CN115337876B - Porous structure luminous hydrogel material and preparation and application thereof - Google Patents
Porous structure luminous hydrogel material and preparation and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 101
- 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 44
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 41
- 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 31
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 30
- 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 rare earth europium ions Chemical class 0.000 claims abstract description 17
- 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
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229920002678 cellulose Polymers 0.000 claims abstract description 4
- 239000001913 cellulose Substances 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
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 33
- 238000007710 freezing Methods 0.000 claims description 26
- 230000008014 freezing Effects 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 26
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 22
- 238000000502 dialysis Methods 0.000 claims description 20
- 238000010257 thawing Methods 0.000 claims description 16
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 14
- 238000002791 soaking Methods 0.000 claims description 14
- 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 12
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 12
- 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
- 238000001704 evaporation Methods 0.000 claims description 2
- 238000000703 high-speed centrifugation Methods 0.000 claims description 2
- 230000001413 cellular effect Effects 0.000 claims 1
- 238000010791 quenching Methods 0.000 abstract description 6
- 230000000171 quenching effect Effects 0.000 abstract description 6
- 239000011148 porous material Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 63
- 239000000203 mixture Substances 0.000 description 26
- 238000000034 method Methods 0.000 description 13
- 238000000295 emission spectrum Methods 0.000 description 9
- 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
- 230000005284 excitation Effects 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 7
- 238000010586 diagram Methods 0.000 description 5
- 238000004020 luminiscence type Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 238000000695 excitation spectrum Methods 0.000 description 3
- 239000004964 aerogel Substances 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 239000002149 hierarchical pore Substances 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229920001059 synthetic polymer Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- TXBBUSUXYMIVOS-UHFFFAOYSA-N thenoyltrifluoroacetone Chemical compound FC(F)(F)C(=O)CC(=O)C1=CC=CS1 TXBBUSUXYMIVOS-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- FHUDAMLDXFJHJE-UHFFFAOYSA-N 1,1,1-trifluoropropan-2-one Chemical group CC(=O)C(F)(F)F FHUDAMLDXFJHJE-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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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- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The scheme belongs to the technical field of hydrogel materials, and discloses a porous structure luminous 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 MFC and PC, eu in the rare earth europium complex is combined with the three-dimensional network through coordination bonds, MFC is microfibrillated cellulose, PC is 2, 3-pyridine dicarboxylic acid chitosan, eu is rare earth europium ions, and TTa is 2-thiophene formyl trifluoroacetone sodium salt. According to the scheme, PC and MFC are used as matrixes, and the carboxyl functional groups of PC are coordinated with Eu, so that the rare earth europium complex formed by the 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 to achieve a molecular level, so that the fluorescence quenching phenomenon of a material prepared by traditional physical doping is avoided, and meanwhile, the hydrogel material belongs to an environment-friendly material, and has a multistage pore structure, high rebound 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 luminous hydrogel material, and preparation and application thereof.
Background
The rare earth europium complex has excellent luminescence property and is widely paid attention to by scientific researchers. In order to make practical use of luminescent rare earth europium complexes, it is often necessary to incorporate the rare earth europium complex into some suitable matrix. The traditional method is to introduce rare earth europium complex into some synthetic polymer or silicon dioxide matrix. However, silica and synthetic polymer materials have some inherent disadvantages, such as poor biocompatibility and low biodegradability. 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. Currently, research on luminescent hydrogel composite materials with hierarchical pore structures and good mechanical properties is less by scientific researchers in various fields.
Disclosure of Invention
In view of the above, the present invention aims to overcome at least one of the disadvantages in the prior art, and provides a porous structure luminescent hydrogel material with excellent mechanical properties and easy degradation.
In order to solve the technical problems, the following technical scheme is adopted:
in the 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 MFC and PC, eu in the rare earth europium complex is combined with the three-dimensional network through coordination bonds, MFC is microfibrillated cellulose, PC is 2, 3-pyridine dicarboxylic acid chitosan, eu is rare earth europium ion, and TTa is 2-thiophene formyl trifluoroacetone sodium salt.
