CN115301166A - Green luminescent hydrogel material with high mechanical property and preparation and application thereof - Google Patents
Green luminescent hydrogel material with high mechanical property and preparation and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 108
- 239000000017 hydrogel Substances 0.000 title claims abstract description 100
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 68
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 68
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 38
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 36
- 229920001661 Chitosan Polymers 0.000 claims abstract description 34
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-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 22
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 8
- 125000000524 functional group Chemical group 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 72
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 54
- 238000003756 stirring Methods 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 36
- 239000008367 deionised water Substances 0.000 claims description 26
- 229910021641 deionized water Inorganic materials 0.000 claims description 26
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 22
- 238000000502 dialysis Methods 0.000 claims description 18
- 238000007710 freezing Methods 0.000 claims description 16
- 230000008014 freezing Effects 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 238000002791 soaking Methods 0.000 claims description 13
- 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
- -1 rare earth terbium ions Chemical class 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 9
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 238000000354 decomposition reaction Methods 0.000 claims description 5
- 238000010382 chemical cross-linking Methods 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims 26
- 238000010791 quenching Methods 0.000 abstract description 6
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- 238000000295 emission spectrum Methods 0.000 description 6
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- 238000010257 thawing Methods 0.000 description 3
- 150000001217 Terbium Chemical class 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 238000000703 high-speed centrifugation Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
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- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004964 aerogel Substances 0.000 description 1
- 230000009286 beneficial effect Effects 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 green luminous hydrogel material with high mechanical property and preparation and application thereof. The luminescent hydrogel material is PVA/PC/Tb, a rare earth terbium complex formed by PC and Tb is uniformly distributed in a three-dimensional network formed by the PVA and the PC, tb in the rare earth terbium complex is combined with the three-dimensional network through a coordination bond, the PVA is polyvinyl alcohol, the PC is 2, 3-pyridinedicarboxylic acid chitosan, and the Tb is rare earth terbium ion. According to the scheme, PVA and PC are taken as matrixes to form a skeleton network, and a carboxyl functional group of the PC is coordinated with Tb, so that a rare earth terbium complex formed by the coordination of the PC and Tb can be uniformly distributed in the 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 good compressive strain performance, tensile strain performance and thermal stability.
Description
Technical Field
The scheme belongs to the technical field of hydrogel materials, and particularly relates to a green luminescent hydrogel material with high mechanical properties, and preparation and application thereof.
Background
The rare earth terbium complex has excellent luminescence property, so the rare earth terbium complex is widely concerned by scientific researchers. In order for the luminescent terbium complexes to be useful in practice, it is generally necessary to incorporate the terbium complexes into some suitable matrix. The materials such as silicate/rare earth, metal organic framework/rare earth and the like prepared by the traditional method have the defects of complex preparation process, poor water solubility, weak stability and large pollution of decomposition products. In addition, in the rare earth composite material prepared by the traditional method, the mechanical property of the material needs to be further improved. At present, reports on hydrogel composite materials which have excellent stress-strain properties and tensile properties and also have excellent luminescence properties are not common at present.
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 green luminescent hydrogel material with high mechanical properties.
In order to solve the technical problem, the following technical scheme is adopted:
in a first aspect, the green luminescent hydrogel material with high mechanical property is PVA/PC/Tb, a terbium complex formed by PC and Tb is uniformly distributed in a three-dimensional network formed by PVA and PC, tb in the terbium complex is combined with the three-dimensional network through coordination bonds, PVA is polyvinyl alcohol, PC is 2, 3-pyridinedicarboxylic acid chitosan, and Tb is terbium ion.
The scheme takes PC and PVA as substrates, wherein the PC is prepared from natural biomacromolecule chitosan, the PVA is a biodegradable water-soluble high polymer material, and the PVA and the water-soluble high polymer material are both easy to degrade and belong to environment-friendly materials. PVA is combined with PC through hydrogen bonds to form a stable three-dimensional network, namely a hydrogel network framework; then, chemical crosslinking is carried out between PVA and PVA molecular chains in the three-dimensional network, so that the three-dimensional network becomes compact; and finally, tb is combined with a carboxyl functional group of PC in a three-dimensional network by a coordination bond so as to be stably connected with a hydrogel network framework, so that the rare earth terbium complex can be uniformly distributed in the framework network of the matrix, the fluorescence quenching phenomenon of the material prepared by traditional physical doping is avoided, and the green fluorescent material with excellent luminescence is formed.
