Preparation method of lanthanide series luminescent hydrogel film

Abstract

The application belongs to the technical field of supramolecular luminescent hydrogel, and particularly relates to a preparation method of lanthanide series luminescent hydrogel film. The raw materials used in the application have low cost, good repeatability and simple preparation steps; the lanthanide series luminescent hydrogel film obtained by the application has lanthanide ion characteristic fluorescence and response characteristics to external temperature stimulation, can be used for temperature assembly sensors; and the high mechanical strength of the lanthanide series luminescent hydrogel film can also be applied to the fields of cell culture, dressings and tissue engineering.

Description

Technical Field

[0001] This invention belongs to the field of supramolecular luminescent hydrogel technology, specifically relating to a method for preparing a lanthanide luminescent hydrogel film. Background Technology

[0002] Supramolecular hydrogels, constructed based on non-covalent interactions, possess unique dynamic response properties and are widely used in tissue engineering, sensing, and the assembly of intelligent actuators. Lanthanide luminescent materials, with their long fluorescence lifetime, high quantum yield, and excellent physicochemical properties, have attracted considerable attention in the assembly of optical devices, detection and diagnostics, and cell culture. Combining the excellent photophysical properties of lanthanide ions with supramolecular hydrogels endows materials with stable optical properties and unique dynamic responsiveness, greatly expanding their application range. However, most lanthanide-based supramolecular hydrogel systems are derived from synthetic molecules or small biomolecules, resulting in cumbersome preparation processes and poor mechanical strength, limiting their practical applications in the biomedical field.

[0003] Thin-film temperature sensors are widely used in aerospace, medical, and other fields. Currently, most developed thin-film temperature sensors are assembled using precious metals such as platinum, which suffers from drawbacks such as insensitive temperature response and high cost. Therefore, developing a temperature sensor with high responsiveness, high accuracy, wearability, and low cost is an urgent problem to be solved. Summary of the Invention

[0004] The purpose of this invention is to provide a method for preparing luminescent hydrogel films that is simple to prepare and has good mechanical strength, in order to address the problems existing in the prior art.

[0005] The present invention provides a method for preparing a lanthanide luminescent hydrogel film, comprising the following steps: Step 1: Prepare a soluble lanthanide ion hydrochloride aqueous solution with a mass concentration of 1%-10%, and prepare an amino acid aqueous solution with a mass concentration of 1%-10%. Step 2: Disperse hydroxypropyl cellulose and polyethylene glycol in dimethyl sulfoxide, add deionized water and heat to 80-90℃ to dissolve, to obtain solution A with a mass concentration of 2%-5%.

[0006] Step 3: Add the soluble lanthanide ion hydrochloride aqueous solution and amino acid aqueous solution obtained in Step 1 to solution A in Step 2 and mix them evenly to obtain solution B. Adjust the pH of solution B to 7-9. Pour solution B into a mold and perform a freeze-thaw process: cool solution B to room temperature and let it stand for 2 hours, freeze it at -20℃ for 8-12 hours, and let it stand at room temperature for 3 hours. Repeat the freeze-thaw process 3-5 times to obtain a lanthanide luminescent gel film.

[0007] Preferably, in step three, the volume ratio of the soluble lanthanide ion hydrochloride aqueous solution, the amino acid aqueous solution, and solution A is 1:1:4. Preferably, the soluble lanthanide hydrochloride used to prepare the aqueous solution of the soluble lanthanide ion hydrochloride is TbCl3·6H2O or EuCl3·6H2O; Preferably, the amino acid used to prepare the amino acid aqueous solution is L(D)-alanine, L(D)-serine, L(D)-histidine, or L(D)-proline.

[0008] The present invention has the following beneficial effects: The raw materials used in this invention are inexpensive, highly reproducible, and the preparation steps are simple. The lanthanide luminescent hydrogel film obtained by this invention has the characteristic fluorescence of lanthanide ions and responds to external temperature stimuli, and can be used for temperature-equipped sensors. Its high mechanical strength can also be applied to cell culture, dressings, and tissue engineering. Attached Figure Description

[0009] Figure 1 This is a photograph of the lanthanide luminescent hydrogel film prepared in Example 1 under fluorescent light. Figure 2 This is a photograph of the lanthanide luminescent hydrogel film prepared in Example 1 under ultraviolet light irradiation; Figure 3 This is the fluorescence emission spectrum of the lanthanide luminescent hydrogel film prepared in Example 1; Figure 4 This is a rheological curve of the lanthanide luminescent hydrogel film prepared in Example 1; Figure 5 The image shows the emission spectrum of the lanthanide luminescent hydrogel film used as a temperature sensor in Example 1 in response to temperature. Detailed Implementation

[0010] Example 1 A method for preparing a lanthanide luminescent hydrogel film includes the following steps: Step 1: Prepare a 1% (w / w) TbCl3·6H2O aqueous solution and a 1% (w / w) L-alanine aqueous solution. Step 2: Disperse hydroxypropyl cellulose and polyethylene glycol in dimethyl sulfoxide, add deionized water and heat to 80°C to dissolve, to obtain solution A with a mass concentration of 2%.

