CN115337876A - Porous structure luminescent hydrogel material and preparation and application thereof - Google Patents
Porous structure luminescent hydrogel material and preparation and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 102
- 239000000017 hydrogel Substances 0.000 title claims abstract description 93
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 47
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 38
- 229920001661 Chitosan Polymers 0.000 claims abstract description 36
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims abstract description 28
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 27
- GJAWHXHKYYXBSV-UHFFFAOYSA-N quinolinic acid Chemical compound OC(=O)C1=CC=CN=C1C(O)=O GJAWHXHKYYXBSV-UHFFFAOYSA-N 0.000 claims abstract description 24
- -1 2-thenoyltrifluoroacetone sodium salt Chemical compound 0.000 claims abstract description 22
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 6
- 125000000524 functional group Chemical group 0.000 claims abstract description 6
- 239000001913 cellulose Substances 0.000 claims abstract description 4
- 229920002678 cellulose Polymers 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 75
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 66
- 238000003756 stirring Methods 0.000 claims description 43
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 30
- 238000007710 freezing Methods 0.000 claims description 26
- 230000008014 freezing Effects 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- 238000000502 dialysis Methods 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 15
- 238000002791 soaking Methods 0.000 claims description 12
- MCQOWYALZVKMAR-UHFFFAOYSA-N furo[3,4-b]pyridine-5,7-dione Chemical compound C1=CC=C2C(=O)OC(=O)C2=N1 MCQOWYALZVKMAR-UHFFFAOYSA-N 0.000 claims description 11
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 11
- 238000001704 evaporation Methods 0.000 claims description 10
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 6
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 4
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 abstract description 8
- 238000010791 quenching Methods 0.000 abstract description 6
- 230000000171 quenching effect Effects 0.000 abstract description 6
- 239000002149 hierarchical pore Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 51
- 239000011259 mixed solution Substances 0.000 description 26
- 239000000203 mixture Substances 0.000 description 9
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- NNMXSTWQJRPBJZ-UHFFFAOYSA-K europium(iii) chloride Chemical compound Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-UHFFFAOYSA-K 0.000 description 8
- 235000015110 jellies Nutrition 0.000 description 8
- 239000008274 jelly Substances 0.000 description 8
- 238000000295 emission spectrum Methods 0.000 description 7
- 230000005284 excitation Effects 0.000 description 7
- 238000004020 luminiscence type Methods 0.000 description 6
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- 238000010586 diagram Methods 0.000 description 4
- TXBBUSUXYMIVOS-UHFFFAOYSA-N thenoyltrifluoroacetone Chemical compound FC(F)(F)C(=O)CC(=O)C1=CC=CS1 TXBBUSUXYMIVOS-UHFFFAOYSA-N 0.000 description 4
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- 238000000703 high-speed centrifugation Methods 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 239000004964 aerogel Substances 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
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- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
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- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0052—Preparation of gels
- B01J13/0065—Preparation of gels containing an organic phase
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Abstract
The scheme belongs to the technical field of hydrogel materials, and discloses a porous structure luminescent hydrogel material and preparation and application thereof. The hydrogel material is MFC/PC/Eu/TTa, a rare earth europium complex formed by Eu and TTa is uniformly distributed in a three-dimensional network formed by the MFC and the PC, eu in the rare earth europium complex is combined with the three-dimensional network through a coordination bond, the MFC is microfibrillated cellulose, the PC is 2,3-pyridinedicarboxylic acid chitosan, eu is rare earth europium ion, and TTa is 2-thenoyltrifluoroacetone sodium salt. According to the scheme, the PC and the MFC are used as the matrix, and the carboxyl functional group of the PC is coordinated with the Eu, so that the rare earth europium complex formed by coordination of TTa and the Eu can be uniformly distributed in a skeleton network of the matrix and is uniformly connected with a three-dimensional network to reach a molecular level, the fluorescence quenching phenomenon of the material prepared by traditional physical doping is avoided, and meanwhile, the hydrogel material belongs to an environment-friendly material, not only has a hierarchical pore structure, but also has high resilience performance and good thermal stability.
Description
Technical Field
The scheme belongs to the technical field of hydrogel materials, and particularly relates to a porous structure luminescent hydrogel material and preparation and application thereof.
