CN110527115B - Multifunctional self-repairing hydrogel, preparation method thereof and application thereof in biogenic amine detection - Google Patents
Multifunctional self-repairing hydrogel, preparation method thereof and application thereof in biogenic amine detection Download PDFInfo
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- C08J3/075—Macromolecular gels
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Abstract
The invention discloses a multifunctional self-repairing hydrogel, a preparation method thereof and application thereof in biogenic amine detection; the preparation method comprises the following steps: and dissolving salicylaldehyde-terminated polyethylene glycol in a buffer solution, fully oscillating at room temperature, adding polyethyleneimine, and uniformly mixing to prepare the self-repairing hydrogel. The self-repairing hydrogel can completely recover the original performance within 60s at room temperature after being damaged, and the storage modulus reaches 104Pa, loss modulus of 103Pa, pH and ion responsiveness. The hydrogel prepared by the invention has excellent mechanical properties, has multiple functions of rapid self-repairing, ion response, pH response, biogenic amine detection and the like, can widen the application range of the polyethylene glycol-based self-repairing hydrogel material, and is expected to be applied to the industries of food storage, self-repairing materials, fluorescent printing and the like.
Description
Technical Field
The invention relates to a self-repairing hydrogel, in particular to a multifunctional self-repairing hydrogel, a preparation method thereof and application thereof in biogenic amine detection.
Background
Hydrogels are three-dimensional gel materials formed by the immobilization of water molecules in a polymer backbone by surface tension and capillary forces. In recent years, research on self-healing hydrogels has become a hot spot to reduce material loss and reduce environmental burden. However, most of the existing self-repairing hydrogels have the problems of poor mechanical property, single function and long self-repairing period.
In order to solve the problem of poor mechanical property, two common methods are available; one is to build a double gel network, and the other is to increase the crosslink density of the hydrogel. The double-network hydrogel is an interpenetrating network formed by two polymers with different properties, one layer is a polyelectrolyte cross-linked network which is rigid and brittle due to close cross-linking, and the other layer is a neutral cross-linked network which is loose in cross-linking, soft and tough. The double-network hydrogel has extremely high mechanical strength and toughness, and can be compared favorably with rubber; but the gelling time can be prolonged, the gelling condition is more rigorous, and even the self-repairing period of the product is prolonged. For example, the Chinese patent application CN 108727610A discloses a double-network hydrogel with high toughness, shape memory and self-repairing characteristics and a preparation method thereof, the method forms a dynamic imine bond through the action of chitosan and polyethylene glycol with aldehyde groups at two ends to construct a first heavy network, and the second heavy network is a polyacrylamide cross-linked network; but the gel needs to react for at least 24 hours at the temperature of 30-50 ℃, the gel forming period is long, the temperature needs to be controlled, and the conditions are harsh.
To increase the functionality of the hydrogel, it is generally possible to introduce monomers containing specific functional groups directly or by grafting specific functional groups. The Chinese patent application CN 107987286A obtains the self-repairing hydrogel material with temperature response and pH response by mixing poly-dopamine methyl acrylate-N-isopropyl acrylamide and poly-N-isopropyl acrylamide-4-vinyl phenylboronic acid and adding water for dissolution, but the maximum value of the storage modulus (G') of the hydrogel is only 103Pa, its mechanical properties need to be improved.
Polyethylene glycol (PEG) is a material with extremely strong biocompatibility, is nontoxic and nonirritating, and is widely applied to various pharmaceutical preparations. The hydroxyl at the end of polyethylene glycol is easy to be chemically modified to introduce various functional groups, and is often used for preparing hydrogel systems. Forming Schiff base hydrogel with self-repairing performance by using aldehyde-terminated polyethylene glycol and a gel factor containing amino; however, the hydrogel only consists of the simplest aldehyde group (-CHO) and amine group (-NH)2) Crosslinking to form gel, single function, mostly only suitable for cell culture and poor mechanical property, and limits the application of the polyethylene glycol-based hydrogel.
The prior art can not prepare hydrogel which has good mechanical property, multiple functions and quick self-repairing performance.
Disclosure of Invention
Aiming at the defects of poor mechanical property, single function and long self-repairing time of the existing hydrogel, the invention provides the self-repairing hydrogel which can completely recover the original property within 60s at room temperature after being damaged and has the storage modulus of 104Pa, loss modulus of 103Pa, and has pH and ion responsiveness, and a preparation method thereof.
The invention also aims to provide application of the multifunctional self-repairing hydrogel in biogenic amine detection.
The purpose of the invention is realized by the following technical scheme:
the preparation method of the multifunctional self-repairing hydrogel comprises the following steps
1) Mixing polyformaldehyde and salicylaldehyde, carrying out ice bath, and slowly dropwise adding concentrated hydrochloric acid; stirring at room temperature for 24-48 h, washing with deionized water after the reaction is finished until the pH value is 6-7, recrystallizing, and drying to obtain 5-chloromethyl-2-hydroxy-benzaldehyde (CHBA);
2) under the ice bath condition, dissolving polyethylene glycol and triethylamine in a first organic solvent, slowly dropwise adding methanesulfonyl chloride into a mixed solution of the polyethylene glycol and the triethylamine, stirring at room temperature for 48-60 h, removing the solvent after the reaction is finished, washing, precipitating, and drying to obtain polyethylene glycol disulfonate (DE-PEG);
3) adding polyethylene glycol disulfonate (DE-PEG), imidazole and cesium carbonate into a second organic solvent, stirring at room temperature for 48-56 h, after the reaction is finished, carrying out suction filtration, removing the solvent, and adding one or more of dichloromethane, ethyl acetate and butyl acetate; washing, precipitating and drying to obtain imidazole-terminated polyethylene glycol (Im-PEG);
4) dissolving imidazole-terminated polyethylene glycol (Im-PEG) and 5-chloromethyl-2-hydroxy-benzaldehyde (CHBA) in a third organic solvent, reacting for 24-48 h at 70-120 ℃, removing the solvent after the reaction is finished, adding deionized water, washing, and drying to obtain salicylaldehyde-terminated polyethylene glycol;
5) the self-repairing hydrogel is formed by blending gel factor salicylaldehyde-terminated polyethylene glycol (SIm-PEG) and a cross-linking agent Polyethyleneimine (PEI) at room temperature and self-assembling in a PBS (phosphate buffer solution) with the pH of 4-13.