[0011] Step 3: Add the TbCl3·6H2O aqueous solution and L-alanine aqueous solution obtained in Step 1 to solution A in Step 2 and mix thoroughly to obtain solution B. The volume ratio of the TbCl3·6H2O aqueous solution, L-alanine aqueous solution and solution A is 1:1:4. Add dilute ammonia to solution B to adjust its pH value to 7. Pour solution B into a mold and perform a freeze-thaw process: cool to room temperature for 2 hours, freeze at -20℃ for 8 hours, and place at room temperature for 3 hours. Repeat the above freeze-thaw process 3 times to obtain a lanthanide luminescent gel film.

[0012] Depend on Figure 1 It can be seen that the lanthanide luminescent gel film obtained in Example 1 is transparent and colorless under fluorescent light; Depend on Figure 2 It can be seen that the lanthanide luminescent gel film obtained in Example 1 exhibits fluorescent green color under ultraviolet light irradiation; Figure 3 The rheological curve of the lanthanide luminescent gel film obtained in Example 1 shows that the lanthanide luminescent gel film exhibits terbium ion characteristic fluorescence and good photophysical properties, which increases the application value of the lanthanide luminescent hydrogel film.

[0013] Figure 3 The rheological curve of the lanthanide luminescent gel film obtained in Example 1 shows that the obtained lanthanide luminescent gel film has strong mechanical properties, further enhancing the practical application value of the lanthanide luminescent hydrogel film.

[0014] The lanthanide luminescent gel film obtained in Example 1 was placed in an environment of -20°C, such as... Figure 5 As shown, the fluorescence intensity of the hydrogel weakens, indicating that the lanthanide luminescent hydrogel film has a fluorescence response to low temperature. Taking advantage of its response to external low temperature stimuli, the hydrogel can be used for the assembly of a low-temperature fluorescence sensor.

[0015] The lanthanide luminescent gel film obtained in Example 1 was placed in an environment at 65°C, such as... Figure 5 The fluorescence intensity of the hydrogel shown is reduced. The rare earth nucleoside white light hydrogel has a fluorescence response to high temperature. Taking advantage of its response to external high temperature stimuli, the hydrogel is used for the assembly of a high temperature fluorescence sensor.

[0016] The lanthanide luminescent gel film obtained in Example 1 was placed in an environment of 25°C, and then the temperature was increased every 10°C, such as... Figure 5 As shown, the fluorescence intensity of the hydrogel gradually decreases with increasing temperature; this indicates that the lanthanide luminescent hydrogel film is extremely sensitive to temperature stimulation and can be used for the assembly of temperature-sensitive fluorescence sensors.

[0017] Example 2 A method for preparing a lanthanide luminescent hydrogel film includes the following steps: Step 1: Prepare a 3% (w / w) TbCl3·6H2O aqueous solution and a 3% (w / w) D-alanine aqueous solution. Step 2: Disperse hydroxypropyl cellulose and polyethylene glycol in dimethyl sulfoxide, add deionized water and heat to 85°C to dissolve, to obtain solution A with a mass concentration of 3%.

[0018] Step 3: Add the TbCl3·6H2O aqueous solution and D-alanine aqueous solution obtained in Step 1 to solution A in Step 2 and mix thoroughly to obtain solution B. 3· The volume ratio of 6H2O aqueous solution, D-alanine aqueous solution and solution A is 1:1:4; dilute ammonia is added to solution B to adjust its pH value to 7; solution B is poured into a mold and subjected to a freeze-thaw process: cooled to room temperature for 2 hours, frozen at -20℃ for 10 hours, and placed at room temperature for 3 hours; the above freeze-thaw process is repeated 4 times to obtain a lanthanide luminescent gel film.

[0019] The lanthanide luminescent hydrogel film obtained in Exercise 2 is colorless and transparent under fluorescent light.

[0020] The lanthanide luminescent hydrogel film obtained in Experiment 2 exhibits green fluorescence, indicating that it has good photophysical properties.

[0021] Example 3 A method for preparing a lanthanide luminescent hydrogel film includes the following steps: Step 1: Prepare a 10% (w / w) EuCl3·6H2O aqueous solution and a 10% (w / w) D-alanine aqueous solution. Step 2: Disperse hydroxypropyl cellulose and polyethylene glycol in dimethyl sulfoxide, add deionized water and heat to 90°C to dissolve, to obtain solution A with a mass concentration of 3%.