Background
The rare earth europium complex has excellent luminescence property, so that the rare earth europium complex is widely concerned by scientific researchers. In order for the luminescent rare earth europium complexes to be useful in practice, it is generally necessary to incorporate the rare earth europium complexes into some suitable matrix. The traditional method is to introduce rare earth europium complexes into some artificially synthesized macromolecules or silicon dioxide matrixes. However, silica and synthetic polymer materials have some inherent disadvantages, such as poor biocompatibility and difficulty in biodegradation. In addition, in the rare earth composite material prepared by the traditional method, the hierarchical pore structure and the mechanical property of the material need to be further improved. At present, researchers in various fields have few researches on luminescent hydrogel composite materials which have a hierarchical pore structure 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 luminescent hydrogel material with a porous structure, which has excellent mechanical properties and is easy to degrade.
In order to solve the technical problem, the following technical scheme is adopted:
in a first aspect, the porous structure luminescent hydrogel material is MFC/PC/Eu/TTa, a rare earth europium complex formed by Eu and TTa is uniformly distributed in a three-dimensional network formed by the MFC and the PC, eu in the rare earth europium complex is combined with the three-dimensional network through a coordination bond, the MFC is microfibrillated cellulose, the PC is 2,3-pyridinedicarboxylic acid chitosan, eu is a rare earth europium ion, and TTa is 2-thenoyltrifluoroacetone sodium salt.
The scheme takes natural biomacromolecule MFC and chitosan as matrixes, is easy to degrade, and belongs to an environment-friendly material. MFC is connected with PC through hydrogen bond to form a stable three-dimensional network, namely a hydrogel network skeleton; eu is firstly combined with a carboxyl functional group of PC in a three-dimensional network through a coordination bond to achieve the aim of stably connecting with a hydrogel network framework, and is uniformly distributed in the hydrogel network framework; TTa is further coordinated with Eu through carbonyl functional groups to form rare earth europium complexes, so that the rare earth europium complexes can be uniformly distributed in a network framework of a matrix, the fluorescence quenching phenomenon of the material prepared by traditional physical doping is avoided, and a stable red fluorescent material with excellent luminescence is formed.
In a second aspect, a method for preparing the above luminescent hydrogel material with porous structure comprises the following steps:
pre-freezing: dissolving PC in MFC, stirring at room temperature until the PC is fully dissolved, and pre-freezing at-25 ℃;
freezing: adding epichlorohydrin and sodium hydroxide, stirring, pouring into a mold, and freezing at-25 deg.C;
unfreezing: unfreezing in Eu solution, and washing with a large amount of deionized water;
soaking: soaked in TTa solution and washed with copious amounts of deionized water.
The method adopts freezing-unfreezing to prepare the hydrogel material, and leads the PC, the MFC and the rare earth europium complex to be connected through coordination bonds, thereby leading the rare earth europium complex to be uniformly distributed in a skeleton network of a matrix and avoiding the fluorescence quenching phenomenon of the material prepared by the traditional physical doping. The experiment is simple to operate, and the post-treatment of the material is convenient and easy to implement; has good processability and can be processed into different forms according to different requirements, so that the form of the hydrogel material can be designed according to requirements. The preparation method can be applied to other rare earth ion luminescent systems and natural biological macromolecule systems.
In a third aspect, a luminescent hydrogel material with a porous structure is used as a fluorescent material. In the scheme, the hydrogel material has excellent luminescence, a red emission spectrum is obtained under 378nm excitation, the maximum emission peak is 613nm, and is a pure positive red fluorescence emission peak of a typical rare earth europium complex, the color purity is high, and the hydrogel material can be applied as a red fluorescent material. The porous structure luminescent hydrogel material has excellent recognition performance on formaldehyde, and can be applied to recognition of formaldehyde.
This scheme compares with prior art has following beneficial effect:
firstly, PC and MFC are taken as substrates, 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 substrates 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.
Secondly, the hydrogel material has good luminescence property and formaldehyde recognition property, a red emission spectrum is obtained under 378nm excitation, the maximum emission peak is at 613nm, the maximum emission peak is a pure normal red fluorescence emission peak of a typical rare earth europium complex, and the color purity is high.
In addition, the matrix of the luminescent hydrogel material is easy to degrade, belongs to an environment-friendly material, and has a porous structure, high resilience and good thermal stability (the decomposition temperature is 251 ℃).
