compression. As can be seen from the figure, the hydrogel has good mechanical properties.
FIG. 3 is a fluorescence spectrum of the fluorescent hydrogel prepared in example 1.
FIG. 4 is a CIE diagram of the fluorescent hydrogel prepared in example 1. As can be seen, the fluorescence is shown in the bluish region.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1
(1) An aggregation-induced emission hydrogel is formed by copolymerizing and crosslinking vinyl-modified styrene derivatives, acrylamide and acrylic acid monomers. The method comprises the following steps:
firstly, 0.2g of fluorescent molecular monomer is added into 19.64g of deionized water and fully stirred at the temperature of 30 ℃ to form a uniform solution;
secondly, adding 1.4g of acrylamide and 1.4g of acrylic acid monomer into the solution, and stirring for 2 hours to obtain uniform monomer mixed solution;
(III) weighing 0.03g N, adding N-Methylene Bisacrylamide (MBAA) into the monomer mixed solution obtained in the previous step, stirring for 10min, adding 0.03g of Ammonium Persulfate (APS) after uniformly mixing, continuously stirring for 10min at room temperature, adding 5 microliters of accelerator (TEMED), and continuously stirring for 2 min;
and (IV) injecting the precursor solution obtained in the step (III) into a mould, and reacting for 3 hours in a water bath at the temperature of 60 ℃ to obtain the bluish fluorescent hydrogel. The resulting hydrogel was repeatedly washed with deionized water to remove unreacted materials. A part of the hydrogel was taken, and after freeze-drying treatment, the solid content was measured to be 15%.
(2) The fluorescent molecular monomer is a vinyl-modified styrene derivative, and has a specific structural formula:
Figure BDA0002324021860000071
wherein R is1、R2、R3Is any one of hydrogen, hydroxyl, amino, alkyl or carboxyl with 1 to 3 carbon atoms, R1、R2、R3The same or different.
Comparison of FTIR of aggregation-induced emission hydrogel products with FTIR of fluorescent molecules showed no 1640cm-1、3000cm-1The characteristic absorption peak of the ethylene carbonyl group indicates that the carbon-carbon double bond connected with the carbonyl group is polymerized, thus indicating that the polymer hydrogel is formed.
(3) The preparation method of the vinyl modified styrene derivative comprises the following steps:
taking nitrile styrene derivative as a raw material, dissolving 2.0g of nitrile styrene derivative in 10mL of DMSO, adding 1g of CDI, adjusting the pH value to 4, and refluxing for 8 hours at 90 ℃; adding a small amount of dilute hydrochloric acid into the reaction solution, filtering under reduced pressure to remove the precipitated imidazole salt, and repeating for three times; mixing the filtrate with a proper amount of n-butane, extracting, separating liquid to remove dimethyl sulfoxide, and repeating the steps for three times to obtain a purified water phase product; finally, freeze drying treatment is carried out to obtain a dry intermediate amidated styrene derivative, wherein the specific structural formula of the nitrile styrene derivative is as follows:
Figure BDA0002324021860000072
；
dissolving the intermediate obtained in the step (one) in 10mL of dichloromethane, adding 2.0g of pyridine, stirring uniformly, adding 5.0g of acryloyl chloride, and refluxing in ice-water bath at 0 ℃ for 12 hours; fully mixing the reaction solution with a proper amount of toluene, filtering under normal pressure to obtain a solid, and repeating for 3 times to obtain a solid, namely a crude product; adding a small amount of distilled water to dissolve the crude product, and carrying out reduced pressure distillation at 60 ℃ to obtain a purified product; finally, the purified product was dried in a vacuum oven at 50 ℃ for 6h to give the final product vinyl-modified styrene derivative, with a yield of 75%. FTIR of the product showed 2220cm-1Is located at 3120cm of characteristic absorption peak of nitrile group-1Is a characteristic peak of amide group at 1600cm-1、1580cm-1、1605cm-11630cm as the vibration peak of benzene ring skeleton-1Is located at 3350cm, which is a stretching vibration peak of a carbon-carbon double bond connected with a benzene ring-1Is at 1640cm, which is the absorption peak of phenolic hydroxyl-1、3000cm-1The simultaneous peak indicates the presence of an ethylene carbonyl group, thus demonstrating the successful attachment of a vinyl group to a fluorescent molecule.