The scheme takes natural biological macromolecule MFC and chitosan as matrixes, is easy to degrade, and belongs to an environment-friendly material. The MFC is connected with the PC through a hydrogen bond to form a stable three-dimensional network, namely a hydrogel network framework; eu is firstly combined with a carboxyl functional group of PC in a three-dimensional network through coordination bonds, so that the aim of stable connection with a hydrogel network skeleton is fulfilled, and the Eu is uniformly distributed in the hydrogel network skeleton; TTa is then further coordinated with Eu through carbonyl functional groups to form a rare earth europium complex, so that the rare earth europium complex can be uniformly distributed in a network skeleton of a matrix, the fluorescence quenching phenomenon of the material prepared by traditional physical doping is avoided, and a stable and excellent-luminescence red fluorescent material is formed.
In a second aspect, a method for preparing the porous luminescent hydrogel material includes the following steps:
pre-freezing: dissolving PC in MFC, stirring at room temperature until the PC is fully dissolved, and pre-freezing at-25deg.C;
freezing: adding epichlorohydrin and sodium hydroxide, stirring, pouring into a mold, and freezing at-25deg.C;
thawing: thawing in Eu solution, washing with a large amount of deionized water;
soaking: soaking in TTa solution, washing with a large amount of deionized water.
The method adopts a simple and easy method of freezing and thawing to prepare the hydrogel material, and leads PC and MFC to be connected with the rare earth europium complex 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 traditional physical doping. 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, and can be 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 porous structured luminescent hydrogel material is used as a fluorescent material. In the scheme, the hydrogel material emits light excellently, a red emission spectrum is obtained under 378nm excitation, the maximum emission peak is 613nm, and the hydrogel material is a typical pure red fluorescence emission peak of a rare earth europium complex, has high color purity, and can be used as a red fluorescent material. The porous structure luminous hydrogel material has excellent formaldehyde recognition performance, and can be applied to formaldehyde recognition.
Compared with the prior art, the scheme has the following beneficial effects:
firstly, PC and MFC are used as matrixes, and the carboxyl functional group of PC is coordinated with Eu, so that the rare earth europium complex formed by the 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 to achieve a molecular level, thereby avoiding the fluorescence quenching phenomenon of materials prepared by traditional physical doping.
Secondly, the hydrogel material has good luminescence property and formaldehyde recognition property, a red emission spectrum is obtained under 378nm excitation, and the maximum emission peak is 613nm, which is a typical pure red fluorescence emission peak of rare earth europium complex, and the color purity is high.
Furthermore, the matrix of the luminescent hydrogel material is easy to degrade, belongs to an environment-friendly material, has a porous structure, and has high rebound performance and good thermal stability (the decomposition temperature is 251 ℃).
Finally, a simple and feasible method is used for connecting PC and MFC with the rare earth europium complex through coordination bonds, the prepared hydrogel material has good processability, can be processed into different forms according to different requirements, and is simple and feasible in post-treatment.
Drawings
FIG. 1 is a thermogravimetric diagram of a porous structured luminescent hydrogel material after drying.
FIG. 2 is a scanning electron microscope image of a porous structured luminescent hydrogel material after drying.
FIG. 3 is a Eu element distribution diagram of a porous luminescent hydrogel material after drying.
FIG. 4 is a graph of a cellular structure luminescent hydrogel material under sunlight.
FIG. 5 is a diagram of a porous structured luminescent hydrogel material under irradiation of an ultraviolet lamp.
FIG. 6 is a graph of excitation and emission spectra of a porous structured luminescent hydrogel material.
FIG. 7 is a graph showing the emission spectrum of a porous luminescent hydrogel material after being immersed 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 luminous hydrogel material, which is characterized in that the hydrogel material is MFC/PC/Eu/TTa, eu and TTa form a rare earth europium complex, the MFC and the 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 coordination bonds, the MFC is microfibrillated cellulose, the PC is 2, 3-pyridine dicarboxylic acid chitosan, the Eu is rare earth europium ions, and the TTa is 2-thiophene formyl trifluoroacetone sodium salt.
Wherein PC is connected with MFC to form a three-dimensional network, then is combined with Eu through coordination bond, and TTa is combined with Eu connected with the three-dimensional network to form a rare earth europium complex.
Specifically, the carbonyl functional group of TTa is combined with Eu in a coordination bond to form the rare earth europium complex, the MFC and PC are connected in a hydrogen bond to form the three-dimensional network, and the carboxyl functional group of PC is combined with Eu in a coordination bond.