In a second aspect, a method for preparing the green emitting hydrogel material with high mechanical properties comprises the following steps:
adding PVA into the PC solution, and stirring at 60 ℃ until the PVA is fully dissolved;
adding epoxy chloropropane solution, and fully and uniformly stirring;
adding sodium hydroxide solution, and fully and uniformly stirring;
pouring into a mould, and freezing at-25 ℃;
thawing in water, and washing with large amount of deionized water;
soaking to TbCl 3 In solution, then washed with copious amounts of deionized water.
The scheme adopts a freezing and thawing simple and easy method to prepare a hydrogel material, PVA is added into a PC solution to react, the PVA and the PC solution are combined through hydrogen bonds to form a stable three-dimensional network, epichlorohydrin is used as a cross-linking agent to chemically cross-link PVA molecular chains in the three-dimensional network, the three-dimensional network is more compact to obtain the hydrogel with a network framework, tb is coordinated with a carboxyl functional group of the PC in the three-dimensional network by soaking Tb solution, so that a rare earth terbium complex formed by the PC and Tb is stably connected with the three-dimensional network formed by the PC and PVA, the rare earth terbium complex can be uniformly distributed in the framework 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, 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 requirement, and the preparation method can be applied to other rare earth ion luminescent systems and natural biomacromolecule systems.
In a third aspect, a green emitting hydrogel material with high mechanical properties as described above is used as a fluorescent material. The hydrogel material obtains a green emission spectrum under the excitation of 277nm, the maximum emission peak is at 544nm, the hydrogel material is a pure green fluorescence emission peak of a typical rare earth terbium complex, the color purity is high, and the hydrogel material can be used as a green fluorescent material. The triethylamine-based composite material has excellent identification performance on triethylamine, and can be used as an environment-friendly triethylamine identification material.
This scheme compares with prior art has following beneficial effect:
firstly, PVA and PC are taken as substrates to form a skeleton network, and a carboxyl functional group of the PC is coordinated with Tb, so that a rare earth terbium complex formed by the coordination of the PC and Tb can be uniformly distributed in the 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 the traditional physical doping is avoided.
Secondly, the luminescent hydrogel material has good luminescent property and triethylamine recognition property, a green emission spectrum is obtained under the excitation of 277nm, the maximum emission peak is at 544nm, the luminescent hydrogel material is a pure green fluorescence emission peak of a typical rare earth terbium complex, and the color purity is high.
Furthermore, the luminescent hydrogel material has good compressive strain property, tensile strain property and thermal stability (the decomposition temperature is 215 ℃).
Finally, the method of freezing and melting is used for preparing the luminescent hydrogel material, 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 green emitting hydrogel material with high mechanical properties after drying.
FIG. 2 is a scanning electron microscope image of a green luminescent hydrogel material with high mechanical properties after being dried.
Fig. 3 is a distribution diagram of Tb elements of a green luminescent hydrogel material with high mechanical properties after being dried.
FIG. 4 is a graph of a green emitting hydrogel material with high mechanical properties under UV lamp irradiation.
FIG. 5 shows the excitation and emission spectra of a green emitting hydrogel material with high mechanical properties.
FIG. 6 is a spectrum diagram of the emission light of green luminescent hydrogel material with high mechanical properties after soaking in triethylamine with different concentrations.
FIG. 7 is a stress-strain diagram of a green emitting hydrogel material with high mechanical properties.
FIG. 8 is a graph of tensile stress for green-emitting hydrogel materials with high mechanical properties.