For further achieving the purpose of the invention, preferably, the molar ratio of the polyformaldehyde to the salicylaldehyde is 1: 2-1: 4; the molar ratio of the polyethylene glycol to the triethylamine to the methanesulfonyl chloride is 1 (2-10) to (2-10); the molar ratio of the polyethylene glycol disulfonate to the imidazole to the cesium carbonate is 1: (2-10): (2-10); the molar ratio of the imidazole-terminated polyethylene glycol to the 5-chloromethyl-2-hydroxy-benzaldehyde is 1: 2-1: 12; the molar ratio of the gel factor salicylaldehyde-terminated polyethylene glycol to the cross-linking agent polyethyleneimine is 1: 0.3-1: 0.5.
Preferably, the weight average molecular weight of the polyethylene glycol is 800-10000; the weight average molecular weight Mw of the polyethyleneimine is 600-10000.
Preferably, the first organic solvent can be one or more of dichloromethane, acetone and dimethyl sulfoxide; the second organic solvent is one or more of acetone, N-dimethylformamide and 2-butanone; the third organic solvent is one or more of toluene, acetonitrile and dimethyl sulfoxide.
Preferably, the concentration of the concentrated hydrochloric acid in the step 1) is 12 mol/L, and the molar ratio of the salicylaldehyde to the concentrated hydrochloric acid is 1: 5-1: 10.
Preferably, in the step 3), 2-4 m L m of one or more of dichloromethane, ethyl acetate and butyl acetate is added to 1mmol of polyethylene glycol dimethyl sulfonate (DE-PEG), and 1-2 m L of deionized water is added to 1mol of imidazole-terminated polyethylene glycol in the step 4).
Preferably, the recrystallization in step 1) is recrystallization in n-hexane; the precipitation in step 2) and step 3) is in diethyl ether; the washing of the step 2) and the step 3) is washing by deionized water; the washing of the step 4) is washing by one or more of diethyl ether, ethyl acetate and butyl acetate.
Preferably, the mass sum of the gel factor and the cross-linking agent in the step 5) is 10-20% of the mass of the PBS buffer solution.
The multifunctional self-repairing hydrogel prepared by the preparation method can completely recover the original performance within 60s at room temperature after being damaged, and the storage modulus reaches 104Class Pa, loss modulus of 103Pa grade, excellent mechanical property, pH responsiveness, ion responsiveness and other functions.
The multifunctional self-repairing hydrogel disclosed by the invention can be used for detecting biogenic amine, can be subjected to color change under the stimulation of biogenic amine, and can be used for identifying biogenic amine by naked eyes;
the self-repairing hydrogel is applied to biological medicines, food storage, self-repairing materials and fluorescent printing.
Imidazole is introduced into a polyethylene glycol chain, and salicylaldehyde-terminated polyethylene glycol (SIm-PEG) is prepared through ionization of the imidazole and is used as a raw material of the polyethylene glycol-based self-repairing hydrogel. The water-soluble polyethyleneimine of polyamine is used as a gel factor, and forms a reversible imine bond with a phenolic group of the salicylaldehyde-terminated polyethylene glycol, so that the hydrogel has self-repairing performance, pH responsiveness and ion responsiveness.
As shown in fig. 1, the dotted line part in fig. 1 (a) is a dynamic imine bond formed by an aldehyde group on salicylaldehyde and an amino group on polyethyleneimine, which endows the hydrogel prepared by the invention with pH responsiveness, so that the hydrogel can generate color change under different pH conditions. As is clear from examples 1 to 7, the hydrogel was pale yellow at a pH of 4 to 9 and orange-red at a pH of 10 to 13. In the process of storing the food and the hydrogel in a sealing manner, the hydrogel absorbs biogenic amine generated by the food to increase the pH value of the food, and when the pH value is more than 10, the biogenic amine can be detected by observing the color change of the hydrogel by naked eyes, so that whether the food can be safely eaten or not is judged.
FIG. 1 (b) shows that the aldehyde group on the salicylaldehyde and the amino group on the polyethyleneimine form a dynamic imine bond and a phenolic hydroxyl group to endow the hydrogel prepared by the invention with ion responsiveness, 1mol Zn2+Can be complexed with 3mol of phenolic hydroxyl and 3mol of imine bond to generate blue fluorescence. By dipping in Zn2+The mold of the solution is lightly printed on the surface of the hydrogel, and strong blue fluorescence can be observed in the corresponding area under the irradiation of 365nm ultraviolet light, so that the method can be used in the fluorescent printing industry.