Finally, PC, MFC and rare earth europium complex are connected through coordination bonds by using a simple and easy 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 to implement, and the preparation method can be applied to other rare earth ion luminescent systems and natural biomacromolecule systems.
Drawings
FIG. 1 is a thermogram of a porous structure luminescent hydrogel material after drying.
FIG. 2 is a scanning electron microscope image of the porous structure luminescent hydrogel material after being dried.
FIG. 3 is a distribution diagram of Eu element after drying of porous structure luminescent hydrogel material.
FIG. 4 is a diagram of a porous structure luminescent hydrogel material under solar irradiation.
FIG. 5 is a graph of a porous structure light emitting hydrogel material under UV irradiation.
FIG. 6 shows excitation and emission spectra of a porous luminescent hydrogel material.
FIG. 7 is a spectrum of light emission of the porous structure luminescent hydrogel material after soaking in formaldehyde solutions of different concentrations.
FIG. 8 is a stress-strain diagram of a porous-structured luminescent hydrogel material.
Detailed Description
The scheme provides a porous structure luminescent hydrogel material, the hydrogel material is MFC/PC/Eu/TTa, eu and TTa form a rare earth europium complex, MFC 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, MFC is microfibrillated cellulose, PC is 2,3-pyridinedicarboxylic acid chitosan, eu is rare earth europium ion, and TTa is 2-thenoyltrifluoroacetone sodium salt.
PC is firstly connected with MFC to form a three-dimensional network, then is combined with Eu through coordination bonds, and TTa is combined with Eu connected with the three-dimensional network to form a rare earth europium complex.
Specifically, a carbonyl functional group of TTa is combined with Eu in a coordination bond to form the rare earth europium complex, MFC and PC are connected in a hydrogen bond mode to form the three-dimensional network, and a carboxyl functional group of PC is combined with Eu in a coordination bond mode.
The scheme takes natural biomacromolecule MFC and chitosan as matrixes, is easy to degrade, and belongs to an environment-friendly material. MFC is connected with PC through hydrogen bond to form a stable three-dimensional network, namely a hydrogel network skeleton; eu is firstly combined with a carboxyl functional group of PC in a three-dimensional network through a coordination bond to achieve the aim of being stably connected with a hydrogel network framework and is uniformly distributed in the hydrogel network framework; TTa is further coordinated with Eu through the carbonyl functional group of TTa to form the rare earth europium complex, so that the rare earth europium complex can be uniformly distributed in the network framework of the matrix, the fluorescence quenching phenomenon of the material prepared by the traditional physical doping is avoided, and the stable red fluorescent material with excellent luminescence is formed.
The scheme also provides a method for preparing the luminescent hydrogel material with the porous structure, which comprises the following steps:
s1, pre-freezing: dissolving PC in MFC, stirring at room temperature until the PC is fully dissolved, and pre-freezing at-25 ℃;
s2, freezing: adding epichlorohydrin and sodium hydroxide, stirring, pouring into a mold, and freezing at-25 deg.C;
s3, unfreezing: unfreezing in Eu solution, and washing with a large amount of deionized water;
s4, soaking: soaked in TTa solution and washed with copious amounts of deionized water.
The method adopts freezing-unfreezing to prepare the hydrogel material, so that PC, MFC and the rare earth europium complex are connected through coordination bonds, the rare earth europium complex can be uniformly distributed in a skeleton network of a 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, can be processed into different forms according to different requirements, so that the form of the hydrogel material can be designed according to the requirement, and the obtained hydrogel material has excellent mechanical properties. The preparation method can be applied to other rare earth ion luminescent systems and natural biological macromolecule systems.
Preferably, in step S1, the mass percentage concentration of PC in MFC is 1% to 3.8%, more preferably 1% to 3.3%.
Preferably, in step S1, the prefreezing time is 30min.
Preferably, in step S2, the volume percentage of epichlorohydrin in MFC is between 5% and 25%, more preferably between 10% and 20%.
Preferably, in step S2, the concentration of sodium hydroxide in MFC is 0.6-3.6% by mass.
Preferably, in step S2, the freezing time is 12 to 48 hours, more preferably 16 to 40 hours.
Preferably, in step S3, the molar concentration of the Eu solution is 0.01 to 0.2M, and more preferably 0.05 to 0.16M.
Preferably, in step S4, the molar concentration of the TTa solution is 0.01-0.2M, more preferably 0.02-0.15M.
