CN115304786A - Luminescent hydrogel material with high resilience performance and preparation and application thereof - Google Patents

Luminescent hydrogel material with high resilience performance and preparation and application thereof Download PDF

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CN115304786A
CN115304786A CN202111504001.6A CN202111504001A CN115304786A CN 115304786 A CN115304786 A CN 115304786A CN 202111504001 A CN202111504001 A CN 202111504001A CN 115304786 A CN115304786 A CN 115304786A
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gas
tta
hydrogel material
luminescent
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刘丰祎
解蜀
吴琦
李飞
代天卫
李昌静
张旭锋
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Yunnan Normal University
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Abstract

The scheme belongs to the technical field of hydrogel materials, and discloses a luminescent hydrogel material with high resilience, and preparation and application thereof. The luminescent hydrogel material is PAA/PC/Eu/TTa, a rare earth europium complex formed by TTa and Eu is uniformly distributed in a three-dimensional network formed by PAA and PC, eu in the rare earth europium complex is combined with the three-dimensional network through a coordination bond, PAA is sodium polyacrylate, PC is 2,3-chitosan dipicolinate, eu is rare earth europium ion, and TTa is 2-thiophene formyl trifluoroacetone sodium salt. According to the scheme, PAA and PC are taken as matrixes, and a carboxyl functional group of the PC is coordinated with Eu, so that a rare earth europium complex formed by coordination of TTa and Eu can be uniformly distributed in a skeleton network of the matrixes and is uniformly connected with a three-dimensional network at a molecular level, and the fluorescence quenching phenomenon of the material prepared by traditional physical doping is avoided; meanwhile, the luminescent hydrogel material belongs to an environment-friendly material, and has high resilience and good thermal stability.

Description

Luminescent hydrogel material with high resilience performance and preparation and application thereof
Technical Field
The scheme belongs to the technical field of hydrogel materials, and particularly relates to a luminescent hydrogel material with high resilience, and preparation and application thereof.
Background
Luminescent hydrogels are of great interest because of their unique optical, intelligent, and biocompatibility properties. There is an urgent need to develop a luminescent hydrogel having excellent mechanical properties. The hydrogel material prepared by the traditional method has the defects of poor stability, poor biocompatibility, difficult degradation and the like. In addition, in the hydrogel material prepared by the traditional method, the porous structure, the mechanical modulus and the mechanical property of the material need to be further improved. At present, scientific researchers in various fields report few hydrogel composite materials with excellent luminescent properties and good mechanical properties.
Disclosure of Invention
In view of this, the present solution aims to overcome at least one of the deficiencies in the prior art and provide a new luminescent hydrogel material with high resilience performance.
In order to solve the technical problem, the following technical scheme is adopted:
in a first aspect, a luminescent hydrogel material with high resilience performance is PAA/PC/Eu/TTa, a rare earth europium complex formed by TTa and Eu is uniformly distributed in a three-dimensional network formed by PAA and PC, eu in the rare earth europium complex is connected with the three-dimensional network through a coordination bond, PAA is sodium polyacrylate, PC is 2,3-chitosan dipicolinate, eu is rare earth europium ion, and TTa is 2-thenoyltrifluoroacetone sodium salt.
The scheme takes PAA and PC as matrixes, wherein the PC is prepared from natural biomacromolecule chitosan, and the PAA is obtained by simple chemical crosslinking, is easy to degrade and belongs to an environment-friendly material. PAA and PC are connected through hydrogen bonds to form a stable three-dimensional network, namely a hydrogel network skeleton; eu is firstly coordinated with a carboxyl functional group of PC, so that Eu is stably connected with a hydrogel network framework through a coordination bond and is uniformly distributed in the hydrogel network framework; and then TTa is further coordinated with Eu to form a rare earth europium complex, so that the rare earth europium complex can be uniformly distributed in a skeleton network of a matrix, the fluorescence quenching phenomenon of the material prepared by traditional physical doping is avoided, and a red fluorescent material with excellent luminescence is formed.
In a second aspect, a method for preparing the above luminescent hydrogel material with high resilience performance comprises the following steps:
s1, preparing a PC solution: dissolving PC in distilled water;
s2, preparing an AA solution: adjusting the pH value of the sodium acrylate to be neutral by using a NaOH solution, and fixing the volume;
s3, forming hydrogel: fully mixing the PC solution and the sodium acrylate solution, adding a cross-linking agent MBA and an initiator ammonium persulfate, uniformly mixing, pouring into a mould, heating for forming, and air-drying;
s4, soaking Eu: soaking the substrate in an ethanol solution of Eu;
s5, soaking TTa: soak into TTa solution.
