CN114560968A - Ultrasonic response type high-molecular fluorescent hydrogel material, preparation method and application - Google Patents
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Abstract
The invention discloses a preparation method of an ultrasonic response type high-molecular fluorescent hydrogel material with both visualization and morphological stability, which comprises the following steps: (1) adding a gel-forming monomer, a fluorescent response molecule, a cross-linking agent and a free radical thermal initiator into an organic solvent, completely dissolving to obtain a gel pre-polymerization liquid A, and polymerizing the gel pre-polymerization liquid A into gel to obtain a fluorescent oil gel B; (2) soaking the fluorescent hydrogel B in water, and replacing the solvent to obtain a fluorescent hydrogel C; (3) and (3) soaking the fluorescent hydrogel C in a salt solution containing lanthanide metal ions for coordination, taking out and drying to obtain the ultrasonic response type macromolecular fluorescent hydrogel material. The ultrasonic response type high molecular fluorescent hydrogel material prepared by the method has the advantages of visualization, high contrast ratio and good stability, and has wide application prospects in the fields of diagnosis and treatment imaging, nondestructive inspection and the like.
Description
Technical Field
The invention relates to the field of ultrasonic response type gel, in particular to an ultrasonic response type high-molecular fluorescent hydrogel material with both visualization and morphological stability, a preparation method and application.
Background
Ultrasonic sensing materials based on piezoelectric materials (ceramics and inorganic titanates), magnetic materials (iron-vanadium-cobalt alloys and ferrites containing zinc and nickel) and the like have been developed and widely applied, for example, Chinese patent publication No. CN110257142A discloses an ultrasonic response type boron nitride nano gel lubricating material which is obtained by mixing urea-based modified boron nitride two-dimensional nanosheets as gel factors in a dispersion liquid with base oil and performing ultrasonic treatment. The gel lubricating material has special ultrasonic response gelling property, and can form a stable gel structure under the mild condition below 60 ℃ under the action of ultrasonic waves.
However, the above-mentioned ultrasound sensing material is difficult to convert an ultrasound signal into a visual signal visible to the naked eye. It is worth mentioning that the visualized conversion of the ultrasonic signals is beneficial to the miniaturization of related instruments (such as B-ultrasonic and flaw detectors), the improvement of the information processing efficiency and the like. However, how to convert the received ultrasonic signals into visualized signals remains a problem to be solved by the current technology .
The ultrasonic response type polymer gel material can convert an ultrasonic signal into a photophysical signal visible to naked eyes, and visual display of the ultrasonic signal is realized. Holten-Andersen et al reported an ultrasound-Responsive gel material whose fluorescence color could be changed from White to Light blue (White-Light-Emitting blue metals with fluorescent Luminescence and Reversible Stimuli-Responsive properties. J.Am.chem.Soc.2015,137, 11590). Hodgkin et al reported that polymeric fluorescent hydrogel materials undergo a reversible change from red to pale red upon sonication (Dynamic Coordination of Eu-Iminodizate to Control fluorescent Response of Polymer Hydrogels to Multi stimuli.Adv.Mater.2018,30,1706526). These reported ultrasound-responsive fluorescent gel materials indicate the possibility of converting an ultrasound signal into a fluorescence signal visible to the naked eye, and have the advantages of good biocompatibility, high transparency and the like. However, these materials undergo sol transformation in response to ultrasound, are unstable in morphology, and are difficult to meet the requirements of further applications.
Disclosure of Invention
The invention provides a preparation method of an ultrasonic response type high-molecular fluorescent hydrogel material with both visualization and morphological stability, and the prepared ultrasonic response type high-molecular fluorescent hydrogel material has the advantages of visualization, high contrast and good stability, and has wide application prospects in the fields of diagnosis and treatment imaging, nondestructive inspection and the like.
The technical scheme is as follows:
a preparation method of an ultrasonic response type high molecular fluorescent hydrogel material comprises the following steps:
(1) adding a gel-forming monomer, a fluorescent response molecule, a cross-linking agent and a free radical thermal initiator into an organic solvent, completely dissolving to obtain a gel pre-polymerization liquid A, and polymerizing the gel pre-polymerization liquid A into gel to obtain a fluorescent oil gel B;
(2) soaking the fluorescent hydrogel B in water, and replacing the solvent to obtain a fluorescent hydrogel C;
(3) and (3) soaking the fluorescent hydrogel C in a salt solution containing lanthanide metal ions for coordination, taking out and drying to obtain the ultrasonic response type macromolecular fluorescent hydrogel material.