Detailed Description
The scheme provides a green luminescent hydrogel material with high mechanical property, which is PVA/PC/Tb, wherein a rare earth terbium complex is formed by PC and Tb, the PVA and the PC form a three-dimensional network, the rare earth terbium complex is uniformly distributed in the three-dimensional network, tb in the rare earth terbium complex is combined with the three-dimensional network through a coordination bond, the PVA is polyvinyl alcohol, the PC is 2, 3-pyridinedicarboxylic acid chitosan, and the Tb is rare earth terbium ion.
And then Tb is combined with the PC in the three-dimensional network to form the rare earth terbium complex.
Specifically, a carboxyl functional group of PC and Tb are combined by a coordination bond to form the rare earth terbium complex, PVA and PC are connected by a hydrogen bond to form the three-dimensional network, and chemical crosslinking is performed between molecular chains of PVA and PVA by epichlorohydrin.
The scheme takes PC and PVA as substrates, wherein the PC is prepared from natural biomacromolecule chitosan, the PVA is a biodegradable water-soluble high polymer material, and the PVA and the water-soluble high polymer material are both easy to degrade and belong to environment-friendly materials. PVA is combined with PC through hydrogen bonds to form a stable three-dimensional network, namely a hydrogel network framework; then, chemical crosslinking is carried out between PVA and PVA molecular chains in the three-dimensional network, so that the three-dimensional network becomes compact; and finally, the Tb is coordinated with a carboxyl functional group of the PC in the three-dimensional network, so that the Tb is stably connected with the hydrogel network skeleton by a coordination bond, the Tb complex can be uniformly distributed in the skeleton network of the matrix, the fluorescence quenching phenomenon of the material prepared by the traditional physical doping is avoided, and the green fluorescent material with excellent luminescence is formed.
The scheme also provides a preparation method of the green luminescent hydrogel material with high mechanical property, which comprises the following steps:
s1, preparing a PC solution, adding PVA into the PC solution, and stirring at 60 ℃ until the PVA is fully dissolved;
s2, adding an epoxy chloropropane solution, and fully and uniformly stirring;
s3, adding a sodium hydroxide solution, and fully and uniformly stirring;
s4, pouring the mixture into a mold, and then freezing the mixture at the temperature of minus 25 ℃;
s5, unfreezing in water, and washing with a large amount of deionized water;
s6, soaking the fabric into Tb solution, and then washing the fabric with a large amount of deionized water.
The scheme adopts a freezing and thawing simple and easy method to prepare the hydrogel material, PVA is firstly added into a PC solution to react, the PVA and the PC solution are combined through hydrogen bonds to form a stable three-dimensional network, epichlorohydrin is taken as a cross-linking agent to chemically cross-link PVA molecular chains in the three-dimensional network, the three-dimensional network is more compact to obtain the hydrogel with a network framework, tb is coordinated with carboxyl functional groups of PC in the three-dimensional network by soaking Tb solution to form a rare earth terbium complex combined by the coordination bonds of PC and Tb, so that the rare earth terbium complex formed by PC and Tb is stably combined with the three-dimensional network formed by PC and PVA, the rare earth terbium complex can be uniformly distributed in the framework 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, can be processed into different forms according to different requirements, so that the form of the hydrogel material can be conveniently designed according to requirements, and 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 the PC solution is 1.9 to 3.8%, and more preferably 2.0 to 3.0%.
Preferably, in step S1, the mass percentage concentration of PVA in the PC solution is 2 to 12%.
Preferably, in step S2, the volume percentage of epichlorohydrin in the PC solution is 7 to 15%, more preferably 8 to 12%.
Preferably, in step S3, the molar concentration of sodium hydroxide is 0.01 to 0.06M, more preferably 0.02 to 0.04M.
Preferably, in step S4, the freezing time is 12 to 48 hours, more preferably 16 to 40 hours.
Preferably, in step S6, the Tb solution is TbCl 3 The molar concentration of the solution is 0.01 to 0.20M, and more preferably 0.02 to 0.16M.
Further, before step S1, the method further includes the steps of: s0, preparing PC, wherein the preparation comprises the following steps:
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 molar concentration of the pyridine solution of 2, 3-pyridinedicarboxylic acid anhydride is 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 2.9M.