Example 2
(1) An aggregation-induced emission hydrogel is formed by copolymerizing and crosslinking a vinyl-modified styrene derivative and acrylamide and N-isopropylacrylamide (NIPAM) monomers and is prepared by the following steps:
firstly, 0.6g of fluorescent molecular monomer is added into 19.64g of deionized water and fully stirred at the temperature of 30 ℃ to form a uniform solution;
adding 1.2g of acrylamide and 1.2g of NIPAM monomer into the solution, and stirring for 2 hours to obtain a uniform monomer mixed solution;
(III) weighing 0.03g N, adding N-Methylene Bisacrylamide (MBAA) into the monomer mixed solution obtained in the previous step, stirring for 10min, adding 0.03g of Ammonium Persulfate (APS) after uniformly mixing, continuing stirring for 10min at room temperature, adding 8 microliter of accelerant (TEMED), and continuing stirring for 2 min;
and (IV) injecting the precursor solution obtained in the step (III) into a mould, and reacting for 3 hours in a water bath at the temperature of 60 ℃ to obtain the bluish fluorescent hydrogel. The resulting hydrogel was repeatedly washed with deionized water to remove unreacted materials. A part of the hydrogel was taken, and after freeze-drying treatment, the solid content was measured to be 15%.
(2) The fluorescent molecular monomer is a vinyl-modified styrene derivative, and the structure is the same as that in example 1.
Comparison of FTIR of aggregation-induced emission hydrogel products with FTIR of fluorescent molecules showed no 1630cm-1、3020cm-1The characteristic absorption peak of the ethylene carbonyl group indicates that the carbon-carbon double bond connected with the carbonyl group is polymerized, thus indicating that the polymer hydrogel is formed.
(3) The preparation method of the vinyl modified styrene derivative comprises the following steps:
taking nitrile styrene derivative as a raw material, dissolving 2.0g of nitrile styrene derivative in 10mL of DMSO, adding 1.5g of CDI, adjusting the pH value to 4, and refluxing for 8 hours at 90 ℃; adding a small amount of dilute hydrochloric acid into the reaction solution, filtering under reduced pressure to remove the precipitated imidazole salt, and repeating for three times; mixing the filtrate with a proper amount of n-butane, extracting, separating liquid to remove dimethyl sulfoxide, and repeating the steps for three times to obtain a purified water phase product; finally, freeze drying treatment is carried out to obtain a dry intermediate amidated styrene derivative, wherein the specific structural formula of the nitrile styrene derivative is as follows:
Figure BDA0002324021860000091
；
dissolving the intermediate obtained in the step (one) in 10mL of dichloromethane, adding 2.0g of pyridine, stirring uniformly, adding 3.0g of acryloyl chloride, and refluxing in ice-water bath at 0 ℃ for 12 hours; mixing the reaction solution withMixing the obtained mixture with toluene fully, filtering the mixture under normal pressure to obtain a solid, and repeating the filtering for 3 times to obtain the solid which is a crude product; adding a small amount of distilled water to dissolve the crude product, and carrying out reduced pressure distillation at 60 ℃ to obtain a purified product; finally, the purified product was dried in a vacuum oven at 50 ℃ for 6 hours to give the final product vinyl-modified styrene derivative, with a yield of 67% determined. FTIR of the product showed 2230cm-1Is located at 3120cm of characteristic absorption peak of nitrile group-1Is a characteristic peak of amide group at 1600cm-1、1590cm-1、1605cm-1Is the vibration peak of benzene ring skeleton, 1650cm-1Is located at 3360cm, which is a stretching vibration peak of a carbon-carbon double bond connected with a benzene ring-1Is located at 1630cm of absorption peak of phenolic hydroxyl-1、3020cm-1The simultaneous peak indicates the presence of an ethylene carbonyl group, thus demonstrating the successful attachment of a vinyl group to a fluorescent molecule.