The method adopts free radical polymerization, namely a simple and feasible method to prepare the hydrogel, adopts N, N' -methylene bisacrylamide as a cross-linking agent to combine AA molecules in a chemical cross-linking mode to obtain PAA, and in the process, the PAA and the PC are connected through hydrogen bonds to obtain the hydrogel with a network framework. Then, the Eu and the carboxyl functional group of the PC are combined by coordination bonds through soaking Eu in ethanol solution, so that the Eu and the PC are stably connected with the hydrogel network framework; and then the TTa solution is soaked to further coordinate the TTa and Eu to form the rare earth europium complex, so that the rare earth europium complex can be uniformly distributed in a skeleton network of the matrix, and the fluorescence quenching phenomenon of the material prepared by the traditional physical doping is avoided. The experiment is simple to operate, and the post-treatment of the material is convenient and easy to implement; the hydrogel material has good processability, and can be processed into different forms according to different requirements, so that the form of the hydrogel material can be conveniently designed according to the requirements; the preparation method can be applied to other rare earth ion luminescent systems and natural biological macromolecule systems.
In a third aspect, a use of a luminescent hydrogel material with high resilience as described above as a characterizing material. The hydrogel material has excellent luminescence, obtains a red emission spectrum under the excitation of 369nm, has a maximum emission peak at 617nm, is a pure positive red fluorescence emission peak of a typical rare earth terbium complex, has high color purity, and can be used as a red fluorescent material. The benzaldehyde has excellent identification performance, and can be used as an environment-friendly benzaldehyde fluorescent identification material.
This scheme compares with prior art has following beneficial effect:
firstly, PAA and PC are used as matrixes, and a carboxyl functional group of the PC is coordinated with Eu, so that rare earth europium complexes formed by coordination of TTa and Eu can be uniformly distributed in a framework network of the matrixes and are uniformly connected with a three-dimensional network to reach a molecular level, and the fluorescence quenching phenomenon of the materials prepared by traditional physical doping is avoided.
Secondly, the luminescent hydrogel material has good luminescent property and recognition property to benzaldehyde, a red emission spectrum is obtained under the excitation of 369nm, the maximum emission peak is 617nm, the luminescent hydrogel material is a pure normal red fluorescence emission peak of a typical rare earth europium complex, and the color purity is high.
Moreover, the matrix of the luminescent hydrogel material is easy to degrade, belongs to an environment-friendly material, and has high resilience and good thermal stability (the decomposition temperature is 244 ℃).
Finally, a simple and easy method is used for preparing the luminescent hydrogel material, wherein the three-dimensional network is prepared by adopting a free radical polymerization method, the prepared hydrogel material has good processability, can be processed into different forms according to different requirements, the post-treatment is simple and easy, and the preparation method can be applied to other rare earth ion luminescent systems and natural biological macromolecule systems.
Drawings
FIG. 1 is a thermogram of a high resilience luminescent hydrogel material after drying.
FIG. 2 is a scanning electron microscope image of a high resilience luminescent hydrogel material after drying.
FIG. 3 is a distribution diagram of Eu element after drying for a high resilience luminous hydrogel material.
FIG. 4 is a graph of a high resilience performance luminescent hydrogel material under solar irradiation.
Figure 5 is a graph of a high resilience light emitting hydrogel material under ultraviolet light.
FIG. 6 is a graph of excitation and emission spectra of a high resilience performance luminescent hydrogel material.
FIG. 7 is a graph of the emission spectra of a high resilience performance luminescent hydrogel material soaked with benzaldehyde at different concentrations.
Figure 8 is a stress strain plot of a high resilience luminescent hydrogel material.
Detailed Description
The scheme provides a luminescent hydrogel material with high resilience, which is PAA/PC/Eu/TTa, wherein TTa and Eu form a rare earth europium complex, PAA and PC form a three-dimensional network, the rare earth europium complex is uniformly distributed in the three-dimensional network, eu in the rare earth europium complex is combined with the three-dimensional network through a coordination bond, PAA is sodium polyacrylate, PC is 2,3-chitosan dipicolinate, eu is rare earth europium ion, and TTa is 2-thenoyltrifluoroacetone sodium salt.