Further, before step S1, the following steps are also included:
s0. preparation: the preparation of PC specifically comprises:
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-pyridinedicarboxylic acid anhydride has a molar concentration of 0.35 to 0.6M, more preferably 0.39 to 0.6M.
Preferably, in step S03, the molar concentration of the sodium hydroxide solution is 2 to 3M, more preferably 2.4 to 2.9M.
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
Dissolving 1.5g of chitosan in 100mL of acetic acid solution with volume percentage concentration of 2.5%, adding 30mL of pyridine solution of 2,3-pyridine dicarboxylic anhydride with molar concentration of 0.35M into the chitosan acetic acid solution, fully stirring, adjusting the pH of the mixed solution to =7 by using sodium hydroxide with molar concentration of 2.0M, fully stirring for 24h, transferring the mixed solution into a dialysis bag for dialysis for one week, taking out the mixed solution, centrifuging at high speed, and evaporating to dryness to obtain 2,3-pyridine dicarboxylic acid chitosan (PC). 50mg of PC was added to 5mL of MFC sol, magnetically stirred at room temperature until the PC was fully dissolved, and pre-frozen at-25 ℃ for 30min. And then adding 0.25mL of epoxy chloropropane, stirring uniformly, adding 30mg of sodium hydroxide, stirring uniformly, placing the mixture in a refrigerator at the temperature of-25 ℃ for freezing for 12h, unfreezing the obtained jelly in 20mL of europium chloride solution with the molar concentration of 0.01M, washing with a large amount of deionized water, soaking the hydrogel in 20mL of TTa aqueous solution with the molar concentration of 0.01M for 12h, and washing with a large amount of deionized water to obtain the luminescent hydrogel material.
Example 2
Dissolving 1.5g of chitosan in 100mL of acetic acid solution with the volume percentage concentration of 2.5%, adding 40mL of pyridine solution of 2,3-pyridine dicarboxylic anhydride with the molar concentration of 0.39M into the chitosan acetic acid solution, fully stirring, adjusting the pH of the mixed solution to be =7 by using sodium hydroxide with the molar concentration of 2.2M, fully stirring for 24 hours, transferring the mixed solution to a dialysis bag for dialysis for one week, taking out the mixed solution, centrifuging the mixed solution under high-speed centrifugation, and evaporating the solution to dryness to obtain 2,3-pyridine dicarboxylic acid chitosan (PC). Adding 100mg PC into 5ml LMFC sol, magnetically stirring at room temperature until PC is fully dissolved, and pre-freezing at-25 deg.C for 30min. And then adding 0.5mL of epoxy chloropropane, stirring uniformly, adding 40mg of sodium hydroxide, stirring uniformly, placing the mixture in a refrigerator at the temperature of-25 ℃ for freezing for 18h, unfreezing the obtained jelly in 20mL of europium chloride solution with the molar concentration of 0.02M, washing with a large amount of deionized water, soaking the hydrogel in 20mL of TTa aqueous solution with the molar concentration of 0.05M for 12h, and washing with a large amount of deionized water to obtain the luminescent hydrogel material.
Example 3
Dissolving 1.5g of chitosan in 100mL of acetic acid solution with volume percentage concentration of 2.5%, adding 40mL of pyridine solution of 2,3-pyridine dicarboxylic anhydride with molar concentration of 0.5M into the chitosan acetic acid solution, fully stirring, adjusting the pH of the mixed solution to =7 by using sodium hydroxide with molar concentration of 2.4M, fully stirring for 36h, transferring the mixed solution into a dialysis bag for dialysis for one week, taking out the mixed solution, centrifuging at high speed, and evaporating to dryness to obtain 2,3-pyridine dicarboxylic acid chitosan (PC). 140mg of PC was added to 5mL of MFC sol, magnetically stirred at room temperature until the PC was fully dissolved, and pre-frozen at-25 ℃ for 30min. And then adding 0.7mL of epoxy chloropropane, stirring uniformly, adding 80mg of sodium hydroxide, stirring uniformly, placing the mixture in a refrigerator at the temperature of-25 ℃ for freezing for 24h, unfreezing the obtained jelly in 20mL of europium chloride solution with the molar concentration of 0.05M, washing with a large amount of deionized water, soaking the hydrogel in 20mL of TTa aqueous solution with the molar concentration of 0.08M for 12h, and washing with a large amount of deionized water to obtain the luminescent hydrogel material.