Example 3
(1) An aggregation-induced emission hydrogel is formed by copolymerizing and crosslinking a vinyl-modified styrene derivative and acrylamide and 2-acrylamido-2-methyl propyl sodium sulfonate (AMPS) monomers, and is prepared by the following steps:
firstly, 0.2g of fluorescent molecular monomer is added into 17.964g of deionized water and fully stirred at the temperature of 30 ℃ to form a uniform solution;
adding 0.9g of acrylamide and 0.9g of AMPS monomer into the solution, and stirring for 2 hours to obtain a uniform monomer mixed solution;
weighing 0.016g N and adding N-Methylene Bisacrylamide (MBAA) into the monomer mixed solution obtained in the previous step, stirring for 10min, adding 0.02g of Ammonium Persulfate (APS) after uniformly mixing, continuously stirring for 10min at room temperature, adding 10 microliter of accelerator (TEMED), and continuously stirring for 2 min;
and (IV) injecting the precursor solution obtained in the step (III) into a mould, and reacting for 3 hours in a water bath at the temperature of 60 ℃ to obtain the bluish fluorescent hydrogel. The resulting hydrogel was repeatedly washed with deionized water to remove unreacted materials. A part of the hydrogel was taken, and after freeze-drying treatment, the solid content was measured to be 10%.
(2) The fluorescent molecular monomer is a vinyl-modified styrene derivative, and the structure is the same as that in example 1.
Comparison of FTIR of aggregation-induced emission hydrogel products with FTIR of fluorescent molecules showed no 1620cm-1、3030cm-1The characteristic absorption peak of the ethylene carbonyl group indicates that the carbon-carbon double bond connected with the carbonyl group is polymerized, thus indicating that the polymer hydrogel is formed.
(3) The preparation method of the vinyl modified styrene derivative comprises the following steps:
taking nitrile styrene derivative as a raw material, dissolving 2.0g of nitrile styrene derivative in 10mL of DMSO, adding 1.0g of CDI, adjusting the pH value to be 5, and refluxing for 8 hours at 90 ℃; adding a small amount of dilute hydrochloric acid into the reaction solution, filtering under reduced pressure to remove the precipitated imidazole salt, and repeating for three times; mixing the filtrate with a proper amount of n-butane, extracting, separating liquid to remove dimethyl sulfoxide, and repeating the steps for three times to obtain a purified water phase product; finally, freeze drying treatment is carried out to obtain a dry intermediate amidated styrene derivative, wherein the specific structural formula of the nitrile styrene derivative is as follows:
Figure BDA0002324021860000111
；
dissolving the intermediate obtained in the step (one) in 10mL of dichloromethane, adding 2.0g of pyridine, stirring uniformly, adding 2.0g of acryloyl chloride, and refluxing in ice-water bath at 0 ℃ for 12 hours; fully mixing the reaction solution with a proper amount of toluene, filtering under normal pressure to obtain a solid, and repeating for 3 times to obtain a solid, namely a crude product; adding a small amount of distilled water to dissolve the crude product, and carrying out reduced pressure distillation at 60 ℃ to obtain a purified product; finally, the purified product was dried in a vacuum oven at 50 ℃ for 6h to give the final product vinyl-modified styrene derivative in a 58% yield. FTIR of the product showed 2230cm-1Is located at 3120cm of characteristic absorption peak of nitrile group-1Is a characteristic peak of amide group at 1610cm-1、1590cm-1、1605cm-1Is benzene ring skeleton vibration peak, 1640cm-1Is located at 3360cm, which is a stretching vibration peak of a carbon-carbon double bond connected with a benzene ring-1Is shown as the absorption peak of the phenolic hydroxyl group, 1620cm-1、3030cm-1While taking placeThe peak indicates the presence of the ethylene carbonyl group, thus demonstrating the successful attachment of the vinyl group to the fluorescent molecule.