The PC is firstly connected with the PAA to form a three-dimensional network, then is combined with the Eu through a coordination bond, and the TTa is combined with the Eu connected with the three-dimensional network to form the rare earth europium complex.
Specifically, a carbonyl functional group of TTa is combined with Eu in a coordination bond to form a rare earth europium complex; PAA and PC are connected through hydrogen bonds to form a three-dimensional network, the PAA is obtained by combining AA molecules in a chemical crosslinking mode by taking N, N' -methylene bisacrylamide as a crosslinking agent, wherein AA is sodium acrylate; the carboxyl functional group of PC is bonded to Eu by coordination bond.
The scheme takes PAA and PC as matrixes, wherein the PC is prepared from natural biomacromolecule chitosan, and the PAA is obtained by simple chemical crosslinking, is easy to degrade and belongs to an environment-friendly material. PAA and PC are connected through hydrogen bonds to form a stable three-dimensional network, namely a hydrogel network skeleton; eu is coordinated and combined with a carboxyl functional group of PC, so that the Eu is stably connected with a hydrogel network framework in a coordination bond mode, and the rare earth europium complex is uniformly distributed in the hydrogel network framework; and then TTa is further coordinated with Eu to form rare earth europium complex, so that the rare earth europium complex can be uniformly distributed in a skeleton network of the matrix, the fluorescence quenching phenomenon of the material prepared by traditional physical doping is avoided, and the red fluorescent material with excellent luminescence is formed.
The scheme also provides a method for preparing the luminescent hydrogel material with high resilience performance, which comprises the following steps:
s1, preparing a PC solution: dissolving PC in distilled water;
s2, preparing an AA solution: adjusting the pH value of the sodium acrylate to be neutral by using NaOH solution, and fixing the volume;
s3, forming hydrogel: fully mixing the PC solution and the sodium acrylate solution, adding a cross-linking agent MBA and an initiator ammonium persulfate, uniformly mixing, pouring into a mould, heating for forming, and air-drying;
s4, soaking Eu: soaking the substrate in an ethanol solution of Eu;
s5, soaking TTa: soaking in TTa ethanol solution.
The method adopts free radical polymerization, namely a simple and feasible method to prepare the hydrogel, adopts N, N' -methylene bisacrylamide as a cross-linking agent to combine AA molecules in a chemical cross-linking mode to obtain PAA, and in the process, the PAA and the PC are connected through hydrogen bonds to obtain the hydrogel with a network framework. Then, soaking Eu in ethanol solution to combine Eu and carboxyl functional groups of PC by coordination bonds, so as to stably connect the Eu and the PC with the hydrogel network framework; and then soaking TTa solution to further coordinate TTa and Eu to form rare earth europium complex, so that the rare earth europium complex can be uniformly distributed in a skeleton network of the matrix, and the fluorescence quenching phenomenon of the material prepared by traditional physical doping is avoided. The experiment is simple to operate, and the post-treatment of the material is convenient and easy to implement; the hydrogel material has good processability, and can be processed into different forms according to different requirements, so that the form of the hydrogel material can be conveniently designed according to the requirements; the preparation method can be applied to other rare earth ion luminescent systems and natural biological macromolecule systems.
Preferably, in step S1, the PC solution has a mass percent concentration of 2 to 5%, more preferably 2.5 to 3%.
Preferably, in step S2, the volume is determined to obtain an AA solution with a volume fraction of 40%.
Preferably, in step S3, the mass of the crosslinking agent MBA is 1 to 2%, more preferably 1.2 to 1.7% of the mass of AA.
Preferably, in step S3, the mass of the initiator ammonium persulfate is 0.5 to 2.0% of the mass of AA, more preferably 0.9 to 1.7%.
Preferably, in the step S3, the temperature for heating and forming is 55-85 ℃, and more preferably 60-80 ℃; the time for thermoforming is 0.5 to 4.5 hours, more preferably 1 to 4 hours.
Preferably, in the step S3, the air drying temperature is 30 ℃; the air drying time is 18-48 h, more preferably 20-36 h;
preferably, in step S4, the ethanol solution of Eu is EuCl 3 The ethanol solution of (3) having a molar concentration of 0.02 to 0.2M, more preferably 0.05 to 0.16M; the soaking time is 4 to 8 hours, and more preferably 5.5 to 6.5 hours.