The gel-forming monomer comprises an acrylamide monomer and a terpyridine functional monomer, wherein the structural formula of the terpyridine functional monomer is shown as a formula (I):
preferably, the acrylamide monomer comprises acrylamide or N-methylol acrylamide.
Preferably, the structural formula of the fluorescence response molecule is shown as formula (II):
according to the invention, an acrylamide monomer and a terpyridine functional monomer are used as gel forming monomers, the acrylamide monomer and the terpyridine functional monomer (the terpyridine functional monomer can be coordinated with lanthanide metal ions) can be copolymerized to form a three-dimensional polymer network, and fluorescence response molecules with a specific structure are doped, and the introduction of an ultrasonic response element is realized by regulating the type of the lanthanide metal ions and the content of the fluorescence response molecules, so that an ultrasonic response type high-molecular fluorescent hydrogel material is prepared; under the action of ultrasound, weak coordination bonds formed by terpyridine and lanthanide metal ions are dissociated, and fluorescence response molecules gradually capture the dissociated lanthanide metal ions to form a more stable complex, so that the fluorescence color emitted by the hydrogel material is changed.
Preferably, the cross-linking agent is N, N' -methylene bisacrylamide; the free radical thermal initiator is azobisisobutyronitrile; the organic solvent comprises dimethyl sulfoxide or dimethylformamide.
Preferably, the addition amount of the acrylamide monomer is 18-25 wt% of the total weight of the organic solvent;
the weight ratio of the acrylamide monomer, the terpyridine functionalized monomer, the cross-linking agent, the fluorescent response molecule and the free radical thermal initiator is 100: 0.6-0.8: 0.4-1.1: 0.012-0.07: 0.07-0.1.
Preferably, the polymerization glue forming mode of the step (1) is as follows: putting the gel pre-polymerization liquid A into an oven at the temperature of 60-70 ℃, and gelling and polymerizing for 6-10 hours.
Preferably, in the step (3), the salt solution containing lanthanide metal ions is any one of lanthanum nitrate, europium nitrate and terbium nitrate, and the concentration is 0.1-0.5M.
The invention also provides an ultrasonic response type high molecular fluorescent hydrogel material with both visualization and morphological stability, which is prepared by the preparation method of the ultrasonic response type high molecular fluorescent hydrogel material.
In the current research, the ultrasound response material is mostly based on piezoelectric materials such as titanate, and when the ultrasound response material is displayed in an imaging mode, an ultrasound signal needs to be converted into a current signal, and a corresponding image is further simulated through a complex data processing system. Different from the ultrasonic response materials, the ultrasonic response type macromolecular fluorescent hydrogel material can convert an ultrasonic signal into a fluorescent signal which can be seen by naked eyes.
The invention also provides application of the ultrasonic response type high molecular fluorescent hydrogel material in the fields of ultrasonic diagnosis and treatment, imaging and industrial nondestructive inspection.
The ultrasonic response type high molecular fluorescent hydrogel material has the advantages of visualization, high contrast, good stability and the like, and has wide application prospects in the fields of ultrasonic diagnosis and treatment, imaging, industrial nondestructive inspection and the like.
Compared with the prior art, the invention has the beneficial effects that:
(1) the ultrasonic response type high-molecular fluorescent hydrogel material can convert an ultrasonic signal into a macroscopic fluorescent signal, and realizes the in-situ visualization of the ultrasonic signal.
(2) The lanthanide series metal is rich in selection, and the ultrasonic response type high molecular fluorescent hydrogel material constructed by the coordination of different lanthanide series metal ions shows different fluorescence changes during imaging.
(3) The ultrasonic response type high molecular fluorescent hydrogel material prepared by the invention has the advantages of visualization (visible by naked eyes), high contrast (yellow to red fluorescence change), good stability (can stand 300W ultrasonic for 10h, and does not generate sol conversion), and the like.
(4) The preparation method is simple, has low equipment requirement and is easy for industrial production.
Drawings
Fig. 1 is a synthetic route of a terpyridine functionalized monomer and a fluorescence response molecule used in the examples, wherein (a) is a synthetic route of the terpyridine functionalized monomer, and (b) is a synthetic route of the fluorescence response molecule.
FIG. 2 is a synthesis route diagram of the ultrasound-responsive polymer fluorescent hydrogel material.
FIG. 3 is an SEM picture of the ultrasound-responsive polymer fluorescent hydrogel material prepared in example 1.