Example 4
(1) An aggregation-induced emission hydrogel is formed by copolymerizing and crosslinking a vinyl-modified styrene derivative and acrylamide and N, N-Dimethylacrylamide (DMAA) monomers, and is prepared by the following steps:
firstly, 0.2g of fluorescent molecular monomer is added into 19.64g of deionized water and fully stirred at the temperature of 30 ℃ to form a uniform solution;
adding 1.0g of acrylamide and 0.8g of DMAA monomer into the solution, and stirring for 2 hours to obtain a uniform monomer mixed solution;
weighing 0.016g N and adding N-Methylene Bisacrylamide (MBAA) into the monomer mixed solution obtained in the previous step, stirring for 10min, adding 0.02g of Ammonium Persulfate (APS) after uniformly mixing, continuously stirring for 10min at room temperature, adding 10 microliter of accelerator (TEMED), and continuously stirring for 2 min;
and (IV) injecting the precursor solution obtained in the step (III) into a mould, and reacting for 3 hours in a water bath at the temperature of 60 ℃ to obtain the bluish fluorescent hydrogel. The resulting hydrogel was repeatedly washed with deionized water to remove unreacted materials. A part of the hydrogel was taken, and after freeze-drying treatment, the solid content was measured to be 10%.
(2) The fluorescent molecular monomer is a vinyl-modified styrene derivative, and the structure is the same as that in example 1.
Comparison of FTIR of aggregation-induced emission hydrogel products with FTIR of fluorescent molecules showed no 1640cm-1、3020cm-1The characteristic absorption peak of the ethylene carbonyl group indicates that the carbon-carbon double bond connected with the carbonyl group is polymerized, thus indicating that the polymer hydrogel is formed.
(3) The preparation method of the vinyl modified styrene derivative comprises the following steps:
taking nitrile styrene derivative as a raw material, dissolving 2.0g of nitrile styrene derivative in 10mL of DMSO, adding 1.8g of CDI, adjusting the pH value to 4, and refluxing for 8 hours at 90 ℃; adding a small amount of dilute hydrochloric acid into the reaction solution, filtering under reduced pressure to remove the precipitated imidazole salt, and repeating for three times; mixing the filtrate with a proper amount of n-butane, extracting, separating liquid to remove dimethyl sulfoxide, and repeating the steps for three times to obtain a purified water phase product; finally, freeze drying treatment is carried out to obtain a dry intermediate amidated styrene derivative, wherein the specific structural formula of the nitrile styrene derivative is as follows:
Figure BDA0002324021860000121
；
dissolving the intermediate obtained in the step (one) in 10mL of dichloromethane, adding 2.0g of pyridine, stirring uniformly, adding 3.0g of acryloyl chloride, and refluxing in ice-water bath at 0 ℃ for 12 hours; fully mixing the reaction solution with a proper amount of toluene, filtering under normal pressure to obtain a solid, and repeating for 3 times to obtain a solid, namely a crude product; adding a small amount of distilled water to dissolve the crude product, and carrying out reduced pressure distillation at 60 ℃ to obtain a purified product; finally, the purified product was dried in a vacuum oven at 50 ℃ for 6h to give the final product vinyl-modified styrene derivative, with a yield of 73%. FTIR of the product showed 2220cm-1Is located at 3120cm of characteristic absorption peak of nitrile group-1Is a characteristic peak of amide group at 1610cm-1、1590cm-1、1600cm-11630cm as the vibration peak of benzene ring skeleton-1Is located at the stretching vibration peak of the carbon-carbon double bond connected with the benzene ring, 1690cm-1Is located at the vibration absorption peak of carboxyl, 1640cm-1、3020cm-1The simultaneous peak indicates the presence of an ethylene carbonyl group, thus demonstrating the successful attachment of a vinyl group to a fluorescent molecule.