Preferably, in step S5, the molar concentration of the ethanol solution of TTa is 0.01-0.2M, more preferably 0.02-0.15M; the soaking time is 2 to 12 hours, and more preferably 4 to 10 hours.
Further, before step S1, the method further includes the steps of: s0. preparation of PC, which includes:
s01, adding chitosan into an acetic acid solution, and stirring at room temperature until the chitosan is fully dissolved;
s02, adding a pyridine solution of 2,3-pyridine dicarboxylic acid anhydride, and fully stirring;
s03, adjusting the pH value to be neutral by using a sodium hydroxide solution, and fully reacting;
s04, transferring the mixture into a dialysis bag for dialysis;
s05, evaporating water to dryness after high-speed centrifugation.
Preferably, in step S01, the acetic acid solution has a concentration of 2 to 5% by volume, more preferably 2.5 to 4.5% by volume.
Preferably, in step S01, the chitosan concentration in the acetic acid solution is 1.5% by mass.
Preferably, in step S02, the pyridine solution of 2,3-pyridine dicarboxylic anhydride has a molar concentration of 0.35 to 0.46M, more preferably 0.39 to 0.42M.
Preferably, in step S03, the molar concentration of the sodium hydroxide solution is 2 to 3M, more preferably 2.4 to 2.8M.
Further, the preparation method of the luminescent hydrogel material with high resilience performance comprises the following steps:
s0. preparation of PC:
s01, adding chitosan into an acetic acid solution, and stirring at room temperature until the chitosan is fully dissolved;
s02, adding a pyridine solution of 2,3-pyridine dicarboxylic acid anhydride, and fully stirring;
s03, adjusting the pH value to be neutral by using a sodium hydroxide solution, and fully reacting;
s04, transferring the mixture into a dialysis bag for dialysis;
s05, evaporating water to dryness after high-speed centrifugation;
s1, preparing a PC solution: dissolving PC in distilled water;
s2, preparing an AA solution: adjusting the pH value of the sodium acrylate to be neutral by using NaOH solution, and fixing the volume;
s3, forming hydrogel: fully mixing the PC solution and the sodium acrylate solution, adding a cross-linking agent MBA and an initiator ammonium persulfate, uniformly mixing, pouring into a mould, heating for forming, and air-drying;
s4, soaking Eu: soaking the substrate in an ethanol solution of Eu;
s5, soaking TTa: soaking in TTa ethanol solution.
In order to make those skilled in the art better understand the technical solution of the present invention, the following detailed description is made with reference to specific embodiments. The process methods used in the examples are all conventional methods unless otherwise specified; the materials used, unless otherwise specified, are commercially available.
Example 1
1.5g of chitosan was added to 100mL of 2% strength by volume acetic acid solution and stirred magnetically at room temperature until the chitosan was fully dissolved. Then adding 50mL of 2,3-pyridine dicarboxylic acid anhydride pyridine solution with the molar concentration of 0.35M, stirring uniformly, adding 2.0M sodium hydroxide into the solution to adjust to neutrality, putting the solution into a dialysis bag for dialysis, centrifuging the dialyzed solution at a high speed, evaporating water to obtain 2,3-pyridine dicarboxylic acid chitosan (PC), and dissolving the PC in distilled water to prepare the PC solution with the mass percent concentration of 2%. Adjusting the pH value of AA to be neutral (pH = 7) by using a sodium hydroxide solution, fixing the volume to obtain a sodium acrylate solution with the volume percentage of 40%, fully mixing a PC solution and the sodium acrylate solution, adding a cross-linking agent MBA with the mass of 1% of AA and an initiator ammonium persulfate with the mass of 0.5% of AA, pouring the fully mixed solution into a mold, putting the mold into an oven, adjusting the temperature to be 55 ℃, heating for 0.5h, forming to obtain hydrogel, placing the hydrogel sample in the oven with the temperature of 30 ℃, drying for 18h, soaking the obtained hydrogel sample in EuCl with the molar concentration of 0.02M 3 The hydrogel is soaked in 20mL of TTa ethanol solution with the molar concentration of 0.01M for 2 hours, and then the hydrogel is washed by a large amount of ethanol, and finally the luminescent hydrogel material with high resilience is obtained.