The scheme takes natural biological macromolecule MFC and chitosan as matrixes, is easy to degrade, and belongs to an environment-friendly material. The MFC is connected with the PC through a hydrogen bond to form a stable three-dimensional network, namely a hydrogel network framework; eu is combined with a carboxyl functional group of PC in a three-dimensional network through coordination bonds, so that the aim of stable connection with a hydrogel network skeleton is fulfilled, and the Eu is uniformly distributed in the hydrogel network skeleton; TTa is then further coordinated with Eu through carbonyl functional groups to form a rare earth europium complex, so that the rare earth europium complex can be uniformly distributed in a network skeleton of a matrix, the fluorescence quenching phenomenon of the material prepared by traditional physical doping is avoided, and a stable and excellent-luminescence red fluorescent material is formed.
The scheme also provides a method for preparing the porous structure luminescent hydrogel material, 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-25deg.C;
s2, freezing: adding epichlorohydrin and sodium hydroxide, stirring, pouring into a mold, and freezing at-25deg.C;
s3, thawing: thawing in Eu solution, washing with a large amount of deionized water;
s4, soaking: soaking in TTa solution, washing with a large amount of deionized water.
The method adopts a simple and easy method of freezing and thawing to prepare the hydrogel material, so that PC and MFC are connected with the rare earth europium complex 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 requirements, 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 the MFC is between 5% and 25%, more preferably between 10% and 20%.
Preferably, in step S2, the mass percentage concentration of sodium hydroxide in MFC is 0.6-3.6%.
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, more preferably 0.05 to 0.16M.
Preferably, in step S4, the molar concentration of TTa solution is 0.01 to 0.2M, more preferably 0.02 to 0.15M.
Further, before step S1, the method further includes the following steps:
s0. preparation: the preparation method of PC specifically comprises the following steps:
s01, adding chitosan into 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 after high-speed centrifugation.
Preferably, in step S01, the concentration of the acetic acid solution is 2 to 5% by volume, more preferably 2.5 to 4.5%.
Preferably, in step S01, the mass percentage concentration of chitosan in the acetic acid solution is 1.5%.
Preferably, in step S02, the molar concentration of the pyridine solution of 2, 3-pyridinedicarboxylic acid anhydride is from 0.35 to 0.6M, more preferably from 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 enable those skilled in the art to better understand the technical solution of the present solution, the present solution is described in further detail below with reference to specific embodiments. The process methods used in the examples are conventional methods unless otherwise specified; the materials used, unless otherwise specified, are all commercially available.
Example 1
1.5g of chitosan was dissolved in 100mL of 2.5% by volume acetic acid solution, 30mL of a pyridine solution of 0.35M molar concentration of 2, 3-pyridine dicarboxylic acid anhydride was added to the chitosan acetic acid solution, and the mixture was sufficiently stirred, adjusted to ph=7 with 2.0M molar concentration of sodium hydroxide, and sufficiently stirred for 24 hours, and after the mixture was transferred to a dialysis bag for dialysis, the solution was removed and centrifuged at high speed and evaporated 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 PC was sufficiently dissolved, and pre-frozen at-25℃for 30min. Then adding 0.25mL of epichlorohydrin, stirring uniformly, adding 30mg of sodium hydroxide, stirring uniformly, placing the mixture in a refrigerator at the temperature of minus 25 ℃ for freezing for 12 hours, thawing the obtained jelly in 20mL of 0.01M europium chloride solution, washing with a large amount of deionized water, soaking the hydrogel in 20mL of 0.01M TTa aqueous solution for 12 hours, washing with a large amount of deionized water, and finally obtaining the luminous hydrogel material.
Example 2
1.5g of chitosan was dissolved in 100mL of 2.5% by volume acetic acid solution, 40mL of a pyridine solution of 0.39M molar concentration of 2, 3-pyridine dicarboxylic acid anhydride was added to the chitosan acetic acid solution, and the mixture was sufficiently stirred, adjusted to ph=7 with 2.2M molar concentration of sodium hydroxide, and sufficiently stirred for 24 hours, and after the mixture was transferred to a dialysis bag for dialysis, the solution was removed and centrifuged at high speed and evaporated to dryness to obtain 2, 3-pyridine dicarboxylic acid chitosan (PC). 100mg of PC was added to the 5 mM FC sol, magnetically stirred at room temperature until PC was sufficiently dissolved, and pre-frozen at-25℃for 30min. Then adding 0.5mL of epichlorohydrin, stirring uniformly, adding 40mg of sodium hydroxide, stirring uniformly, placing the mixture in a refrigerator at the temperature of minus 25 ℃ for freezing for 18 hours, thawing 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 aqueous solution of TTa with the molar concentration of 0.05M for 12 hours, washing with a large amount of deionized water, and finally obtaining the luminous hydrogel material.