The preparation method and the prepared hydrogel have the following advantages and beneficial effects:
(1) according to the invention, the crosslinking reaction of the salicylaldehyde-terminated polyethylene glycol and the polyamine is adopted to form reversible covalent bond hydrazone, the hydrogel has stimulation responsiveness to pH, biogenic amine, heat and the like, can endow the hydrogel with excellent self-repairing performance, can complete self-repairing within 60s after the hydrogel is damaged, can be used for detecting biogenic amine, and expands the application range of the polyethylene glycol-based Schiff base hydrogel.
(2) The invention self-assembles into gel by blending two low-viscosity solutions respectively containing amido and phenolic groups at room temperature, and has the advantages of mild gelling condition, short time, simple and convenient operation, and the like.
Drawings
FIG. 1 is a schematic diagram of pH response and ion response of hydrogel prepared by the present invention.
FIG. 2 is a strain scan of the multifunctional self-healing hydrogel obtained in example 1 with increased shear.
FIG. 3 is the self-repairing process (visual observation) of the multifunctional self-repairing hydrogel obtained in example 1 and example 3.
FIG. 4 is a step-by-step strain-scan of the multifunctional self-healing hydrogel obtained in example 1.
FIG. 5 is a graph showing the color change of the multifunctional self-repairing hydrogel obtained in example 1 caused by pork decay.
FIG. 6 shows Zn for the multifunctional self-repairing hydrogel obtained in example 12+And (5) performing fluorescent printing on the effect picture.
Detailed Description
For a better understanding of the present invention, the present invention will be described in further detail below with reference to examples and drawings, but the present invention is not limited thereto.
In the following examples, the properties of the self-healing hydrogels were tested using the following methods, unless otherwise indicated:
(1) rheological Properties measurements the change in storage modulus and loss modulus of the hydrogels at a frequency of 1rad/s in the stress range of 0.1 to 1000% was recorded using a G2-ARES stress controlled rheometer (TA Instruments, USA) using 25mm parallel plates at 25 ℃;
(2) performing hydrogel self-repairing test (visual inspection), namely dividing the hydrogels prepared in two groups of different embodiments into two parts at random, taking half of the hydrogels to approach each other (the gap is smaller than 0.5mm), standing for 60s, observing the change of the gap between the two parts, and randomly and lightly picking up one end to observe whether the hydrogel at the other end falls off;
(3) step-by-step strain sweep testing by alternating 100% (60s) and 800% (30s) stress sweeps at 25 ℃ using a G2-ARES stress controlled rheometer (TA Instruments, USA) to record the storage and loss moduli of the hydrogel as a function of time;
(4) detection of biogenic amine by hydrogel A meat sample (pork) weighing about 10g was cut into pieces and placed in a petri dish together with a bottle cap containing hydrogel (weighing about 100mg), the device was kept sealed, both sets of samples were stored in thermostatic chambers at 25 ℃ and 4 ℃ (controlled variable), respectively, and photo-photographs were taken every 24h for 3 days.
(5) Testing the fluorescent printing performance of the hydrogel, namely soaking a die carved with the character of 'SCUT' in 0.3 mol/L Zn2+And (3) placing the mold above the hydrogel for 5s in the solution, taking down the mold, observing whether the surface of the hydrogel has a 'SCUT' character with bright blue fluorescence under the irradiation of 365nm ultraviolet light, and judging whether the prepared multifunctional self-repairing hydrogel can be used for fluorescent printing.
(6) Detection of biogenic amine by hydrogel: meat samples (pork) weighing about 10g were cut into pieces and placed in a petri dish together with a bottle cap containing hydrogel (weighing about 100mg), the device was kept sealed, the two groups of samples were stored in thermostatic chambers at 25 ℃ and 4 ℃ (controlled variable), respectively, and optical photographs were taken every 24h for 3 days.
Example 1
A preparation method of multifunctional self-repairing hydrogel comprises the following steps:
(1) preparation of 5-chloromethyl-2-hydroxy-benzaldehyde (CHBA) 50mmol of polyoxymethylene and 100mmol of salicylaldehyde were added to a flask, and concentrated hydrochloric acid (12 mol/L) 84m L was slowly added dropwise in an ice bath, stirred at room temperature for 48 hours, washed with deionized water after the reaction was completed to pH 7, recrystallized in n-hexane, and dried.
(2) Preparation of polyethylene glycol disulfonate (DE-PEG): under the ice bath condition, adding 10mmol of polyethylene glycol 4000 and 40mmol of triethylamine into a dichloromethane solution, slowly dropwise adding 40mmol of methanesulfonyl chloride, stirring at room temperature for 48 hours, removing dichloromethane after the reaction is finished, washing with deionized water, precipitating with diethyl ether, and drying.
(3) Preparation of imidazole-terminated polyethylene glycol (Im-PEG) 10mmol of polyethylene glycol disulfonate (DE-PEG), 40mmol of imidazole and 40mmol of cesium carbonate were added to N, N-dimethylformamide, stirred at room temperature for 56h, suction filtered at the end of the reaction, the solvent was removed, dichloromethane 20m L was added, washed with deionized water and precipitated in diethyl ether, and dried.
(4) Preparation of salicylaldehyde-terminated polyethylene glycol (SIm-PEG) 5mmol of imidazole-terminated polyethylene glycol (Im-PEG) and 10mmol of 5-chloromethyl-2-hydroxy-benzaldehyde (CHBA) were added to toluene, reacted at 100 ℃ for 36h, after the reaction was completed, the solvent was removed, 5m L of water was added, washed with diethyl ether and dried.