FIG. 4 is a graph of fluorescence emission spectra with time and (b) a graph of chromaticity coordinate value changes of the ultrasound responsive polymeric fluorescent hydrogel material prepared in example 1 under the ultrasound stimulation.
FIG. 5 is a graph showing the change of the ratio of fluorescence emission intensities at 500nm and 615nm of the ultrasound-responsive polymer fluorescent hydrogel materials prepared in examples 1-3 under the action of ultrasound.
FIG. 6 is an optical photograph of the hydrogel of example 1 under a 254nm UV lamp.
FIG. 7 is the IR spectrum analysis before and after the ultrasound effect of the ultrasound-responsive polymer fluorescent hydrogel material prepared in example 1.
FIG. 8 is a photoelectron spectroscopy analysis chart of europium element before and after the ultrasonic action of the ultrasound-responsive polymeric fluorescent hydrogel material prepared in example 1, in which (a) is Eu 3d, and (b) is Eu 4 d.
Detailed Description
The invention is further elucidated with reference to the figures and the examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
In the embodiment of the invention, the structural formula of the terpyridine functionalized monomer is as follows:
the Terpyridine Functionalized monomer is synthesized by two-step nucleophilic substitution reaction according to reported literature (reforming the Supramolecular Nature of Side-Chain Terpylidine-Functionalized Polymer Networks, int.J.mol.Sci.2015,16, 990-.
The structural formula of the adopted fluorescence response molecule is as follows:
the synthetic route of the fluorescence response molecule is shown in (b) of fig. 1.
1. Intermediate 2 (double Synthesis of Novel Bisterpyridines via Suzuki-Type Cross-coupling.org.Lett.,2007,9,559) and intermediate 3 (Metal-Organic-Framework-Assisted In Vivo Bacterial Metabolic laboratory and Precise antibiotic therapy.adv.Mater.2018,30,1706831) were synthesized separately with reference to the reported literature.
2. Intermediate 2(395mg,0.82mmol,0.45equiv.), intermediate 3(1.0g,1.82mmol,1.0equiv.), Pd (PPh)3)4(47mg, 41. mu. mol) and K2CO3(566mg,4.1mmol) was charged in a 100mL Schlenk flask containing magnetons, and 21mL of toluene, 21mL of distilled water, and 7mL of t-butanol were injected under a nitrogen atmosphere, followed by reaction in an oil bath at 85 ℃ for 24 hours. After the reaction was completed, it was extracted with 100mL and 50mL of distilled water, the organic phase was spin-dried, and further subjected to column chromatography on neutral aluminum dioxide (gradient elution, eluent: petroleum ether/dichloromethane: 5/1-1/1) to obtain a bright yellow fluorescent responsive molecule in a yield of 42%.
Example 1
In this embodiment, a synthetic route map of the ultrasound-responsive polymer fluorescent hydrogel material is shown in fig. 2.
Adding 1.5g of acrylamide (AAm), 10mg of the terpyridine functionalized monomer, 1mg of the fluorescence response molecule, 15mg of N, N' -Methylene Bisacrylamide (MBAA) and 1.2mg of Azobisisobutyronitrile (AIBN) into 6.2mL of dimethyl sulfoxide, and oscillating and dissolving to obtain a transparent and uniform gel pre-polymerization liquid A;
injecting the gel pre-polymerization liquid A into a mold with the thickness of 1mm at room temperature, and then transferring the gel pre-polymerization liquid A into a 60 ℃ drying oven to polymerize a synthetic gel for 6 hours to obtain an oleogel B;
transferring the oleogel B into 15mL of deionized water to be soaked for 20min, and performing solvent replacement for three times to obtain a fluorescent hydrogel C;
and finally, soaking the fluorescent hydrogel C in 0.1M europium nitrate solution for coordination for 15min, taking out the hydrogel after coordination is finished, and thoroughly washing non-coordinated europium ions by using 50mL of deionized water to obtain the ultrasonic response type high-molecular fluorescent hydrogel material.
Testing the ultrasonic response type polymer fluorescent hydrogel material prepared by the embodiment, wherein an SEM picture of the ultrasonic response type polymer fluorescent hydrogel material after freeze drying treatment is shown in figure 3 and has a microscopic porous cross-linked network structure; as shown in fig. 4 (a), under the action of ultrasound, the fluorescence intensity of the ultrasound-responsive polymer fluorescent hydrogel material at 500nm (fluorescence emission of the fluorescence-responsive molecule) gradually decreases until reaching an equilibrium state after being subjected to ultrasound for about 45 minutes; as shown in FIG. 4 (b), the fluorescence chromaticity coordinate value of the ultrasound-responsive polymer fluorescent hydrogel material changes from (0.35, 0.44) before ultrasound to (0.52, 0.37) in an equilibrium state under the action of ultrasound, and the display material has good visualization and high contrast performance.