Example 3
1.5g of chitosan was dissolved in 100mL of 2.5% by volume acetic acid solution, 40mL of a pyridine solution of 0.5M molar concentration of 2, 3-pyridine dicarboxylic acid anhydride was added to the chitosan acetic acid solution, and the mixture was sufficiently stirred, adjusted to ph=7 with 2.4M molar concentration of sodium hydroxide, and sufficiently stirred for 36 hours, and after the mixture was transferred to a dialysis bag for dialysis for one week, the solution was removed and centrifuged at high speed and evaporated 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 PC was sufficiently dissolved, and pre-frozen at-25℃for 30min. Then adding 0.7mL of epichlorohydrin, stirring uniformly, adding 80mg of sodium hydroxide, stirring uniformly, placing the mixture in a refrigerator at the temperature of minus 25 ℃ for freezing for 24 hours, thawing 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 aqueous solution with the molar concentration of TTa of 0.08M for 12 hours, washing with a large amount of deionized water, and finally obtaining the luminous hydrogel material.
Example 4
1.5g of chitosan was dissolved in 100mL of an acetic acid solution with a volume percentage concentration of 2.5%, 40mL of a pyridine solution of 2, 3-pyridine dicarboxylic acid anhydride with a molar concentration of 0.55M was added to the chitosan acetic acid solution, and the mixture was sufficiently stirred, adjusted to ph=7 with sodium hydroxide with a molar concentration of 2.6M, and sufficiently stirred for 36 hours, and after the mixture was transferred to a dialysis bag for dialysis for one week, the solution was taken out and centrifuged at high speed and evaporated to dryness to obtain 2, 3-pyridine dicarboxylic acid chitosan (PC). 120mg of PC was added to 5mL of MFC sol, magnetically stirred at room temperature until PC was sufficiently dissolved, and pre-frozen at-25℃for 30min. Then adding 0.8mL of epichlorohydrin, stirring uniformly, adding 100mg of sodium hydroxide, stirring uniformly, placing the mixture in a refrigerator at the temperature of minus 25 ℃ for freezing for 36 hours, thawing 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 aqueous solution with the molar concentration of TTa of 0.10M for 12 hours, washing with a large amount of deionized water, and finally obtaining the luminous hydrogel material.
Example 5
1.5g of chitosan was dissolved in 100mL of an acetic acid solution with a volume percentage concentration of 2.5%, 50mL of a pyridine solution of 0.57M 2, 3-pyridine dicarboxylic anhydride was added to the chitosan acetic acid solution, and the mixture was sufficiently stirred, adjusted to ph=7 with 2.8M sodium hydroxide, and sufficiently stirred for 48 hours, and after the mixture was transferred to a dialysis bag for dialysis for one week, the solution was removed and centrifuged at high speed and evaporated 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 PC was sufficiently dissolved, and pre-frozen at-25℃for 30min. Then adding 0.9mL of epichlorohydrin, stirring uniformly, adding 180mg of sodium hydroxide, stirring uniformly, placing the mixture in a refrigerator at the temperature of minus 25 ℃ for freezing for 48 hours, thawing 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 aqueous solution of TTa with the molar concentration of 0.15M for 12 hours, washing with a large amount of deionized water, and finally obtaining the luminous hydrogel material.
Example 6
1.5g of chitosan was dissolved in 100mL of 2.5% by volume acetic acid solution, 50mL of a pyridine solution of 0.6M molar concentration of 2, 3-pyridine dicarboxylic acid anhydride was added to the chitosan acetic acid solution, and the mixture was sufficiently stirred, adjusted to ph=7 with 2.9M molar concentration of sodium hydroxide, and sufficiently stirred for 48 hours, and after the mixture was transferred to a dialysis bag for dialysis for one week, the solution was removed and centrifuged at high speed and evaporated 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 sufficiently dissolved, and pre-frozen at-25℃for 30min. Then adding 1.0mL of epichlorohydrin, stirring uniformly, adding 180mg of sodium hydroxide, stirring uniformly, placing the mixture in a refrigerator at the temperature of minus 25 ℃ for freezing for 48 hours, thawing 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 aqueous solution of TTa with the molar concentration of 0.18M for 12 hours, washing with a large amount of deionized water, and finally obtaining the luminous hydrogel material.