(5) And (3) preparing the self-repairing hydrogel, namely dissolving 100mg of salicylaldehyde-terminated polyethylene glycol (SIm-PEG) in 870 mu L of PBS buffer solution (pH is 7), adding 30mg of polyethyleneimine (PEI 600) to oscillate, and self-assembling at room temperature to obtain the multifunctional self-repairing hydrogel.
As can be seen from FIG. 2, the product prepared in example 1 has a storage modulus (G') greater than a loss modulus (G "), demonstrating the formation of a hydrogel; the hydrogel prepared had a linear viscoelastic region of up to 40%, outside of which the storage modulus (G') of the hydrogel dropped rapidly and at 400% strain to less than its loss modulus (G "). The 400% strain is considered to be the critical strain value of the hydrogel, which indicates the rupture of the gel network and the transformation to the liquid state under this condition. Wherein the storage modulus (G') is up to 104Pa (20000Pa), which is obviously higher than CN 107987286A, shows that the prepared hydrogel has high hardness and good mechanical properties.
The test result of the hydrogel self-repairing test (visual observation) is shown in fig. 3, and the visual observation result of fig. 3 shows that the hydrogel prepared in example 1 can complete self-repairing within 60 s.
FIG. 4 is a step-by-step strain scanning of the hydrogel prepared in example 1, and it can be seen that after scanning for 30s at a large strain of 800%, the storage modulus (G ') is smaller than the loss modulus (G "), the gel network is destroyed to be in a liquid state, then the gel network is acted for 60s at a small strain of 100%, the hydrogel cross-linked network is reformed, and both the storage modulus (G') and the loss modulus (G") are restored to the original values, thereby further verifying the self-repairing performance of the hydrogel. Compared with the supramolecular hydrogel prepared in the Chinese patent application CN 107955186A, the self-repairing period of the supramolecular hydrogel is 30min, the hydrogel prepared in the embodiment only needs 60s for self-repairing, and the supramolecular hydrogel has the advantage of rapid self-repairing.
The detection test of the hydrogel on the biogenic amine is shown in fig. 5, the left side is an experimental device diagram, the dotted line part is the hydrogel weighing 100mg, and the color change of the hydrogel in 1-3 days in two groups of control groups at 25 ℃ and 4 ℃ is recorded respectively in order to facilitate observation and amplification to the right side; as can be seen from FIG. 5, when 10g of pork was placed in a sealed condition at 25 ℃ for 3 days, biogenic amines generated by the deterioration of the pork caused a visible color change (light yellow → red orange) in the hydrogel (100mg) prepared in this example, while the color of the hydrogel in the control group at 4 ℃ did not change significantly.
The dynamic imine bond formed by the aldehyde group on the salicylaldehyde and the amino group on the polyethyleneimine has pH responsiveness, and the combination of the following examples 1-7 shows that the hydrogel is light yellow in pH range of 4-9, and orange in pH range of 10-13. During the food storage process, the pH value of the hydrogel is increased by absorbing biogenic amine generated by food, and the color of 100mg of hydrogel can be changed by hermetically storing 10g of pork at 25 ℃ for 3 days, so that the hydrogel prepared in the embodiment has the capability of detecting biogenic amine, can be used for monitoring food spoilage, and has great application potential in food storage.
With the improvement of the social living standard, people pay more attention to food safety. The self-repairing hydrogel prepared by the invention can be stored in a sealed manner with meat, vegetables, fruits and other foods, whether the hydrogel can be safely eaten or not can be judged according to the color change of the hydrogel during eating, and the hydrogel has the characteristics of small occupied space, convenience in use, safety and reliability. The existing food spoilage detector generally adopts a circuit method, the instrument occupies a large space, food needs to be connected into a circuit during detection, and the operation is complex and part of food is wasted. The hydrogel for biogenic amine detection prepared by the invention can be used for monitoring food spoilage, is a good helper for ensuring food hygiene of people, and has the advantages of small volume, convenient use, safety, reliability and the like.
As shown in FIG. 6, the mold engraved with the word "SCUT" was immersed in 0.3 mol/L Zn2+Putting the mold in the solution for 3s5s above the hydrogel prepared in example 1, the mold is taken down, and a bright blue fluorescent character 'SCUT' can be observed on the surface of the hydrogel by irradiating the hydrogel with 365nm ultraviolet light, which proves that the multifunctional self-repairing hydrogel prepared in the embodiment can be used for fluorescent printing.
Example 2
A preparation method of multifunctional self-repairing hydrogel comprises the following steps:
(1) preparation of 5-chloromethyl-2-hydroxy-benzaldehyde (CHBA) 50mmol of polyoxymethylene and 100mmol of salicylaldehyde were added to a flask, and concentrated hydrochloric acid (12 mol/L) 42m L was slowly added dropwise in an ice bath, stirred at room temperature for 24 hours, washed with deionized water after the reaction was completed to pH 6, recrystallized in n-hexane, and dried.
(2) Preparation of polyethylene glycol disulfonate (DE-PEG): under the ice bath condition, adding 10mmol of polyethylene glycol 800 and 20mmol of triethylamine into the acetone solution, slowly dropwise adding 20mmol of methanesulfonyl chloride, stirring at room temperature for 60h, removing acetone after the reaction is finished, washing by deionized water, precipitating by diethyl ether, and drying.