Example 2
1.5g of chitosan was added to 100mL of 2.5% by volume acetic acid solution and stirred magnetically at room temperature until the chitosan was fully dissolved. Then 50mL of a 0.37M solution of 2,3-pyridinedicarboxylic acid anhydride in pyridine was added, and after stirring, the solution was added to a solution of 0.63 molar concentrationAdjusting the pH value of 2.2M sodium hydroxide to be neutral, putting the solution into a dialysis bag for dialysis, centrifuging the dialyzed solution at a high speed, evaporating the water to obtain 2,3-pyridinedicarboxylic acid chitosan (PC), and dissolving the PC in distilled water to prepare a 2.5 mass percent PC solution. Adjusting the pH value of AA to be neutral (pH = 7) by using a sodium hydroxide solution, fixing the volume to obtain a sodium acrylate solution with the volume percentage of 40%, fully mixing a PC solution and the sodium acrylate solution, adding a cross-linking agent MBA with the mass of 1.2% of AA and an initiator ammonium persulfate with the mass of 0.9% of AA, pouring the fully mixed solution into a mold, putting the mold into an oven, adjusting the temperature to be 60 ℃, heating for 1h to obtain hydrogel, forming to obtain hydrogel, placing the hydrogel sample in the oven with the temperature of 30 ℃ for air drying for 20h, and soaking the hydrogel sample in EuCl with the molar concentration of 0.05M 3 The hydrogel is soaked in 20mL of ethanol solution of TTa with the molar concentration of 0.02M for 4 hours, and then the hydrogel is washed by a large amount of ethanol, and finally the luminescent hydrogel material with high resilience performance is obtained.
Example 3
To 100mL of 3.4 vol.% acetic acid solution, 1.5g of chitosan was added and the mixture was magnetically stirred at room temperature until the chitosan was sufficiently dissolved. Then adding 50mL of 2,3-pyridine dicarboxylic acid anhydride pyridine solution with the molar concentration of 0.39M, stirring uniformly, adding 2.4M sodium hydroxide into the solution to adjust to neutrality, putting the solution into a dialysis bag for dialysis, centrifuging the dialyzed solution at a high speed, evaporating water to obtain 2,3-pyridine dicarboxylic acid chitosan (PC), and dissolving the PC in distilled water to prepare the PC solution with the mass percent of 3%. Adjusting the pH value of AA to be neutral (pH = 7) by using a sodium hydroxide solution, obtaining a sodium acrylate solution with the volume percentage of 40% after constant volume, then fully mixing a PC solution and the sodium acrylate solution, adding a cross-linking agent MBA with the mass of 1.5% of AA and an initiator ammonium persulfate with the mass of 1.3% of AA, pouring the fully mixed solution into a mold, putting the mold into an oven, adjusting the temperature to be 70 ℃, heating for 2 hours to obtain hydrogel, drying the hydrogel sample in the oven with the temperature of 30 ℃ for 24 hours, and soaking the obtained hydrogel sample in EuCl with the molar concentration of 0.1M 3 Then adding a large amount of ethanolAnd (3) washing with alcohol, then soaking the hydrogel into 20mL of TTa ethanol solution with the molar concentration of 0.06M for 6h, and then washing with a large amount of ethanol to finally obtain the luminescent hydrogel material with high resilience performance.
Example 4
To 100mL of an acetic acid solution having a volume percentage of 4.5%, 1.5g of chitosan was added, and the mixture was magnetically stirred at room temperature until the chitosan was sufficiently dissolved. Then adding 50mL of 2,3-pyridine dicarboxylic acid anhydride pyridine solution with the molar concentration of 0.42M, stirring uniformly, adding 2.6M sodium hydroxide into the solution to adjust to neutrality, putting the solution into a dialysis bag for dialysis, centrifuging the dialyzed solution at a high speed, evaporating water to obtain 2,3-pyridine dicarboxylic acid chitosan (PC), and dissolving the PC in distilled water to prepare the PC solution with the mass percent of 3.5%. Adjusting the pH value of AA to be neutral (pH = 7) by using a sodium hydroxide solution, obtaining a sodium acrylate solution with the volume percentage of 40% after constant volume, fully mixing a PC solution and the sodium acrylate solution, adding a cross-linking agent MBA with the mass of 1.7% of AA and an initiator ammonium persulfate with the mass of 1.7% of AA, pouring the fully mixed solution into a mould, putting the mould into an oven, adjusting the temperature to be 80 ℃, heating for 3 hours, forming to obtain hydrogel, placing the hydrogel sample in the oven with the temperature of 30 ℃, drying for 36 hours, and soaking the obtained hydrogel sample in EuCl with the molar concentration of 0.12M 3 Then washing with a large amount of ethanol, then soaking the hydrogel into 20mL of ethanol solution of TTa with the molar concentration of 0.1M for 8h, and then washing with a large amount of ethanol to finally obtain the luminescent hydrogel material with high resilience.