As shown in fig. 5, when the ultrasound-responsive polymer fluorescent hydrogel material prepared in example 1 is subjected to ultrasound, the ratio of fluorescence intensities at 500nm and 615nm gradually decreases until reaching an equilibrium state after ultrasound for about 45 minutes, so that a significant fluorescence color change occurs. Meanwhile, the hydrogel material always keeps a stable form in the ultrasonic process, and has good stability; the fluorescent color before ultrasound was light yellow, while the fluorescent color after ultrasound exposure was orange, showing its ability to visualize ultrasound signals and having high contrast.
Fig. 6 is an optical image of the hydrogel prepared in this example under an ultraviolet lamp of 254nm, in which the left side is a fluorescent hydrogel C, the middle is an ultrasound-responsive fluorescent hydrogel material, and the rightmost side is an ultrasound-responsive fluorescent hydrogel material that reaches an equilibrium state after being subjected to ultrasound. Before and after the ultrasonic treatment, the physical form of the hydrogel material is intact, and the hydrogel material has good stability.
As shown in FIG. 7, the absorption peaks of the ultrasound-responsive fluorescent hydrogel material in the infrared spectrum before and after the ultrasound are obviously changed, which proves that the pyridine ring vibration absorption peak on the fluorescence-responsive molecule is from 1600.6cm-1Blue shift to 1598.6cm-1The ultrasonic response mechanism is disclosed, wherein the fluorescent response molecules capture free europium ions in gel under the action of ultrasonic waves, so that coordination occurs.
As shown in (a) and (b) of FIG. 8, the binding energy of the ultrasound-responsive fluorescent hydrogel material in photoelectron spectroscopy before and after ultrasound is significantly changed, and after ultrasound, the binding energy is 1152.4eV (Eu 3 d)3/2) And 1122.4eV (Eu 3 d)5/2) Blue-shifted to 1151.4eV and 1121.8eV, respectively, and the binding energy is 131.6eV (Eu 4 d)3/2) And 126.0eV (Eu 4 d)5/2) The fluorescence response molecules are respectively moved to the low fields of 131.2eV and 125.7eV, and the fact that the fluorescence response molecules are coordinated under the action of ultrasound is further proved, and then fluorescence emission changes are caused.
Example 2
In this example, the addition amount of the fluorescence responsive molecule is 0.6mg, and other parameters and methods are the same as those in example 1, so as to prepare the ultrasound responsive polymer fluorescent hydrogel material.
As shown in FIG. 5, when the ultrasound-responsive polymer fluorescent hydrogel material prepared in this example is subjected to ultrasound, the ratio of fluorescence intensities at 500nm and 615nm gradually decreases until the equilibrium state is reached after ultrasound for 35 minutes. Meanwhile, the hydrogel material always keeps a stable form in the ultrasonic process, has good stability, and the fluorescence emission is changed from light yellow to light red fluorescence, so that obvious macroscopic change is presented.
Example 3
In this example, the addition amount of the fluorescence responsive molecule is 0.2mg, and other parameters and methods are the same as those in example 1, so as to prepare the ultrasound responsive polymer fluorescent hydrogel material.
As shown in FIG. 5, when the ultrasound-responsive polymer fluorescent hydrogel material prepared in this example is subjected to ultrasound, the ratio of fluorescence intensities at 500nm and 615nm gradually decreases until the equilibrium state is reached after 20 minutes of ultrasound. Meanwhile, the hydrogel material always keeps a stable form in the ultrasonic process, has good stability, and the fluorescence emission is changed from light orange to bright red fluorescence, so that obvious macroscopic change is presented.
Example 4
In this example, a salt solution containing lanthanide metal ions was changed to terbium nitrate solution, acrylamide (AAm) was changed to 1.3g, and N, N' -Methylenebisacrylamide (MBAA) was changed to 8mg, and other parameters and methods were the same as those in example 3, to prepare an ultrasound-responsive polymeric fluorescent hydrogel material.
Example 5
In this example, a salt solution containing lanthanide metal ions was changed to a lanthanum nitrate solution, N' -Methylenebisacrylamide (MBAA) was changed to 8mg, and other parameters and methods were the same as those in example 3, to prepare an ultrasound-responsive polymeric fluorescent hydrogel material.