(3) Preparation of imidazole-terminated polyethylene glycol (Im-PEG) 10mmol of polyethylene glycol disulfonate (DE-PEG), 20mmol of imidazole and 20mmol of cesium carbonate are added to acetone, stirred at room temperature for 48h, suction filtered after the reaction is finished, the solvent is removed, ethyl acetate 40m L is added, washed with deionized water and precipitated in ether, and dried.
(4) Preparation of salicylaldehyde-terminated polyethylene glycol (SIm-PEG) 5mmol of imidazole-terminated polyethylene glycol (Im-PEG) and 60mmol of 5-chloromethyl-2-hydroxy-benzaldehyde (CHBA) were added to acetonitrile, reacted at 70 ℃ for 24h, after the reaction was completed the solvent was removed, 10m L of water was added, washed with ethyl acetate and dried.
(5) And (2) preparing the self-repairing hydrogel, namely dissolving 100mg of salicylaldehyde-terminated polyethylene glycol (SIm-PEG) in PBS (pH 4) of 850 mu L, adding 50mg of polyethyleneimine (PEI 1800) to oscillate, and self-assembling at room temperature to obtain the self-repairing hydrogel for biogenic amine detection.
The hydrogel prepared in this example had a linear viscoelastic region with a strain of up to 38%, a storage modulus (G ') of 17000Pa, a loss modulus (G') of 3500Pa in the linear viscoelastic regionThe strain limit is 380%; the self-repairing period is 65 s; the hydrogel can monitor the putrefaction of pork by changing from light yellow to orange-red within 3 days at 25 ℃; taking down the container with Zn2+After the solution is subjected to the 'SCUT' mold, a character 'SCUT' with bright blue fluorescence can be observed under the irradiation of 365nm ultraviolet light.
Example 3
A preparation method of multifunctional self-repairing hydrogel comprises the following steps:
(1) preparation of 5-chloromethyl-2-hydroxy-benzaldehyde (CHBA) 50mmol of polyoxymethylene and 150mmol of salicylaldehyde were added to a flask, and then concentrated hydrochloric acid (12 mol/L) 70m L was slowly added dropwise in an ice bath, stirred at room temperature for 36 hours, washed with deionized water after the reaction was completed to pH 7, recrystallized in n-hexane, and dried.
(2) Preparation of polyethylene glycol disulfonate (DE-PEG): under the ice bath condition, adding 10mmol of polyethylene glycol 10000 and 100mmol of triethylamine into a dimethyl sulfoxide solution, slowly dropwise adding 100mmol of methanesulfonyl chloride, stirring at room temperature for 56h, removing the dimethyl sulfoxide after the reaction is finished, washing with deionized water, precipitating with diethyl ether, and drying.
(3) Preparing imidazole-terminated polyethylene glycol (Im-PEG) by adding 10mmol polyethylene glycol disulfonate (DE-PEG), 100mmol imidazole and 100mmol cesium carbonate in 2-butanone, stirring at room temperature for 50h, suction filtering after reaction, removing solvent, adding butyl acetate 30m L, washing with deionized water, precipitating in ether, and drying.
(4) Preparation of salicylaldehyde-terminated polyethylene glycol (SIm-PEG) 5mmol of imidazole-terminated polyethylene glycol (Im-PEG) and 30mmol of 5-chloromethyl-2-hydroxy-benzaldehyde (CHBA) were added to dimethyl sulfoxide, reacted at 120 ℃ for 24h, after the reaction was completed, the solvent was removed, 7m L of water was added, washed with butyl acetate, and dried.
(5) And (2) preparing the self-repairing hydrogel, namely dissolving 100mg of salicylaldehyde-terminated polyethylene glycol (SIm-PEG) in 870-L PBS buffer solution (pH is 13), adding 40mg of polyethyleneimine (PEI 1000), oscillating, and self-assembling at room temperature to obtain the self-repairing hydrogel for biogenic amine detection.
The test result of the hydrogel self-repairing test (visual observation) is shown in fig. 3, and the visual observation result of fig. 3 shows that the hydrogels prepared in examples 1 and 3 can complete self-repairing within 60 s.
The hydrogel prepared in the embodiment has the strain of up to 35% in the linear viscoelastic region, the storage modulus (G ') in the linear viscoelastic region is 15000Pa, the loss modulus (G') is 4000Pa, and the critical strain value is 350%; the self-repairing period is 60 s; since the hydrogel is formed in an environment with a pH value of 13 and the color of the gel is orange, the hydrogel cannot realize the conversion of light yellow to orange at 25 ℃ to monitor the putrefaction of pork; taking down the container with Zn2+After the solution is subjected to the 'SCUT' mold, a character 'SCUT' with bright blue fluorescence can be observed under the irradiation of 365nm ultraviolet light.
Example 4
A preparation method of multifunctional self-repairing hydrogel comprises the following steps:
(1) preparation of 5-chloromethyl-2-hydroxy-benzaldehyde (CHBA) 50mmol of polyoxymethylene and 100mmol of salicylaldehyde were added to a flask, and concentrated hydrochloric acid (12 mol/L) 50m L was slowly added dropwise in an ice bath, stirred at room temperature for 24 hours, washed with deionized water after the reaction was completed to pH 7, recrystallized in n-hexane, and dried.
(2) Preparation of polyethylene glycol disulfonate (DE-PEG): under the ice bath condition, adding 10mmol of polyethylene glycol 2000 and 20mmol of triethylamine into a dichloromethane solution, slowly dropwise adding 40mmol of methanesulfonyl chloride, stirring at room temperature for 56h, removing dichloromethane after the reaction is finished, washing with deionized water, precipitating with diethyl ether, and drying.