Example 5
To 100mL of an acetic acid solution having a volume percentage of 4.5%, 1.5g of chitosan was added, and the mixture was magnetically stirred at room temperature until the chitosan was sufficiently dissolved. Then adding 50mL of 2,3-pyridine dicarboxylic acid anhydride pyridine solution with the molar concentration of 0.43M, stirring uniformly, adding sodium hydroxide with the molar concentration of 2.8M into the solution, adjusting to be neutral, putting the solution into a dialysis bag for dialysis, centrifuging the dialyzed solution at a high speed, evaporating water to obtain 2,3-pyridine dicarboxylic acid chitosan (PC), and dissolving the PC in distilled water to prepare a PC solution with the mass percentage of 4%. With sodium hydroxide solutionAdjusting the pH value of AA to be neutral (pH = 7), obtaining a sodium acrylate solution with the volume percentage of 40% after constant volume, then fully mixing a PC solution and the sodium acrylate solution, adding a cross-linking agent MBA with the mass of 1.85% of AA and an initiator ammonium persulfate with the mass of 1.9% of AA, pouring the fully mixed solution into a mold, putting the mold into an oven, adjusting the temperature to 82 ℃, heating for 4h to form hydrogel, placing the hydrogel sample in the oven with the temperature of 30 ℃ for air drying for 42h, soaking the obtained hydrogel sample in EuCl with the molar concentration of 0.16M 3 Then washing with a large amount of ethanol, then soaking the hydrogel into 20mL of ethanol solution of TTa with the molar concentration of 0.15M for 10h, and then washing with a large amount of ethanol to finally obtain the luminescent hydrogel material with high resilience.
Example 6
1.5g of chitosan was added to 100mL of 5.0% by volume acetic acid solution and stirred magnetically at room temperature until the chitosan was fully dissolved. And then adding 50mL of 2,3-pyridine dicarboxylic acid anhydride pyridine solution with the molar concentration of 0.46M, stirring uniformly, adding 3M sodium hydroxide into the solution to adjust to neutrality, putting the solution into a dialysis bag for dialysis, centrifuging the dialyzed solution at a high speed, evaporating water to obtain 2,3-pyridine dicarboxylic acid chitosan PC, and dissolving the PC in distilled water to prepare a 5% PC solution by mass percent. Adjusting the pH value of AA to be neutral (pH = 7) by using a sodium hydroxide solution, obtaining a sodium acrylate solution with the volume percentage of 40% after constant volume, fully mixing a PC solution and the sodium acrylate solution, adding a cross-linking agent MBA with the mass of 2% of AA and an initiator ammonium persulfate with the mass of 2.0% of AA, pouring the fully mixed solution into a mold, putting the mold into an oven, adjusting the temperature to be 85 ℃, heating for 4.5h, forming to obtain hydrogel, placing the hydrogel sample in the oven with the temperature of 30 ℃, drying for 48h, soaking the obtained hydrogel sample in EuCl with the molar concentration of 0.2M 3 Then washing with a large amount of ethanol, then soaking the hydrogel into 20mL of TTa ethanol solution with the molar concentration of 0.2M for 12h, and then washing with a large amount of ethanol to finally obtain the luminescent hydrogel material with high resilience.
The luminescent hydrogel materials prepared in the above examples were tested as follows:
(ii) thermal stability of the luminescent hydrogel material after drying
FIG. 1 is a thermogravimetric plot of the luminescent hydrogel material after vacuum drying, from which it can be seen that the material has good thermal stability and a decomposition temperature of 244 ℃.
(II) morphology of luminescent hydrogel
In order to determine the morphology of the hydrogel, a vacuum drying technique was used to obtain aerogel samples. The aerogel is observed in cross section by using a field emission scanning electron microscope, and as can be seen from fig. 2, the material has a macroporous structure inside.
In order to determine the distribution of the rare earth europium ions, a distribution diagram of the europium element is obtained by using a surface scanning technology, and as can be found from fig. 3, the europium element is uniformly distributed in the material, so that the uniform distribution of the rare earth europium complex in the biomacromolecule network framework is proved.