Preferably, in step S03, the reaction time is from 12 to 48 hours, more preferably from 24 to 48 hours.
Further, the preparation method of the green luminescent hydrogel material with high mechanical property comprises the following steps:
s0, preparing 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, adding PVA into the PC solution, and stirring at 60 ℃ until the PVA is fully dissolved;
s2, adding an epoxy chloropropane solution, and fully and uniformly stirring;
s3, adding a sodium hydroxide solution, and fully and uniformly stirring;
s4, pouring the mixture into a mold, and then freezing the mixture at the temperature of minus 25 ℃;
s5, unfreezing in water, and washing with a large amount of deionized water;
s6, soaking the substrate to TbCl 3 In solution, then washed with copious amounts of deionized water.
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 fraction of 2%, adding 50mL 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 mixed solution to pH =7 with sodium hydroxide with molar concentration of 2.0M, fully stirring for 48h, transferring the mixed solution to a dialysis bag for dialysis for one week, taking out, centrifuging at high speed, and evaporating the solution to dryness to obtain 2, 3-pyridine dicarboxylic acid chitosan (PC). PC was dissolved in distilled water to prepare a 1.9% solution, and 0.2g of PVA was addedTo 10mL of a 1.9% by mass PC solution, the mixture was magnetically stirred at 55 ℃ until the PVA was sufficiently dissolved in the PC solution. Cooling, adding 0.7mL of epoxy chloropropane, stirring uniformly, adding a sodium hydroxide solution with the molar concentration of 0.01M, stirring uniformly again, placing the sol in a refrigerator at the temperature of-25 ℃ for freezing for 12h, unfreezing the obtained jelly in deionized water, washing with a large amount of deionized water, and soaking the hydrogel material into 20mL of TbCl with the molar concentration of 0.01M 3 After 24h in solution, the hydrogel was washed with a large amount of deionized water to obtain a luminescent hydrogel material.
Example 2
Dissolving 1.5g of chitosan in 100mL of acetic acid solution with volume fraction of 2.5%, adding 50mL of pyridine solution of 2, 3-pyridine dicarboxylic anhydride with molar concentration of 0.39M into the chitosan acetic acid solution, fully stirring, adjusting the mixed solution to pH =7 with sodium hydroxide with molar concentration of 2.4M, fully stirring for 40h, transferring the mixed solution to a dialysis bag for dialysis for one week, taking out the mixed solution, centrifuging at high speed, and evaporating the solution to dryness to obtain the 2, 3-pyridine dicarboxylic acid chitosan (PC). PC was dissolved in distilled water to prepare a 2.0% solution, 0.4g of PVA was added to 10mL of a 2.0% by mass PC solution, and magnetic stirring was performed at 60 ℃ until the PVA was sufficiently dissolved in the PC solution. Cooling, adding 0.8mL of epoxy chloropropane, stirring uniformly, adding a sodium hydroxide solution with the molar concentration of 0.02M, stirring uniformly again, placing the sol in a refrigerator at the temperature of-25 ℃ for freezing for 16h, unfreezing the obtained jelly in deionized water, washing with a large amount of deionized water, and soaking the hydrogel material into 20mL of TbCl with the molar concentration of 0.02M 3 After 24h in the solution, the hydrogel is washed with a large amount of deionized water, and finally a luminescent hydrogel material is obtained.