Example 5
(1) An aggregation-induced emission hydrogel is formed by copolymerizing and crosslinking a vinyl-modified styrene derivative and acrylamide and acryloyloxyethyl dimethyl benzyl ammonium chloride (DABC) monomers, and is prepared by the following steps:
firstly, 0.6g of fluorescent molecular monomer is added into 15.928g of deionized water and fully stirred at the temperature of 30 ℃ to form a uniform solution;
secondly, adding 1.5g of acrylamide and 1.9g of DABC monomer into the solution, and stirring for 2 hours to obtain a uniform monomer mixed solution;
weighing 0.032g N, adding N-Methylene Bisacrylamide (MBAA) into the monomer mixed solution obtained in the previous step, stirring for 10min, adding 0.04g of Ammonium Persulfate (APS) after uniformly mixing, continuing stirring for 10min at room temperature, adding 8 microliter of accelerator (TEMED), and continuing stirring for 2 min;
and (IV) injecting the precursor solution obtained in the step (III) into a mould, and reacting for 3 hours in a water bath at the temperature of 60 ℃ to obtain the bluish fluorescent hydrogel. The resulting hydrogel was repeatedly washed with deionized water to remove unreacted materials. A part of the hydrogel was taken, and after freeze-drying treatment, the solid content was measured to be 20%.
(2) The fluorescent molecular monomer is a vinyl-modified styrene derivative, and the structure is the same as that in example 1.
Comparison of FTIR of aggregation-induced emission hydrogel products with FTIR of fluorescent molecules showed no 1610cm-1、3030cm-1The characteristic absorption peak of the ethylene carbonyl group indicates that the carbon-carbon double bond connected with the carbonyl group is polymerized, thus indicating that the polymer hydrogel is formed.
(3) The preparation method of the vinyl modified styrene derivative comprises the following steps:
taking nitrile styrene derivative as a raw material, dissolving 2.0g of nitrile styrene derivative in 10mL of DMSO, adding 2.2g of CDI, adjusting the pH value to be 4, and refluxing for 8 hours at 90 ℃; adding a small amount of dilute hydrochloric acid into the reaction solution, filtering under reduced pressure to remove the precipitated imidazole salt, and repeating for three times; mixing the filtrate with a proper amount of n-butane, extracting, separating liquid to remove dimethyl sulfoxide, and repeating the steps for three times to obtain a purified water phase product; finally, freeze drying treatment is carried out to obtain a dry intermediate amidated styrene derivative, wherein the specific structural formula of the nitrile styrene derivative is as follows:
Figure BDA0002324021860000141
；
dissolving the intermediate obtained in the step (one) in 10mL of dichloromethane, adding 2.0g of pyridine, stirring uniformly, adding 5.0g of acryloyl chloride, and refluxing in ice-water bath at 0 ℃ for 12 hours; fully mixing the reaction solution with a proper amount of toluene, filtering under normal pressure to obtain a solid, and repeating for 3 times to obtain a solid, namely a crude product; adding small amount ofDissolving the crude product with distilled water, and distilling at 60 deg.C under reduced pressure to obtain purified product; finally, the purified product was dried in a vacuum oven at 50 ℃ for 6h to give the final product vinyl-modified styrene derivative, with a yield of 85% determined. FTIR of the product showed 2220cm-1Is located at 3120cm of characteristic absorption peak of nitrile group-1Is shown as a characteristic peak of amide group, 1605cm-1、1590cm-1、1600cm-1Is benzene ring skeleton vibration peak, 1640cm-1Is located at 3420cm from the stretching vibration peak of the carbon-carbon double bond connected with the benzene ring-1The stretching vibration peak of which is an amino group and is 1610cm-1、3030cm-1The simultaneous peak indicates the presence of an ethylene carbonyl group, thus demonstrating the successful attachment of a vinyl group to a fluorescent molecule.
Example 6
(1) An aggregation-induced emission hydrogel is formed by copolymerization and crosslinking of vinyl-modified styrene derivatives and acrylic acid and acryloyloxyethyl dimethyl benzyl ammonium chloride (DABC) monomers, and is prepared by the following steps:
firstly, 0.8g of fluorescent molecular monomer is added into 15.928g of deionized water and fully stirred at the temperature of 30 ℃ to form a uniform solution;
adding 1.6g of acrylic acid and 1.6g of DABC monomer into the solution, and stirring for 2 hours to obtain a uniform monomer mixed solution;
weighing 0.032g N, adding N-Methylene Bisacrylamide (MBAA) into the monomer mixed solution obtained in the previous step, stirring for 10min, adding 0.04g of Ammonium Persulfate (APS) after uniformly mixing, continuing stirring for 10min at room temperature, adding 8 microliter of accelerator (TEMED), and continuing stirring for 2 min;
and (IV) injecting the precursor solution obtained in the step (III) into a mould, and reacting for 3 hours in a water bath at the temperature of 60 ℃ to obtain the bluish fluorescent hydrogel. The resulting hydrogel was repeatedly washed with deionized water to remove unreacted materials. A part of the hydrogel was taken, and after freeze-drying treatment, the solid content was measured to be 20%.