(III) fluorescence Properties of luminescent hydrogel Material
Fig. 4 is a graph of a luminescent hydrogel in sunlight, fig. 5 is a graph under ultraviolet lamp illumination, and it can be seen from fig. 5 that the hydrogel emits pure red light under the ultraviolet lamp illumination.
FIG. 6 shows the excitation and emission spectra of the hydrogel, and it can be seen from FIG. 6 that the excitation is the excited state in which 2-thenoyltrifluoroacetone absorbs ultraviolet light and transfers energy to the rare earth europium ion after intersystem crossing. In the excitation spectrum, 4 f-4 f transition of rare earth europium ion is not found, which indicates that the energy transfer is carried out by 2-thenoyl trifluoroacetone and the transfer efficiency is high, thereby indirectly proving that the 2-thenoyl trifluoroacetone and the rare earth europium ion form a complex. From FIG. 6, it can be seen that the emission spectrum obtained under 369nm excitation has a maximum emission peak at 617nm, which is the red emission peak of a typical rare earth europium ion. The obtained material has high color purity and good monochromaticity. In the emission spectrum of FIG. 6, no emission peak from the ligand was found, which further indicates that 2-thenoyltrifluoroacetone and rare earth europium ion form a complex compound because an organic ligand needs to form a coordinate bond with a rare earth ion in order to achieve high efficiency of energy transfer.
Benzaldehyde recognition performance of (IV) luminescent hydrogel material
FIG. 7 is a fluorescence spectrum of the luminescent hydrogel material after being soaked in benzaldehyde solutions with different concentrations, and it can be found from the fluorescence spectrum that the fluorescence intensity of the hydrogel gradually decreases with the increase of the concentration of the benzaldehyde solution, which shows that the luminescent hydrogel has excellent identification performance for benzaldehyde.
(V) mechanical properties of luminescent hydrogel material
FIG. 8 is a graph of the compressive stress of a high resilience luminescent hydrogel material, from which it can be seen that the hydrogel material after being compressed to different degrees still maintains the original shape after the pressure is released, showing good shape memory properties.
In the above test, the fluorescence spectrum experiment was performed using a Hitachi F-4600 fluorescence spectrometer, and the scanning electron microscope was a NOVA/NANOSE EM-450 field emission electron microscope from FEI, USA; thermogravimetric experiments used a STA449F31 instrument.
From the above test results, it can be seen that the decomposition temperature of the hydrogel material is 244 ℃, and the hydrogel material exhibits excellent mechanical properties, indicating that the obtained luminescent hydrogel material is indeed a hydrogel material with high resilience. The red fluorescent material has excellent luminescence, obtains a red emission spectrum under the excitation of 369nm, has a maximum emission peak at 617nm, is a pure positive red fluorescent emission peak of a typical rare earth europium complex, has high color purity, and can be applied as a red fluorescent material. The fluorescent material can be applied to benzaldehyde recognition.
Based on the scheme, the application of the luminescent hydrogel material with high resilience as a characterization material is further provided, and the luminescent hydrogel material is particularly suitable for characterization and identification of benzaldehyde.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.

Claims (10)

1. A luminescent hydrogel material with high resilience performance is PAA/PC/Eu/TTa, a rare earth europium complex formed by TTa and Eu is uniformly distributed in a three-dimensional network formed by PAA and PC, eu in the rare earth europium complex is combined with the three-dimensional network through a coordination bond, the PAA is sodium polyacrylate, the PC is 2,3-chitosan dipicolinate, the Eu is rare earth europium ion, and the TTa is 2-thenoyltrifluoroacetone sodium salt.
2. The luminescent hydrogel material with high resilience performance according to claim 1, wherein the PC is firstly bonded with PAA to form the three-dimensional network, and then bonded with Eu in coordination bond, and the TTa is then bonded with Eu bonded to the three-dimensional network to form the rare earth europium complex.
3. A luminescent hydrogel material with high resilience properties according to claim 2, characterized in that,
the PAA is obtained by combining AA molecules in a chemical crosslinking mode by using N, N' -methylene bisacrylamide as a crosslinking agent, wherein AA is sodium acrylate; and/or the presence of a gas in the atmosphere,
the carbonyl functional group of TTa is combined with Eu by a coordination bond to form the rare earth europium complex; and/or the presence of a gas in the gas,
the PAA and the PC are connected through hydrogen bonds to form the three-dimensional network; and/or the presence of a gas in the gas,
the carboxyl functional group of the PC is combined with Eu in a coordination bond; and/or the presence of a gas in the atmosphere,
the decomposition temperature of the luminescent hydrogel material was 244 ℃.