Example 3
Dissolving 1.5g chitosan in 100mL of acetic acid solution with volume fraction of 3.0%, adding 50mL of pyridine solution of 2, 3-pyridine dicarboxylic anhydride with molar concentration of 0.42M into the chitosan acetic acid solution, stirring thoroughly, adjusting the mixed solution to pH =7 with sodium hydroxide with molar concentration of 2.9M, stirring thoroughly for 36h, mixing the mixed solutionAnd transferring the solution to a dialysis bag for dialysis for one week, taking out the solution, centrifuging the solution at a high speed, and evaporating the solution to dryness to obtain the 2, 3-pyridinedicarboxylic acid chitosan (PC). Dissolving PC in distilled water to prepare a 2.5% solution, adding 0.65g of PVA into 10mL of the 2.5% mass-fraction PC solution, and magnetically stirring at 60 ℃ until the PVA is fully dissolved in the PC solution. Cooling, adding 1.0mL of epoxy chloropropane, stirring uniformly, adding a sodium hydroxide solution with the molar concentration of 0.03M, stirring uniformly again, placing the sol in a refrigerator at the temperature of-25 ℃ for freezing for 24h, unfreezing the obtained jelly in deionized water, washing with a large amount of deionized water, and soaking the hydrogel material into 20mL of TbCl with the molar concentration of 0.05M 3 After 24h in the solution, the hydrogel is washed with a large amount of deionized water, and finally a luminescent hydrogel material is obtained.
Example 4
Dissolving 1.5g of chitosan in 100mL of acetic acid solution with volume fraction of 3.5%, adding 50mL of pyridine solution of 2, 3-pyridine dicarboxylic anhydride with molar concentration of 0.43M into the chitosan acetic acid solution, fully stirring, adjusting the mixed solution with sodium hydroxide with molar concentration of 2.5M to pH =7, fully stirring for 24h, transferring the mixed solution to a dialysis bag for dialysis for one week, taking out the dialyzed mixed solution, centrifuging at high speed, and evaporating the solution to dryness to obtain 2, 3-pyridine dicarboxylic acid chitosan (PC). PC was dissolved in distilled water to prepare a 3.0% solution, 0.76g of PVA was added to 10mL of a 3.0% by mass PC solution, and magnetic stirring was performed at 60 ℃ until the PVA was sufficiently dissolved in the PC solution. Cooling, adding 1.2mL of epichlorohydrin, stirring uniformly, adding a sodium hydroxide solution with the molar concentration of 0.04M, stirring uniformly again, placing the sol in a refrigerator with the temperature of-25 ℃ for freezing for 32h, unfreezing the obtained jelly in deionized water, washing with a large amount of deionized water, and soaking the hydrogel material into 20mL of TbCl Cl with the molar concentration of 0.1M 3 After 24h in solution, the hydrogel was washed with a large amount of deionized water to obtain a luminescent hydrogel material.
Example 5
Dissolving 1.5g chitosan in 100mL acetic acid solution with volume fraction of 4.5%, adding chitosan acetateThe solution was added with 50mL of a pyridine solution of 2, 3-pyridinedicarboxylic anhydride having a molar concentration of 0.44M, sufficiently stirred, the mixed solution was adjusted to pH =7 with sodium hydroxide having a molar concentration of 2.7M, sufficiently stirred for 18 hours, transferred to a dialysis bag for dialysis for one week, and then centrifuged at high speed, and the solution was evaporated to dryness to obtain 2, 3-pyridinedicarboxylic acid chitosan (PC). Dissolving PC in distilled water to prepare a 3.4% solution, adding 0.85g of PVA into 10mL of the 3.4% mass fraction PC solution, and magnetically stirring at 60 ℃ until the PVA is fully dissolved in the PC solution. Cooling, adding 1.5mL of epoxy chloropropane, stirring uniformly, adding a sodium hydroxide solution with the molar concentration of 0.05M, stirring uniformly again, placing the sol in a refrigerator at the temperature of-25 ℃ for freezing for 40h, unfreezing the obtained jelly in deionized water, washing with a large amount of deionized water, and soaking the hydrogel material into 20mL of TbCl with the molar concentration of 0.16M 3 After 24h in solution, the hydrogel was washed with a large amount of deionized water to obtain a luminescent hydrogel material.