Example 7
1.5g of chitosan was dissolved in 100mL of an acetic acid solution with a volume percentage concentration of 2.5%, 50mL of a pyridine solution of 2, 3-pyridine dicarboxylic acid anhydride with a molar concentration of 0.6M was added to the chitosan acetic acid solution, the mixture was sufficiently stirred, the ph=7 was adjusted with sodium hydroxide with a molar concentration of 3.0M, the mixture was sufficiently stirred for 48 hours, the mixture was transferred to a dialysis bag for dialysis for one week, and the solution was taken out and centrifuged at high speed and evaporated 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 PC was sufficiently dissolved, and pre-frozen at-25℃for 30min. Then adding 1.2mL of epichlorohydrin, stirring uniformly, adding 180mg of sodium hydroxide, stirring uniformly, placing the mixture in a refrigerator at the temperature of minus 25 ℃ for freezing for 48 hours, thawing 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 aqueous solution with the molar concentration of TTa of 0.2M for 12 hours, washing with a large amount of deionized water, and finally obtaining the luminous hydrogel material.
Example 8
1.5g of chitosan was dissolved in 100mL of an acetic acid solution with a volume percentage concentration of 2.5%, 40mL of a pyridine solution of 2, 3-pyridine dicarboxylic acid anhydride with a molar concentration of 0.6M was added to the chitosan acetic acid solution, and the mixture was sufficiently stirred, adjusted to ph=7 with sodium hydroxide with a molar concentration of 3.0M, and sufficiently stirred for 48 hours, and after the mixture was transferred to a dialysis bag for dialysis for one week, the solution was taken out and centrifuged at high speed and evaporated 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 PC was sufficiently dissolved, and pre-frozen at-25℃for 30min. Then adding 1.25mL of epichlorohydrin, stirring uniformly, adding 180mg of sodium hydroxide, stirring uniformly, placing the mixture in a refrigerator at the temperature of minus 25 ℃ for freezing for 48 hours, thawing 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 aqueous solution with the molar concentration of TTa of 0.2M for 12 hours, washing with a large amount of deionized water, and finally obtaining the luminous hydrogel material.
The luminescent hydrogel materials prepared in the above examples were tested as follows:
thermal stability of hydrogel materials after drying
Fig. 1 is a graph showing the thermogravimetric profile of a hydrogel material after freeze-drying, from which it can be found that the hydrogel material has good thermal stability and a decomposition temperature of 251 ℃.
(II) morphology of hydrogel materials
To determine the morphology of the hydrogels, aerogel samples were obtained using freeze-drying techniques. The aerogel was observed in cross section using a field emission scanning electron microscope, and as can be seen from fig. 2, the interior of the material exhibited a macroporous structure.
In order to determine the distribution of rare earth europium ions, a graph of europium elements was obtained using a surface scanning technique, and as can be seen from fig. 3, europium elements are uniformly distributed in the material, thereby proving that rare earth europium complexes are uniformly distributed in the biopolymer network skeleton.
Fluorescence Properties of hydrogel Material
Fig. 4 is a view of the hydrogel material under sunlight, and fig. 5 is a view under irradiation of an ultraviolet lamp, and it can be seen from fig. 5 that the hydrogel emits pure red light under irradiation of the ultraviolet lamp.
FIG. 6 is an excitation and emission spectrum of a hydrogel material, and it can be seen from FIG. 6 that the excitation is an excited state by absorbing ultraviolet light to a 2-thenoyl trifluoroacetone ligand, and transferring energy to rare earth europium ions 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 on 2-thiophenyl formyl trifluoroacetone groups and the transfer efficiency is high, thereby indirectly proving that 2-thiophenyl formyl trifluoroacetone and rare earth europium ions form a complex. As can be seen from fig. 6, an emission spectrum is obtained under 378nm excitation, with a maximum emission peak at 613nm, which is a 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, further illustrating that 2-thenoyltrifluoroacetone and rare earth europium ions form a complex.
Identification performance of hydrogel material on formaldehyde
FIG. 7 is a graph of fluorescence spectra of the luminescent hydrogel material after being soaked in formaldehyde solutions with different concentrations, and as can be seen from the graph, the fluorescence intensity of the hydrogel gradually decreases with the increase of the formaldehyde concentration, so that the luminescent hydrogel material has excellent formaldehyde recognition performance.