(3) Preparation of imidazole-terminated polyethylene glycol (Im-PEG) 10mmol of polyethylene glycol disulfonate (DE-PEG), 20mmol of imidazole and 40mmol of cesium carbonate are added to acetone, stirred at room temperature for 48h, suction filtered after the reaction is finished, the solvent is removed, ethyl acetate, butyl acetate and dichloromethane are added, each 10m L, washed with deionized water and precipitated in ether, and dried.
(4) Preparing salicylaldehyde-terminated polyethylene glycol (SIm-PEG), namely adding 5mmol of imidazole-terminated polyethylene glycol (Im-PEG) and 40mmol of 5-chloromethyl-2-hydroxy-benzaldehyde (CHBA) into toluene, reacting for 48 hours at 80 ℃, removing the solvent after the reaction is finished, adding 5m L of water, washing with diethyl ether and ethyl acetate according to the volume ratio of 1:1, and drying.
(5) And (2) preparing the self-repairing hydrogel, namely dissolving 80mg of salicylaldehyde-terminated polyethylene glycol (SIm-PEG) in 900 mu L of PBS buffer solution (pH is 10), adding 20mg of polyethyleneimine (PEI 1800) to oscillate, and self-assembling at room temperature to obtain the self-repairing hydrogel for biogenic amine detection.
The hydrogel prepared in the embodiment has the linear viscoelastic region with the strain up to 40%, the storage modulus (G ') in the linear viscoelastic region is 18000Pa, the loss modulus (G') is 3800Pa, and the critical strain value is 400%; the self-repairing period is 65 s; since the hydrogel is formed in an environment with a pH value of 10 and the color of the gel is orange, the hydrogel cannot realize the conversion of light yellow to orange at 25 ℃ to monitor the putrefaction of pork; taking down the container with Zn2+After the solution is subjected to the 'SCUT' mold, a character 'SCUT' with bright blue fluorescence can be observed under the irradiation of 365nm ultraviolet light.
Example 5
A preparation method of multifunctional self-repairing hydrogel comprises the following steps:
(1) preparation of 5-chloromethyl-2-hydroxy-benzaldehyde (CHBA) 50mmol of polyoxymethylene and 150mmol of salicylaldehyde were added to a flask, and concentrated hydrochloric acid (12 mol/L) 60m L was slowly added dropwise in an ice bath, stirred at room temperature for 36 hours, washed with deionized water after the reaction was completed to pH 7, recrystallized in n-hexane, and dried.
(2) Preparation of polyethylene glycol disulfonate (DE-PEG): under the ice bath condition, adding 10mmol of polyethylene glycol 4000 and 40mmol of triethylamine into a dichloromethane solution, slowly dropwise adding 40mmol of methanesulfonyl chloride, stirring at room temperature for 48 hours, removing dichloromethane after the reaction is finished, washing with deionized water, precipitating with diethyl ether, and drying.
(3) Preparation of imidazole-terminated polyethylene glycol (Im-PEG) 10mmol of polyethylene glycol disulfonate (DE-PEG), 40mmol of imidazole and 40mmol of cesium carbonate were added to N, N-dimethylformamide, stirred at room temperature for 56h, after the reaction was completed, suction filtration was carried out, the solvent was removed, dichloromethane and ethyl acetate each 10m L were added, washed with deionized water and precipitated in ether, and dried.
(4) Preparing salicylaldehyde-terminated polyethylene glycol (SIm-PEG), namely adding 5mmol of imidazole-terminated polyethylene glycol (Im-PEG) and 10mmol of 5-chloromethyl-2-hydroxy-benzaldehyde (CHBA) into toluene, reacting for 36h at 100 ℃, removing the solvent after the reaction is finished, adding 8m L of water, washing ethyl acetate and butyl acetate according to the volume ratio of 1:1, and drying.
(5) And (2) preparing the self-repairing hydrogel, namely dissolving 150mg of salicylaldehyde-terminated polyethylene glycol (SIm-PEG) in 800 mu L PBS buffer solution (pH is 9), adding 50mg of polyethyleneimine (PEI 600) to oscillate, and self-assembling at room temperature to obtain the self-repairing hydrogel for biogenic amine detection.
The hydrogel prepared in the example has a linear viscoelastic region with a strain of up to 42%, a storage modulus (G ') of 21000Pa, a loss modulus (G') of 4200Pa and a critical strain value of 410%; the self-repairing period is 65 s; the hydrogel was able to monitor the spoilage of pork by changing from pale yellow to orange red within 3 days at 25 ℃; taking down the container with Zn2+After the solution is subjected to the 'SCUT' mold, a character 'SCUT' with bright blue fluorescence can be observed under the irradiation of 365nm ultraviolet light. .
Example 6
A preparation method of multifunctional self-repairing hydrogel comprises the following steps:
(1) preparation of 5-chloromethyl-2-hydroxy-benzaldehyde (CHBA) 50mmol of polyoxymethylene and 200mmol of salicylaldehyde were placed in a flask, ice-cooled, concentrated hydrochloric acid (12 mol/L) 84m L was slowly added dropwise thereto, stirred at room temperature for 36 hours, washed with deionized water after the reaction was completed to pH 6.5, recrystallized in n-hexane, and dried.