[0022] Step 3: Add the EuCl3·6H2O aqueous solution and D-alanine aqueous solution obtained in Step 1 to the A solution in Step 2 and mix thoroughly to obtain the B solution. The volume ratio of the EuCl3·6H2O aqueous solution, D-alanine aqueous solution and A solution is 1:1:4. Add dilute ammonia to the B solution to adjust its pH value to 7. Spread the B solution into a mold and perform a freeze-thaw process: cool to room temperature for 2 hours, freeze at -20℃ for 12 hours, and place at room temperature for 3 hours. Repeat the above freeze-thaw process 5 times to obtain the lanthanide luminescent gel membrane.

[0023] The lanthanide luminescent hydrogel film obtained in Exercise 3 is colorless and transparent under fluorescent light.

[0024] The lanthanide luminescent hydrogel film obtained in Experiment 3 exhibits red fluorescence, indicating its excellent photophysical properties and further enhancing the practical application value of rare earth nucleoside white light hydrogels.

[0025] Example 4 A method for preparing a lanthanide luminescent hydrogel film includes the following steps: By replacing L-alanine in Example 1 with L-serine, and following the same preparation steps as in Example 1, a lanthanide luminescent hydrogel film was obtained.

[0026] The lanthanide luminescent hydrogel film obtained in Example 4 is transparent and colorless under fluorescent light; The lanthanide luminescent hydrogel film obtained in Example 4 exhibits green fluorescence.

[0027] Example 5 A method for preparing a lanthanide luminescent hydrogel film includes the following steps: By replacing L-alanine in Example 1 with D-serine, and following the same preparation steps as in Example 1, a lanthanide luminescent hydrogel film was obtained.

[0028] The lanthanide luminescent hydrogel film obtained in Example 5 is transparent and colorless under fluorescent light; The lanthanide luminescent hydrogel film obtained in Example 5 exhibits green fluorescence.

[0029] Example 6 A method for preparing a lanthanide luminescent hydrogel film includes the following steps: By replacing D-alanine in Example 2 with L-histidine, and following the same preparation steps as in Example 2, a lanthanide luminescent hydrogel film was obtained.

[0030] The lanthanide luminescent hydrogel film obtained in Example 6 is transparent and colorless under fluorescent light; The lanthanide luminescent hydrogel film obtained in Example 6 exhibits green fluorescence.

[0031] Example 7 A method for preparing a lanthanide luminescent hydrogel film includes the following steps: By replacing D-alanine in Example 3 with D-histidine, and following the same preparation steps as in Example 3, a lanthanide luminescent hydrogel film was obtained.

[0032] The lanthanide luminescent hydrogel film obtained in Example 7 is transparent and colorless under fluorescent light; The lanthanide luminescent hydrogel film obtained in Example 7 exhibits red fluorescence.

[0033] Example 8 A method for preparing a lanthanide luminescent hydrogel film includes the following steps: By replacing D-alanine in Example 3 with L-proline, and following the same preparation steps as in Example 3, a lanthanide luminescent hydrogel film was obtained.

[0034] The lanthanide luminescent hydrogel film obtained in Example 8 is transparent and colorless under fluorescent light; The lanthanide luminescent hydrogel film obtained in Example 8 exhibits red fluorescence.

[0035] Example 9 A method for preparing a lanthanide luminescent hydrogel film includes the following steps: By replacing D-alanine in Example 3 with D-proline, and following the same preparation steps as in Example 3, a lanthanide luminescent hydrogel film was obtained.

[0036] The lanthanide luminescent hydrogel film obtained in Example 9 is transparent and colorless under fluorescent light; The lanthanide luminescent hydrogel film obtained in Example 9 exhibits red fluorescence.

Claims

1. A method for preparing a lanthanide luminescent hydrogel film, characterized in that, Includes the following steps: Step 1: Prepare a 1%-10% (w / w) soluble lanthanide hydrochloride aqueous solution and a 1%-10% (w / w) amino acid aqueous solution. Step 2: Disperse hydroxypropyl cellulose and polyethylene glycol in dimethyl sulfoxide, add deionized water, and heat to 80-90℃ to dissolve, obtaining a 2%-5% (w / w) solution A. Step 3: Add the soluble lanthanide hydrochloride aqueous solution and amino acid aqueous solution obtained in Step 1 to solution A in Step 2 and mix thoroughly to obtain solution B. Adjust the pH of solution B to 7-9. Pour solution B into a mold and perform a freeze-thaw cycle: cool solution B to room temperature and let it stand for 2 hours, freeze at -20℃ for 8-12 hours, and place at room temperature for 3 hours. Repeat the freeze-thaw cycle 3-5 times to obtain a lanthanide luminescent gel membrane. The volume ratio of the soluble lanthanide hydrochloride aqueous solution, amino acid aqueous solution, and solution A is 1:1:

4. The soluble lanthanide ion hydrochloride used to prepare the aqueous solution of the soluble lanthanide ion hydrochloride is TbCl3·6H2O or EuCl3·6H2O; The amino acids used to prepare the amino acid aqueous solution are L-alanine, D-alanine, L-serine, D-serine, L-histidine, D-histidine, L-proline, or D-proline.

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