(V) mechanical Properties of hydrogel Material
Fig. 8 is a stress-strain diagram of a luminescent hydrogel material, from which it can be seen that the hydrogel material remains in its original shape after pressure relief after various degrees of compression, 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/NANOSEM-450 field emission electron microscope of FEI Co., U.S.A.; thermal gravimetric experiments used STA449F31 equipment.
The test results show that the hydrogel material has excellent luminescence, and the inside of the hydrogel material presents a macroporous structure, so that the hydrogel material is a porous structure luminescent hydrogel material; the decomposition temperature is 251 ℃, the thermal stability is excellent, the mechanical property is excellent, and the shape memory property is good. The red emission spectrum is obtained under 378nm excitation, the maximum emission peak is 613nm, and the red emission spectrum is a typical pure red fluorescence emission peak of rare earth europium complex, has high color purity, and can be used as a red fluorescent material. The luminescent material can be applied to formaldehyde identification and is a novel excellent composite material.
Based on the above, the scheme also provides an application of the porous structure luminous hydrogel material as a fluorescent material, and the porous structure luminous hydrogel material is particularly suitable for formaldehyde identification.
It is apparent that the above examples of the present solution are merely examples for clearly illustrating the present solution and are not limiting of the embodiments of the present solution. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present solution should be included in the protection scope of the present solution claims.
Claims (7)
1. A porous structure luminous hydrogel material is characterized in that a rare earth europium complex formed by Eu and TTa is uniformly distributed in a three-dimensional network formed by MFC and PC, and Eu in the rare earth europium complex is combined with the three-dimensional network through coordination bonds; the PC is connected with the MFC through a hydrogen bond to form the three-dimensional network, then the carboxyl functional group of the PC is combined with Eu through a coordination bond, and the carbonyl functional group of the TTa is combined with Eu connected with the three-dimensional network through a coordination bond to form the rare earth europium complex; the MFC is microfibrillated cellulose, PC is 2, 3-pyridine dicarboxylic acid chitosan, eu is rare earth europium ion, TTa is 2-thiophene formyl trifluoroacetone sodium salt, and the decomposition temperature of the hydrogel material is 251 ℃; the preparation method of the porous structure luminous hydrogel material comprises the following steps:
pre-freezing: dissolving PC in MFC, stirring at room temperature until the PC is fully dissolved, and pre-freezing at-25deg.C;
freezing: adding epichlorohydrin and sodium hydroxide, stirring, pouring into a mold, and freezing at-25deg.C;
thawing: thawing in Eu solution, washing with a large amount of deionized water;
soaking: soaking in TTa solution, washing with a large amount of deionized water.
2. The porous structured luminescent hydrogel material of claim 1, wherein the porous structured luminescent hydrogel material comprises,
the mass percentage concentration of the PC in the MFC is 1% -3.8%; and/or
The pre-freezing time is 30 min; and/or
The volume percentage of the epichlorohydrin in the MFC is 5% -25%; 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 hours; 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.
3. The porous structured luminescent hydrogel material of claim 2, wherein the porous structured luminescent hydrogel material comprises,
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.
4. The cellular structured luminescent hydrogel material of claim 1, further comprising, prior to prefreezing, a step of preparing PC comprising:
adding chitosan into acetic acid solution, and stirring at room temperature until the chitosan is fully dissolved;
adding pyridine solution of 2, 3-pyridine dicarboxylic acid anhydride, and stirring thoroughly;
adjusting pH to neutrality with sodium hydroxide solution, and fully reacting;
transferring to a dialysis bag for dialysis;
and (5) evaporating the water after high-speed centrifugation.
5. The luminescent hydrogel material of claim 4, 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 chitosan in the acetic acid solution is 1.5%; and/or
The molar concentration of the pyridine solution of the 2, 3-pyridine dicarboxylic acid anhydride is 0.35-0.6M; and/or
The molar concentration of the sodium hydroxide solution is 2-3M.
6. Use of the porous structure luminescent hydrogel material according to any one of claims 1 to 5 as a fluorescent material.
7. The use of a porous structured luminescent hydrogel material as a fluorescent material according to claim 6, wherein the luminescent hydrogel material is used for the recognition of formaldehyde.
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