Example 6
In this example, the solvent of the gel prepolymer a was changed to dimethylformamide, and the other parameters and methods were the same as in example 3, and acrylamide (AAm) was changed to 1.6g, and N, N' -Methylenebisacrylamide (MBAA) was changed to 8mg, to prepare an ultrasound-responsive polymeric fluorescent hydrogel material.
Example 7
In this example, the solvent of the gel prepolymer a was changed to dimethylformamide, and the other parameters and methods were the same as in example 5, to prepare an ultrasound-responsive polymeric fluorescent hydrogel material.
Example 8
In this example, the gel-forming monomer was replaced with N-methylolacrylamide, and the other parameters and methods were the same as in example 3, to prepare an ultrasound-responsive polymeric fluorescent hydrogel material.
Example 9
In this example, the salt solution containing lanthanide metal ions was changed to terbium nitrate solution, and other parameters and methods were the same as in example 8, to prepare the ultrasound-responsive polymeric fluorescent hydrogel material.
Example 10
In this example, a salt solution containing lanthanide metal ions was changed to a lanthanum nitrate solution, and other parameters and methods were the same as in example 8, to prepare an ultrasound-responsive polymeric fluorescent hydrogel material.
The embodiments described above are intended to illustrate the technical solutions of the present invention in detail, and it should be understood that the above-mentioned embodiments are only specific embodiments of the present invention, and are not intended to limit the present invention, and any modification, supplement or similar substitution made within the scope of the principles of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A preparation method of an ultrasonic response type high molecular fluorescent hydrogel material is characterized by comprising the following steps:
(1) adding a gel-forming monomer, a fluorescent response molecule, a cross-linking agent and a free radical thermal initiator into an organic solvent, completely dissolving to obtain a gel pre-polymerization liquid A, and polymerizing the gel pre-polymerization liquid A into gel to obtain a fluorescent oil gel B;
(2) soaking the fluorescent hydrogel B in water, and replacing the solvent to obtain a fluorescent hydrogel C;
(3) and (3) soaking the fluorescent hydrogel C in a salt solution containing lanthanide metal ions for coordination, taking out and drying to obtain the ultrasonic response type macromolecular fluorescent hydrogel material.
2. The method for preparing an ultrasound-responsive polymer fluorescent hydrogel material according to claim 1, wherein the gel-forming monomer comprises an acrylamide monomer and a terpyridine functional monomer;
the acrylamide monomer comprises acrylamide or N-hydroxymethyl acrylamide;
the structural formula of the terpyridine functionalized monomer is shown as the formula (I):
3. the method for preparing an ultrasound-responsive polymer fluorescent hydrogel material according to claim 1, wherein the structural formula of the fluorescence-responsive molecule is shown in formula (II):
4. the method for preparing an ultrasound-responsive polymeric fluorescent hydrogel material according to claim 1, wherein the cross-linking agent is N, N' -methylenebisacrylamide; the free radical thermal initiator is azobisisobutyronitrile; the organic solvent comprises dimethyl sulfoxide or dimethylformamide.
5. The preparation method of the ultrasound-responsive polymer fluorescent hydrogel material according to claim 2, wherein the addition amount of the acrylamide monomer is 18-25 wt% of the total weight of the organic solvent;
the weight ratio of the acrylamide monomer, the terpyridine functionalized monomer, the cross-linking agent, the fluorescent response molecule and the free radical thermal initiator is 100: 0.6-0.8: 0.4-1.1: 0.012-0.07: 0.07-0.1.
6. The method for preparing an ultrasound-responsive polymer fluorescent hydrogel material according to claim 1, wherein the polymerization and gel formation manner in the step (1) is as follows: putting the gel pre-polymerization liquid A into an oven at 60-70 ℃, and gelling and polymerizing for 6-10 hours.
7. The method for preparing an ultrasound-responsive polymer fluorescent hydrogel material according to claim 1, wherein in the step (3), the salt solution containing lanthanide metal ions is any one of lanthanum nitrate, europium nitrate and terbium nitrate, and the concentration is 0.1-0.5M.
8. The ultrasound-responsive polymeric fluorescent hydrogel material with both visualization and morphological stability, which is prepared by the preparation method of the ultrasound-responsive polymeric fluorescent hydrogel material according to any one of claims 1 to 7.
9. The application of the ultrasound-responsive polymer fluorescent hydrogel material according to claim 8 in the fields of ultrasound diagnosis and treatment, imaging and industrial nondestructive inspection.
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