(2) The fluorescent molecular monomer is a vinyl-modified styrene derivative, and the structure is the same as that in example 1.
FTIR and fluorescent molecules of aggregation-induced emission hydrogel productsComparison of FTIR of (A) shows no 1610cm-1、3020cm-1The characteristic absorption peak of the ethylene carbonyl group indicates that the carbon-carbon double bond connected with the carbonyl group is polymerized, thus indicating that the polymer hydrogel is formed.
(3) The preparation method of the vinyl modified styrene derivative comprises the following steps:
taking nitrile styrene derivative as a raw material, dissolving 2.0g of nitrile styrene derivative in 10mL of DMSO, adding 2.0g of CDI, adjusting the pH value to 4, and refluxing for 8 hours at 90 ℃; adding a small amount of dilute hydrochloric acid into the reaction solution, filtering under reduced pressure to remove the precipitated imidazole salt, and repeating for three times; mixing the filtrate with a proper amount of n-butane, extracting, separating liquid to remove dimethyl sulfoxide, and repeating the steps for three times to obtain a purified water phase product; finally, freeze drying treatment is carried out to obtain a dry intermediate amidated styrene derivative, wherein the specific structural formula of the nitrile styrene derivative is as follows:
Figure BDA0002324021860000161
；
dissolving the intermediate obtained in the step (one) in 10mL of dichloromethane, adding 2.0g of pyridine, stirring uniformly, adding 4.0g of acryloyl chloride, and refluxing in ice-water bath at 0 ℃ for 12 hours; fully mixing the reaction solution with a proper amount of toluene, filtering under normal pressure to obtain a solid, and repeating for 3 times to obtain a solid, namely a crude product; adding a small amount of distilled water to dissolve the crude product, and carrying out reduced pressure distillation at 60 ℃ to obtain a purified product; finally, the purified product was dried in a vacuum oven at 50 ℃ for 6h to give the final product vinyl-modified styrene derivative, with a yield of 82%. FTIR of the product showed 2220cm-1Is located at 3130cm of a characteristic absorption peak of a nitrile group-1Is shown as a characteristic peak of amide group, 1605cm-1、1590cm-1、1610cm-1Is benzene ring skeleton vibration peak, 1640cm-1Is at the stretching vibration peak of the carbon-carbon double bond connected with the benzene ring, 3410cm-1The stretching vibration peak of which is an amino group and is 1610cm-1、3020cm-1The simultaneous peak indicates the presence of an ethylene carbonyl group, thus demonstrating the successful attachment of a vinyl group to a fluorescent molecule.
Examples of effects
Table 1 shows the fluorescence stability of the fluorescent hydrogels prepared in example 1. As can be seen from the table, the fluorescence intensity of the hydrogel can be maintained at 95% after being stored at 4 ℃ for 30 days.
TABLE 1
Figure BDA0002324021860000162
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (9)

1. A fluorescent molecular monomer, characterized by the following general structural formula:
Figure FDA0002324021850000011
wherein R is1、R2、R3Each independently selected from any one of hydrogen, hydroxyl, amino, alkyl with 1 to 3 carbon atoms or carboxyl, R1、R2、R3The same or different.