Example 4
Dissolving 1.5g of chitosan in 100mL of acetic acid solution with volume percentage concentration of 2.5%, adding 40mL of pyridine solution of 2,3-pyridine dicarboxylic anhydride with molar concentration of 0.55M into the chitosan acetic acid solution, fully stirring, adjusting the pH of the mixed solution to =7 by using sodium hydroxide with molar concentration of 2.6M, fully stirring for 36h, transferring the mixed solution into a dialysis bag for dialysis for one week, taking out the mixed solution, centrifuging at high speed, and evaporating to dryness to obtain 2,3-pyridine dicarboxylic acid chitosan (PC). 120mg PC was added to 5mL MFC sol, magnetically stirred at room temperature until PC was fully dissolved, and pre-frozen at-25 ℃ for 30min. And then adding 0.8mL of epoxy chloropropane, stirring uniformly, adding 100mg of sodium hydroxide, stirring uniformly, placing the mixture in a refrigerator at the temperature of-25 ℃ for freezing for 36h, unfreezing the obtained jelly in 20mL of europium chloride solution with the molar concentration of 0.10M, washing with a large amount of deionized water, soaking the hydrogel in 20mL of TTa aqueous solution with the molar concentration of 0.10M for 12h, and washing with a large amount of deionized water to obtain the luminescent hydrogel material.
Example 5
Dissolving 1.5g of chitosan in 100mL of acetic acid solution with volume percentage concentration of 2.5%, adding 50mL of pyridine solution of 2,3-pyridine dicarboxylic anhydride with the molar concentration of 0.57M into the chitosan acetic acid solution, fully stirring, adjusting the pH of the mixed solution to =7 by using sodium hydroxide with the molar concentration of 2.8M, fully stirring for 48h, transferring the mixed solution into a dialysis bag for dialysis for one week, taking out the mixed solution, centrifuging at high speed, and evaporating to dryness to obtain 2,3-pyridine dicarboxylic acid chitosan (PC). 130mg of PC was added to 5mL of MFC sol, magnetically stirred at room temperature until the PC was sufficiently dissolved, and pre-frozen at-25 ℃ for 30min. Then adding 0.9mL of epoxy chloropropane, stirring uniformly, adding 180mg of sodium hydroxide, stirring uniformly, placing the mixture in a refrigerator at the temperature of-25 ℃ for freezing for 48h, unfreezing the obtained jelly in 20mL of europium chloride solution with the molar concentration of 0.14M, washing with a large amount of deionized water, soaking the hydrogel in 30mL of TTa aqueous solution with the molar concentration of 0.15M for 12h, and washing with a large amount of deionized water to obtain the luminescent hydrogel material.
Example 6
Dissolving 1.5g of chitosan in 100mL of acetic acid solution with volume percentage concentration of 2.5%, adding 50mL of pyridine solution of 2,3-pyridine dicarboxylic anhydride with molar concentration of 0.6M into the chitosan acetic acid solution, fully stirring, adjusting the pH of the mixed solution to =7 by using sodium hydroxide with molar concentration of 2.9M, fully stirring for 48h, transferring the mixed solution into a dialysis bag for dialysis for one week, taking out the mixed solution, centrifuging at high speed, and evaporating to dryness to obtain 2,3-pyridine dicarboxylic acid chitosan (PC). 150mg of PC was added to 5mL of MFC sol, magnetically stirred at room temperature until PC was fully dissolved, and pre-frozen at-25 ℃ for 30min. And then adding 1.0mL of epoxy chloropropane, stirring uniformly, adding 180mg of sodium hydroxide, stirring uniformly, placing the mixture in a refrigerator at the temperature of-25 ℃ for freezing for 48h, unfreezing the obtained jelly in 20mL of europium chloride solution with the molar concentration of 0.16M, washing with a large amount of deionized water, soaking the hydrogel in 40mL of TTa aqueous solution with the molar concentration of 0.18M for 12h, and washing with a large amount of deionized water to obtain the luminescent hydrogel material.