(2) Preparation of polyethylene glycol disulfonate (DE-PEG): under the ice bath condition, adding 10mmol of polyethylene glycol 2000 and 20mmol of triethylamine into the acetone solution, slowly dropwise adding 100mmol of methanesulfonyl chloride, stirring at room temperature for 48h, removing acetone after the reaction is finished, washing by deionized water, precipitating by diethyl ether, and drying.
(3) Preparation of imidazole-terminated polyethylene glycol (Im-PEG) 10mmol of polyethylene glycol disulfonate (DE-PEG), 20mmol of imidazole and 100mmol of cesium carbonate are added to acetone, stirred at room temperature for 48h, suction filtered after the reaction is finished, the solvent is removed, butyl acetate and dichloromethane are added, each 15m L, washed with deionized water and precipitated in diethyl ether, and dried.
(4) Preparing salicylaldehyde-terminated polyethylene glycol (SIm-PEG), adding 5mmol of imidazole-terminated polyethylene glycol (Im-PEG) and 20mmol of 5-chloromethyl-2-hydroxy-benzaldehyde (CHBA) into acetonitrile, reacting at 80 ℃ for 36h, removing solvent after the reaction is finished, adding 10m L of water, washing with butyl acetate and diethyl ether according to the volume ratio of 1:1, and drying.
(5) And (2) preparing the self-repairing hydrogel, namely dissolving 115mg of salicylaldehyde-terminated polyethylene glycol (SIm-PEG) in PBS (pH 6) of 850 mu L, adding 35mg of polyethyleneimine (PEI 10000) to oscillate, and self-assembling at room temperature to obtain the self-repairing hydrogel for biogenic amine detection.
The hydrogel prepared in the embodiment has the linear viscoelastic region with the strain up to 40%, the storage modulus (G ') in the linear viscoelastic region is 25000Pa, the loss modulus (G') is 3700Pa, and the critical strain value is 40%; the self-repairing period is 70 s; the hydrogel was able to monitor the spoilage of pork by changing from pale yellow to orange red within 3 days at 25 ℃; taking down the container with Zn2+After the solution is subjected to the 'SCUT' mold, a character 'SCUT' with bright blue fluorescence can be observed under the irradiation of 365nm ultraviolet light. .
Example 7
A preparation method of multifunctional self-repairing hydrogel comprises the following steps:
(1) preparation of 5-chloromethyl-2-hydroxy-benzaldehyde (CHBA) 50mmol of polyoxymethylene and 200mmol of salicylaldehyde were added to a flask, and concentrated hydrochloric acid (12 mol/L) 84m L was slowly added dropwise in an ice bath, stirred at room temperature for 48 hours, washed with deionized water after the reaction was completed to pH 7, recrystallized in n-hexane, and dried.
(2) Preparation of polyethylene glycol disulfonate (DE-PEG): under the ice bath condition, adding 10mmol of polyethylene glycol 8000 and 100mmol of triethylamine into a dichloromethane solution, slowly dropwise adding 20mmol of methanesulfonyl chloride, stirring at room temperature for 48h, removing dichloromethane after the reaction is finished, washing by deionized water, precipitating by diethyl ether, and drying.
(3) Preparation of imidazole-terminated polyethylene glycol (Im-PEG) 10mmol of polyethylene glycol disulfonate (DE-PEG), 100mmol of imidazole and 20mmol of cesium carbonate are added to acetone, stirred at room temperature for 36h, suction filtered after the reaction is finished, the solvent is removed, ethyl acetate and butyl acetate are added each 10m L, washed with deionized water and precipitated in ether, and dried.
(4) Preparing salicylaldehyde-terminated polyethylene glycol (SIm-PEG), namely adding 5mmol of imidazole-terminated polyethylene glycol (Im-PEG) and 20mmol of 5-chloromethyl-2-hydroxy-benzaldehyde (CHBA) into acetonitrile, reacting for 36h at 80 ℃, removing the solvent after the reaction is finished, adding 6m of L water, washing with diethyl ether, ethyl acetate and butyl acetate according to the volume ratio of 1: 1:1, and drying.
(5) And (2) preparing the self-repairing hydrogel, namely dissolving 100mg of salicylaldehyde-terminated polyethylene glycol (SIm-PEG) in 850 mu L PBS buffer solution (pH is 5), adding 50mg of polyethyleneimine (PEI 1800) to oscillate, and self-assembling at room temperature to obtain the self-repairing hydrogel for biogenic amine detection.
The hydrogel prepared in the embodiment has the linear viscoelastic region with the strain up to 38%, the storage modulus (G ') in the linear viscoelastic region is 15000Pa, the loss modulus (G') is 4000Pa, and the critical strain value is 380%; the self-repairing period is 55 s; the hydrogel was able to monitor the spoilage of pork by changing from pale yellow to orange red within 3 days at 25 ℃; taking down the container with Zn2+After the solution is subjected to the 'SCUT' mold, a character 'SCUT' with bright blue fluorescence can be observed under the irradiation of 365nm ultraviolet light.
In conclusion, the novel multifunctional self-repairing hydrogel is formed by blending and self-assembling the salicylaldehyde-terminated polyethylene glycol and the polyamine-containing polyethyleneimine, and has quick self-repairing capability, pH response and ion response, so that the hydrogel can be used for detecting biogenic amine to monitor food decay, can also be applied to fluorescent printing, and has great application potential in the fields of biomedicine, food storage, self-repairing materials, fluorescent printing and the like.
The present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents and are included in the scope of the present invention.