2. A method of preparing the fluorescent molecular monomer of claim 1, comprising the steps of:
1) dissolving 5-10 parts by weight of a raw material nitrile styrene derivative in dimethyl sulfoxide (DMSO) as a solvent, adding 2-5 parts by weight of N, N' -carbonyldiimidazole as an activating agent, adjusting the pH value to acidity, refluxing at 85-95 ℃ for reaction, and separating and purifying to obtain an intermediate amidated styrene derivative;
2) dissolving the intermediate amidated styrene derivative obtained in the step 1) in 18-22 parts of dichloromethane, adding 4-6 parts of pyridine, uniformly stirring, adding 8-15 parts of acryloyl chloride, carrying out an ice water bath reflux reaction, separating, purifying, drying and removing a solvent to obtain the vinyl modified styrene derivative, namely the fluorescent molecular monomer.
3. The method of claim 2, wherein:
in step 1): adjusting the pH value to 4-5; the reflux time is 6-10 h;
in step 2): performing ice water bath at 0 ℃; the reflux time is 10-14 h.
4. An aggregation-induced emission hydrogel, characterized by the following general structural formula:
Figure FDA0002324021850000021
wherein a, b and d are mole fractions of monomer units, c is mole fraction of N, N-methylene bisacrylamide unit as a crosslinking agent, a is 0.0001-0.3, b is 0-0.99, c is 0.00001-0.03, d is 0-0.99, and b and d are not 0 at the same time, a (b + d) is 0.0001-0.3: 1; r 'and R' are independently selected from-NH2、-OH、
Figure FDA0002324021850000022
Figure FDA0002324021850000023
Any of (a), R 'is the same as or different from R'; r1、R2、R3Each independently selected from any one of hydrogen, hydroxyl, amino, alkyl with 1 to 3 carbon atoms or carboxyl, R1、R2、R3The same or different.
5. A method for preparing the aggregation-induced emission hydrogel according to claim 4, comprising the steps of:
1) taking 0.001-10 parts by weight of the fluorescent molecular monomer as a first monomer, adding the first monomer into 75-85 parts by weight of deionized water, and fully stirring at 25-35 ℃ to obtain a uniform solution;
2) adding 10-20 parts of a second monomer and a third monomer into the uniform solution obtained in the step 1), and stirring to obtain a uniform monomer mixed solution;
3) adding 0.001-3 mol% of cross-linking agent N, N-methylene bisacrylamide based on the total amount of the monomers into the uniform monomer mixed solution obtained in the step 2), stirring uniformly, adding 0.001-5 mol% of initiator ammonium persulfate based on the total amount of the monomers, stirring at room temperature, adding 0.0001-0.0005 mol% of accelerator tetramethylethylenediamine based on the total amount of the monomers, and continuously stirring for reaction to obtain a precursor solution;
4) injecting the precursor solution obtained in the step 3) into a mold, and reacting for 2-4 hours in a water bath at the temperature of 60-70 ℃ to obtain the aggregation-induced emission hydrogel;
wherein:
the structural formula of the second monomer is
Figure FDA0002324021850000031
The structural formula of the third monomer is
Figure FDA0002324021850000032
R 'and R' are independently selected from-NH2、-OH、
Figure FDA0002324021850000033
Figure FDA0002324021850000034
R 'is the same as or different from R'.
6. The method for preparing an aggregation-inducing luminescent hydrogel according to claim 5, wherein:
in the step 2), stirring for 1-3 h;
in the step 3), stirring at room temperature for 8-12 min; the time for continuing stirring is 1-3 min.
7. An aggregation-inducing luminescent hydrogel prepared by the method for preparing an aggregation-inducing luminescent hydrogel according to claim 5 or 6.
8. The aggregation-induced emission hydrogel according to claim 7, wherein: is blue-blue fluorescent hydrogel.
9. Use of an aggregation-inducing luminescent hydrogel according to claim 4, 7 or 8, wherein: as a fluorescent light-emitting material.
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US4060678A (en) * 1975-02-11 1977-11-29 Plastomedical Sciences, Inc. Cationic hydrogels based on hydroxyalkyl acrylates and methacrylates
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US4060678A (en) * 1975-02-11 1977-11-29 Plastomedical Sciences, Inc. Cationic hydrogels based on hydroxyalkyl acrylates and methacrylates
CN107011469A (en) * 2017-04-19 2017-08-04 湘潭大学 A kind of side chain type liquid crystal macromolecule with aggregation-induced emission performance and preparation method thereof
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