Example 6
Dissolving 1.5g of chitosan in 100mL of acetic acid solution with volume fraction of 5.0%, adding 50mL of pyridine solution of 2, 3-pyridine dicarboxylic anhydride with molar concentration of 0.46M into the chitosan acetic acid solution, fully stirring, adjusting the mixed solution with sodium hydroxide with molar concentration of 3.0M to pH =7, fully stirring for 12h, transferring the mixed solution to a dialysis bag for dialysis for one week, taking out the dialyzed mixed solution, centrifuging at high speed, and evaporating the solution to dryness to obtain 2, 3-pyridine dicarboxylic acid chitosan (PC). Dissolving PC in distilled water to prepare a 3.8% solution, adding 1.2g of PVA into 10mL of the 3.8% mass-fraction PC solution, and magnetically stirring at 60 ℃ until the PVA is fully dissolved in the PC solution. Cooling, adding 1.5mL of epichlorohydrin, stirring uniformly, adding a sodium hydroxide solution with the molar concentration of 0.06M, stirring uniformly again, placing the sol in a refrigerator with the temperature of-25 ℃ for freezing for 48h, unfreezing the obtained jelly in deionized water, washing with a large amount of deionized water, and soaking the hydrogel material into 20mL of TbCl Cl with the molar concentration of 0.2M 3 After 24h in solution, the hydrogel was washed with copious amounts of deionized water to yieldA luminescent hydrogel material.
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 freeze-drying, from which it can be seen that the material has good thermal stability and the decomposition temperature is 215 ℃.
(II) morphology of luminescent hydrogel
In order to determine the morphology of the hydrogel, a hydrogel sample was obtained using a freeze-drying technique. The aerogel is observed in a section by using a field emission scanning electron microscope, and as can be seen from fig. 2, the inside of the material may have a micropore or mesopore structure.
In order to determine the distribution of rare earth terbium ions, a distribution diagram of terbium elements is obtained by using a surface scanning technology, and the uniform distribution of the terbium elements in the material can be found from fig. 3, so that the uniform distribution of the rare earth terbium complexes in the biomacromolecule network framework is proved.
(III) fluorescence Properties of luminescent hydrogel Material
FIG. 4 is a graph of hydrogel material under UV lamp irradiation, and from FIG. 4, it can be seen that the hydrogel emits pure green light under UV lamp irradiation.
FIG. 5 shows the excitation and emission spectra of the hydrogel, and it can be seen from FIG. 5 that no 4f to 4f transition of terbium rare earth ion is found in the excitation spectrum, indicating that the energy transfer is performed by chitosan 2, 3-pyridinedicarboxylate with high transfer efficiency, thereby indirectly demonstrating that chitosan 2, 3-pyridinedicarboxylate forms a complex with terbium rare earth ion. It can be seen from FIG. 5 that the emission spectrum obtained with 277nm excitation has a maximum emission peak at 544nm, which is the green emission peak of a typical rare earth terbium ion. The obtained material has high color purity and good monochromaticity.
Triethylamine identification performance of (IV) luminous hydrogel material
FIG. 6 is a fluorescence spectrum of the luminescent hydrogel material after being soaked in triethylamine solutions with different concentrations, from which it can be found that the fluorescence intensity of the hydrogel gradually decreases with the increase of the triethylamine concentration, showing that the luminescent hydrogel has excellent identification performance for triethylamine.
(V) mechanical properties of luminescent hydrogel material
FIG. 7 is a stress-strain diagram of a luminescent hydrogel material, from which it can be seen that the hydrogel material gradually recovers after being compressed to various degrees after the pressure is released, showing good shape memory properties.
FIG. 8 is a graph of tensile stress of a luminescent hydrogel material, from which it can be seen that the stress strain of the hydrogel is large and good tensile properties are exhibited after the hydrogel material is straightened to break.
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, the hydrogel material has a decomposition temperature of 215 ℃, and exhibits excellent stress-strain function and tensile function, which indicates that the obtained luminescent hydrogel material is a hydrogel material with high mechanical properties. The fluorescent material has excellent luminescence, obtains a green emission spectrum under the excitation of 277nm, has a maximum emission peak at 544nm, is a pure green fluorescence emission peak of a typical rare earth terbium complex, has high color purity, and can be applied as a green fluorescent material. The fluorescent material can be applied to triethylamine recognition.
Based on the scheme, the application of the green luminescent hydrogel material with high mechanical property as a fluorescent material is also provided, and the green luminescent hydrogel material is particularly suitable for identifying triethylamine.