Claims (10)
1. The preparation method of the multifunctional self-repairing hydrogel is characterized by comprising the following steps
1) Mixing polyformaldehyde and salicylaldehyde, carrying out ice bath, and slowly dropwise adding concentrated hydrochloric acid; stirring at room temperature for 24-48 h, washing with deionized water after the reaction is finished until the pH is = 6-7, recrystallizing, and drying to obtain 5-chloromethyl-2-hydroxy-benzaldehyde;
2) under the ice bath condition, dissolving polyethylene glycol and triethylamine in a first organic solvent, slowly dropwise adding methanesulfonyl chloride into a mixed solution of the polyethylene glycol and the triethylamine, stirring at room temperature for 48-60 h, removing the solvent after the reaction is finished, washing, precipitating, and drying to obtain polyethylene glycol disulfonate;
3) adding polyethylene glycol dimethyl sulfonate, imidazole and cesium carbonate into a second organic solvent, stirring at room temperature for 48-56 hours, after the reaction is finished, carrying out suction filtration, removing the solvent, and adding one or more of dichloromethane, ethyl acetate and butyl acetate; washing, precipitating and drying to obtain imidazole-terminated polyethylene glycol;
4) dissolving imidazole-terminated polyethylene glycol and 5-chloromethyl-2-hydroxy-benzaldehyde in a third organic solvent, reacting for 24-48 h at 70-120 ℃, removing the solvent after the reaction is finished, adding deionized water, washing, and drying to obtain salicylaldehyde-terminated polyethylene glycol;
5) the self-repairing hydrogel is formed by blending polyethylene glycol terminated by a gel factor salicylaldehyde and polyethylene imine serving as a cross-linking agent at room temperature and self-assembling in a PBS (phosphate buffer solution) with the pH of 4-13.
2. The preparation method of the multifunctional self-repairing hydrogel according to claim 1, wherein the molar ratio of the polyformaldehyde to the salicylaldehyde is 1: 2-1: 4; the molar ratio of the polyethylene glycol to the triethylamine to the methanesulfonyl chloride is 1 (2-10) to (2-10); the molar ratio of the polyethylene glycol disulfonate to the imidazole to the cesium carbonate is 1: (2-10): (2-10); the molar ratio of the imidazole-terminated polyethylene glycol to the 5-chloromethyl-2-hydroxy-benzaldehyde is 1: 2-1: 12; the molar ratio of the gel factor salicylaldehyde-terminated polyethylene glycol to the cross-linking agent polyethyleneimine is 1: 0.3-1: 0.5.
3. The preparation method of the multifunctional self-repairing hydrogel according to claim 1, wherein the polyethylene glycol has a weight average molecular weight of 800-10000; the weight average molecular weight Mw of the polyethyleneimine is 600-10000.
4. The method for preparing the multifunctional self-repairing hydrogel according to claim 1, wherein the first organic solvent is one or more of dichloromethane, acetone and dimethyl sulfoxide; the second organic solvent is one or more of acetone, N-dimethylformamide and 2-butanone; the third organic solvent is one or more of toluene, acetonitrile and dimethyl sulfoxide.
5. The preparation method of the multifunctional self-repairing hydrogel of claim 1, wherein the concentration of the concentrated hydrochloric acid in the step 1) is 12 mol/L, and the molar ratio of the salicylaldehyde to the concentrated hydrochloric acid is 1: 5-1: 10.
6. The preparation method of the multifunctional self-repairing hydrogel according to claim 1, wherein 2-4 m L of one or more of dichloromethane, ethyl acetate and butyl acetate is added to 1mmol of polyethylene glycol disulfonate (DE-PEG) in step 3), and 1-2 m L of deionized water is added to 1mol of imidazole-terminated polyethylene glycol in step 4).
7. The method for preparing the multifunctional self-repairing hydrogel of claim 1, wherein the recrystallization in the step 1) is a recrystallization in n-hexane; the precipitation in step 2) and step 3) is in diethyl ether; the washing of the step 2) and the step 3) is washing by deionized water; the washing of the step 4) is washing by one or more of diethyl ether, ethyl acetate and butyl acetate.
8. The method for preparing the multifunctional self-repairing hydrogel of claim 1, wherein the sum of the mass of the gel factor and the mass of the cross-linking agent in the step 5) is 10-20% of the mass of the PBS buffer.
9. The multifunctional self-repairing hydrogel is characterized by being prepared by the preparation method of any one of claims 1 to 8, the self-repairing hydrogel completely recovers the original performance within 60s at room temperature after being damaged, and the storage modulus reaches 104Class Pa, loss modulus of 103Pa grade, and has pH and ion responsiveness.
10. The multifunctional self-healing hydrogel of claim 9, which is used in the detection of biogenic amines.
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| CN106983905B (en) * | 2017-05-12 | 2019-10-11 | 深圳华诺生物科技有限公司 | A kind of injectable type self-healing hemostatic material and its preparation method and application |
| CN107007881B (en) * | 2017-05-12 | 2020-11-27 | 深圳华诺生物科技有限公司 | Injectable self-healing gel for loading and releasing medicine and preparation method and application thereof |
| CN108794737B (en) * | 2018-06-26 | 2019-07-02 | 中国科学院长春应用化学研究所 | The agent of blocking modification polyethylene glycol crosslinked and preparation method with ultraviolet light response function and aerogel dressing and preparation method containing the crosslinking agent |
| CN109867747A (en) * | 2019-03-21 | 2019-06-11 | 济南大学 | A kind of preparation method of the hydrogel with double stimuli responsive and self-healing performance |
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