Example 7
Dissolving 1.5g of chitosan in 100mL of acetic acid solution with volume percentage concentration of 2.5%, adding 50mL of pyridine solution of 2,3-pyridine dicarboxylic anhydride with molar concentration of 0.6M into the chitosan acetic acid solution, fully stirring, adjusting the pH of the mixed solution to =7 by using sodium hydroxide with molar concentration of 3.0M, fully stirring for 48h, transferring the mixed solution into a dialysis bag for dialysis for one week, taking out the mixed solution, centrifuging at high speed, and evaporating to dryness to obtain 2,3-pyridine dicarboxylic acid chitosan (PC). 165mg of PC was added to 5mL of MFC sol, magnetically stirred at room temperature until the PC was fully dissolved, and pre-frozen at-25 ℃ for 30min. And then adding 1.2mL of epoxy chloropropane, stirring uniformly, adding 180mg of sodium hydroxide, stirring uniformly, placing the mixture in a refrigerator at the temperature of-25 ℃ for freezing for 48h, unfreezing the obtained jelly in 20mL of europium chloride solution with the molar concentration of 0.18M, washing with a large amount of deionized water, soaking the hydrogel in 40mL of TTa aqueous solution with the molar concentration of 0.2M for 12h, and washing with a large amount of deionized water to obtain the luminescent hydrogel material.
Example 8
Dissolving 1.5g of chitosan in 100mL of acetic acid solution with the volume percentage concentration of 2.5%, adding 40mL of pyridine solution of 2,3-pyridine dicarboxylic anhydride with the molar concentration of 0.6M into the chitosan acetic acid solution, fully stirring, adjusting the pH of the mixed solution to be =7 by using sodium hydroxide with the molar concentration of 3.0M, fully stirring for 48h, transferring the mixed solution to a dialysis bag for dialysis for one week, taking out the mixed solution, centrifuging the mixed solution under high-speed centrifugation, and evaporating the solution to dryness to obtain 2,3-pyridine dicarboxylic acid chitosan (PC). 190mg of PC was added to 5mL of MFC sol, magnetically stirred at room temperature until the PC was fully dissolved, and pre-frozen at-25 ℃ for 30min. And then adding 1.25mL of epoxy chloropropane, stirring uniformly, adding 180mg of sodium hydroxide, stirring uniformly, placing the mixture in a refrigerator at the temperature of-25 ℃ for freezing for 48h, unfreezing the obtained jelly in 20mL of europium chloride solution with the molar concentration of 0.2M, washing with a large amount of deionized water, soaking the hydrogel in 40mL of TTa aqueous solution with the molar concentration of 0.2M for 12h, and washing with a large amount of deionized water to obtain the luminescent hydrogel material.
The luminescent hydrogel materials prepared in the above examples were tested as follows:
(one) thermal stability of hydrogel materials after drying
FIG. 1 is a thermogravimetric plot of a hydrogel material after freeze-drying, from which it can be seen that the hydrogel material has good thermal stability with a decomposition temperature of 251 ℃.
Morphology of (II) hydrogel materials
To determine the morphology of the hydrogel, aerogel samples were obtained using freeze-drying techniques. 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 map 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 hydrogel Material
FIG. 4 is a graph of a hydrogel material in sunlight, FIG. 5 is a graph under UV lamp illumination, and it can be seen from FIG. 5 that the hydrogel emits pure red light under UV lamp illumination.
FIG. 6 shows the excitation and emission spectra of hydrogel materials, and it can be seen from FIG. 6 that excitation is achieved by absorbing UV light with 2-thenoyltrifluoroacetone ligand, and transferring energy to the excited state of rare earth europium ion after intersystem crossing. In the excitation spectrum, 4 f-4 f transition of rare earth europium ions is not found, which indicates that energy transfer is carried out through 2-thenoyl trifluoroacetone groups, and the transfer efficiency is high, thereby indirectly proving that the 2-thenoyl trifluoroacetone and the rare earth europium ions form a complex. From FIG. 6, it can be seen that an emission spectrum is obtained under 378nm excitation, and the maximum emission peak is at 613nm, 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.
(IV) recognition performance of hydrogel material on formaldehyde
FIG. 7 is a fluorescence spectrum of the luminescent hydrogel material after being soaked in formaldehyde solutions of 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 formaldehyde concentration, which shows that the luminescent hydrogel has excellent formaldehyde recognition performance.
(V) mechanical properties of hydrogel materials
FIG. 8 is a stress-strain diagram of a luminescent hydrogel material, from which it can be seen that the hydrogel material, after being compressed to different degrees, still maintains its original morphology 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.