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. This need not be, nor should it be 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 green luminescent hydrogel material with high mechanical property is characterized by being PVA/PC/Tb, a rare earth terbium complex formed by PC and Tb is uniformly distributed in a three-dimensional network formed by PVA and PC, tb in the rare earth terbium complex is combined with the three-dimensional network through coordination bonds, PVA is polyvinyl alcohol, PC is 2, 3-pyridinedicarboxylic acid chitosan, and Tb is rare earth terbium ions.
2. The green emitting hydrogel material with high mechanical properties of claim 1, wherein the PVA combines with PC to form the three-dimensional network, and then Tb combines with PC in the three-dimensional network to form the rare earth terbium complex.
3. Green emitting hydrogel material with high mechanical properties according to claim 2, characterized in that,
the carboxyl functional group of the PC is combined with Tb by a coordination bond to form the rare earth terbium complex; and/or the presence of a gas in the atmosphere,
the PVA is connected with the PC through a hydrogen bond to form the three-dimensional network; and/or the presence of a gas in the gas,
chemical crosslinking is carried out between the PVA and the PVA molecular chain through epoxy chloropropane; and/or the presence of a gas in the gas,
the decomposition temperature of the hydrogel material was 215 ℃.
4. A method for preparing a green emitting hydrogel material with high mechanical properties according to any one of claims 1 to 3, comprising the steps of:
preparing a PC solution, adding PVA into the PC solution, and stirring at 60 ℃ until the PVA is fully dissolved;
adding epoxy chloropropane solution, and fully and uniformly stirring;
adding sodium hydroxide solution, and fully and uniformly stirring;
pouring into a mold, and freezing at-25 deg.C;
unfreezing in water, and washing with a large amount of deionized water;
soaking in TbCl 3 In solution, then washed with copious amounts of deionized water.
5. The method for preparing green emitting hydrogel material with high mechanical properties according to claim 4,
the mass percentage concentration of the PC solution is 1.9-3.8%; and/or the presence of a gas in the gas,
the mass percentage concentration of the PVA in the PC solution is 2-12%; and/or the presence of a gas in the gas,
the volume percentage of the epichlorohydrin in the PC solution is 7-15%; and/or the presence of a gas in the gas,
the molar concentration of the sodium hydroxide is 0.01-0.06M; and/or the presence of a gas in the gas,
the freezing time is 12-48 h; and/or the presence of a gas in the gas,
the Tb solution is TbCl 3 The molar concentration of the solution is 0.01-0.20M.
6. The method for preparing a green emitting hydrogel material with high mechanical properties according to claim 5, characterized in that,
the mass percentage concentration of the PC solution is 2.0-3.0%; and/or the presence of a gas in the gas,
the volume percentage of the epichlorohydrin in the PC solution is 8-12%; and/or the presence of a gas in the atmosphere,
the molar concentration of the sodium hydroxide is 0.02-0.04M; and/or the presence of a gas in the atmosphere,
the freezing time is 16-40 h; and/or the presence of a gas in the gas,
the molar concentration of Tb solution is 0.02-0.16M.
7. The method for preparing a green emitting hydrogel material with high mechanical properties as claimed in claim 4, further comprising a step of preparing PC before adding PVA into the PC solution, which comprises:
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 anhydride, 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 green emitting hydrogel material with high mechanical properties according to claim 7, characterized in that,
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 atmosphere,
the molar concentration of the pyridine solution of the 2, 3-pyridine dicarboxylic anhydride 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
The reaction time is 12-48 h.
9. Use of a green-emitting hydrogel material with high mechanical properties according to any of claims 1 to 3 or a green-emitting hydrogel material with high mechanical properties prepared by a method according to any of claims 4 to 8 as a fluorescent material.
10. Use of a green emitting hydrogel material with high mechanical properties as a fluorescent material according to claim 9, wherein the green emitting hydrogel material is used to identify triethylamine.
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| 焦剑等: "《功能高分子材料》", 西安：西北工业大学出版社, pages: 259 * |
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