4. A method for preparing a luminescent hydrogel material with high resilience as claimed in any one of claims 1 to 3, comprising the steps of:
preparing a PC solution: dissolving PC in distilled water;
preparing an AA solution: adjusting the pH value of the sodium acrylate to be neutral by using a NaOH solution, and fixing the volume;
forming the hydrogel: fully mixing the PC solution and the sodium acrylate solution, adding a cross-linking agent MBA and an initiator ammonium persulfate, uniformly mixing, pouring into a mould, heating for forming, and air-drying;
and (4) soaking Eu: soaking the substrate in an ethanol solution of Eu;
soaking TTa: soaking in TTa ethanol solution.
5. The method for preparing a luminescent hydrogel material with high resilience performance according to claim 4, wherein,
in the step of preparing the PC solution, the mass percentage concentration of the PC solution is 2-5%; and/or the presence of a gas in the gas,
in the step of preparing the AA solution, the volume is determined to obtain the AA solution with the volume fraction of 40 percent; and/or the presence of a gas in the gas,
in the step of forming the hydrogel, the mass of the crosslinking agent MBA is 1-2% of that of AA; and/or the mass of the initiator ammonium persulfate is 0.5-2.0% of that of AA; and/or heating and molding for 0.5-4.5 h at 55-85 ℃; and/or air-drying for 18-48 h at 30 ℃; and/or the presence of a gas in the gas,
in the step of immersing Eu, the molar concentration of the Eu ethanol solution is 0.02-0.2M; and/or the soaking time is 4-8 h; and/or the presence of a gas in the gas,
in the TTa soaking process, the molar concentration of the ethanol solution of the TTa is 0.01-0.2M; and/or the soaking time is 2-12 h.
6. The method for preparing a luminescent hydrogel material with high resilience performance according to claim 5, wherein,
in the step of preparing the PC solution, the mass percentage concentration of the PC solution is 2.5-3%; and/or the presence of a gas in the gas,
in the step of forming the hydrogel, the mass of the crosslinking agent MBA is 1.2-1.7% of that of AA; and/or the mass of the initiator ammonium persulfate is 0.9-1.7% of that of AA; and/or heating and molding for 1-4 h at 60-80 ℃; and/or air-drying at 30 ℃ for 20-36 h; and/or the presence of a gas in the atmosphere,
in the step of immersing Eu, the molar concentration of the Eu ethanol solution is 0.05-0.16M; and/or the soaking time is 5.5-6.5 h; and/or the presence of a gas in the gas,
in the TTa soaking process, the molar concentration of the ethanol solution of the TTa is 0.02-0.15M; and/or the soaking time is 4-10 h.
7. The method for preparing a luminescent hydrogel material with high rebound performance as claimed in claim 4, further comprising a step of preparing PC before the step of preparing PC solution, which comprises:
adding chitosan into acetic acid solution, and stirring at room temperature until the chitosan is fully dissolved;
adding 2,3-pyridine dicarboxylic anhydride pyridine solution, and fully stirring;
adjusting the pH value to be neutral by using a sodium hydroxide solution, and fully reacting;
transferring into a dialysis bag for dialysis;
centrifuging at high speed, and evaporating to remove water.
8. The method for preparing a luminescent hydrogel material with high resilience performance according to claim 7, wherein,
the volume percentage concentration of the acetic acid solution is 2-5%; and/or the presence of a gas in the gas,
the mass percentage concentration of the chitosan in the acetic acid solution is 1.5 percent; and/or the presence of a gas in the gas,
the molar concentration of the 2,3-pyridine dicarboxylic anhydride pyridine solution is 0.35-0.46M; and/or the presence of a gas in the gas,
the molar concentration of the sodium hydroxide solution is 2-3M.
9. Use of a luminescent hydrogel material with high resilience as defined in any one of claims 1 to 3 or a luminescent hydrogel material with high resilience as prepared by a method as defined in any one of claims 4 to 8 as a characterizing material.
10. Use of a luminescent hydrogel material with high resilience as a characterization material according to claim 9, wherein the luminescent hydrogel material is used for characterization and recognition of benzaldehyde.
CN202111504001.6A 2021-12-10 2021-12-10 Luminescent hydrogel material with high resilience performance and preparation and application thereof Pending CN115304786A (en)

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