According to the test results, the hydrogel material has excellent luminescence, and the interior of the hydrogel material presents a macroporous structure, so that the hydrogel material is a luminescent hydrogel material with a porous structure; the decomposition temperature is 251 ℃, the material has excellent thermal stability, and also shows excellent mechanical properties and good shape memory performance. The red fluorescent material can obtain a red emission spectrum under the excitation of 378nm, has a maximum emission peak at 613nm, 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 luminescent material can be applied to the recognition of formaldehyde and is an excellent novel composite material.
Based on the scheme, the application of the porous structure luminescent hydrogel material as a fluorescent material is further provided, and the porous structure luminescent hydrogel material is particularly suitable for identifying formaldehyde.
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 porous structure luminescent hydrogel material is MFC/PC/Eu/TTa, rare earth europium complexes formed by Eu and TTa are uniformly distributed in a three-dimensional network formed by MFC and PC, eu in the rare earth europium complexes is combined with the three-dimensional network through coordination bonds, MFC is microfibrillated cellulose, PC is 2,3-pyridinedicarboxylic acid chitosan, eu is rare earth europium ions, and TTa is 2-thenoyltrifluoroacetone sodium salt.
2. The porous structure luminescent hydrogel material according to claim 1, wherein the PC is first connected to MFC to form the three-dimensional network, and then is bonded to Eu by coordination bonds, and the TTa is then bonded to Eu connected to the three-dimensional network to form the rare earth europium complex.
3. A porous structure light-emitting hydrogel material according to claim 1,
the carbonyl functional group of TTa is combined with Eu by a coordination bond to form the rare earth europium complex; and/or
The MFC and the PC are connected through hydrogen bonds to form the three-dimensional network; and/or
The carboxyl functional group of the PC is combined with Eu in a coordination bond; and/or
The decomposition temperature of the hydrogel material was 251 ℃.
4. A method for preparing a porous structure luminescent hydrogel material according to any one of claims 1 to 3, comprising the steps of:
pre-freezing: dissolving PC in MFC, stirring at room temperature to dissolve completely, and pre-freezing at-25 deg.C;
freezing: adding epichlorohydrin and sodium hydroxide, stirring, pouring into a mold, and freezing at-25 deg.C;
unfreezing: unfreezing in Eu solution, and washing with a large amount of deionized water;
soaking: soaked in TTa solution and washed with copious amounts of deionized water.
5. The method for preparing a porous luminescent hydrogel material according to claim 4, wherein,
the mass percentage concentration of the PC in the MFC is 1-3.8%; and/or
Pre-freezing for 30min; and/or
The volume percentage of the epichlorohydrin in the MFC is 5-25 percent; and/or
The mass percentage concentration of the sodium hydroxide in the MFC is 0.6-3.6%; and/or
The freezing time is 12-48 h; and/or
The molar concentration of the Eu solution is 0.01-0.2M; and/or
The molar concentration of the TTa solution is 0.01-0.2M.
6. The method for preparing a porous structure light-emitting hydrogel material according to claim 5,
the mass percentage concentration of the PC in the MFC is 1-3.3%; and/or
The volume percentage of the epichlorohydrin in the MFC is 10-20%; and/or
The freezing time is 16-40 h; and/or
The molar concentration of the Eu solution is 0.05-0.16M; and/or
The molar concentration of the TTa solution is 0.02-0.15M.
7. The method for preparing a porous structure light-emitting hydrogel material according to claim 4, further comprising a step of preparing PC before pre-freezing, 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 porous structure light-emitting hydrogel material according to claim 7, wherein in the preparation of PC,
the volume percentage concentration of the acetic acid solution is 2-5%; and/or
The mass percentage concentration of the chitosan in the acetic acid solution is 1.5 percent; and/or
The molar concentration of the pyridine solution of 2,3-pyridine dicarboxylic anhydride is 0.35-0.6M; and/or
The molar concentration of the sodium hydroxide solution is 2-3M.
9. Use of a porous structure luminescent hydrogel material according to any of claims 1 to 3 or prepared by a method according to any of claims 4 to 8 as a fluorescent material.
10. Use of the porous luminescent hydrogel material according to claim 9 as a fluorescent material, wherein the luminescent hydrogel material is used for the recognition of formaldehyde.
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