A fast-gelling oxidized sodium alginate / polyvinyl alcohol fluorescent hydrogel, a preparation method and application thereof

Abstract

The application discloses a kind of oxidized sodium alginate / polyvinyl alcohol fluorescent hydrogel that can be quickly gelled, and preparation method and application thereof, belong to the technical field of hydrogel preparation.The preparation method provided by the application comprises the following steps: adding sodium periodate to sodium alginate aqueous solution for oxidation, dialysis, drying to obtain oxidized sodium alginate;Oxidized sodium alginate is dissolved in water, amino phenylboronic acid and activator are added, and phenylboronic acid group oxidized sodium alginate solution is obtained by reaction;Phenylboronic acid group oxidized sodium alginate solution is mixed with polyvinyl alcohol solution, and stirring is carried out for 8-20s, and it is obtained.The preparation method is simple and convenient, gelling is very rapid, equipment cost is low, and it is suitable for large-scale preparation;The prepared hydrogel has excellent swelling performance, emits blue light under ultraviolet light irradiation;Meanwhile, its properties are stable, has the characteristics of pH response and active oxygen response, and can realize self-healing, has good application prospect in the field of tissue repair and fluorescent anti-counterfeiting.

Description

Technical Field

[0001] This invention relates to the field of hydrogel preparation technology, and in particular to a rapidly gelling oxidized sodium alginate / polyvinyl alcohol fluorescent hydrogel, its preparation method, and its application. Background Technology

[0002] The information disclosed in the background section of this invention is intended only to enhance the understanding of the overall background of the invention and is not necessarily to be construed as an admission or in any way implying that such information constitutes prior art known to those skilled in the art.

[0003] Hydrogels are hydrophilic polymers with a three-dimensional cross-linked network structure. Their physical and chemical properties are similar to those of human biological tissues, exhibiting good biocompatibility. Through their unique swelling, water-retention, and high permeability properties, hydrogels can efficiently load and sustain drug delivery. Furthermore, due to their flexibility and excellent adhesion properties, hydrogels can be used as wound dressings to promote wound healing.

[0004] Sodium alginate (SA) is a water-soluble anionic biopolymer extracted from natural seaweed or produced by bacteria. Rich in hydroxyl and carboxyl groups, it exhibits strong affinity for dyes and metal ions. However, single-component SA hydrogels suffer from poor mechanical properties, poor gel formation, and poor adsorption stability, severely limiting their widespread application. Polyvinyl alcohol (PVA) is a common linear polyhydroxy polymer with high film-forming ability and chemical stability. It is non-toxic, biodegradable, and water-soluble, possessing inherent advantages for preparing ideal "green" hydrogels. However, single-component PVA hydrogels are prone to swelling and adhesion, exhibiting poor stability. Combining the two to prepare sodium alginate / PVA hydrogels combines the advantages of both SA and PVA, solving the problems of poor mechanical properties or stability in single-component hydrogel materials.

[0005] Existing technologies typically employ physical crosslinking methods (such as freeze-thaw and calcium ion crosslinking) to prepare SA / PVA composite hydrogels. However, these methods suffer from slow gelation rates and low production efficiency. Existing chemical crosslinking methods usually require specific triggering conditions, such as the addition of catalysts or the application of light, and their gelation rates are also relatively slow. Furthermore, existing SA / PVA composite hydrogels generally lack fluorescent properties, hindering their further applications in anti-counterfeiting and imaging fields. Therefore, providing a method for preparing sodium alginate / polyvinyl alcohol hydrogels that can rapidly gel within 1 minute and possess fluorescent properties, thereby efficiently preparing fluorescent hydrogels applicable to anti-counterfeiting and imaging fields, is an urgent problem to be solved. Summary of the Invention

[0006] In view of this, the present invention provides a rapidly gelling oxidized sodium alginate / polyvinyl alcohol fluorescent hydrogel, its preparation method and application, which solves the problems of slow gelling speed and lack of fluorescent properties of sodium alginate / polyvinyl alcohol hydrogel in the prior art.

[0007] In a first aspect, the present invention provides a method for preparing a rapidly gelling oxidized sodium alginate / polyvinyl alcohol fluorescent hydrogel, comprising the following steps:

[0008] Sodium periodate was added to an aqueous solution of sodium alginate for oxidation. After dialysis and drying, oxidized sodium alginate was obtained.

[0009] Sodium oxidized alginate was dissolved in water, and aminophenylboronic acid and an activator were added to react and obtain a sodium oxidized alginate solution with phenylboronic acid group.

[0010] The sodium alginate solution with phenylboronic acid group is mixed with a polyvinyl alcohol solution and stirred for 8-20 seconds to obtain the product.

[0011] Preferably, the concentration of the sodium alginate aqueous solution is 1-3 wt%.

[0012] Preferably, the mass ratio of sodium alginate to sodium periodate is 2:(0.8-1.2).

[0013] Preferably, the oxidation time is 20-30 hours and the oxidation temperature is 20-30°C; the oxidation process is carried out under light-protected conditions.

[0014] Preferably, in the step of dissolving sodium alginate in water, the concentration of sodium alginate is 1-3 wt%.

[0015] Preferably, the aminophenylboronic acid is selected from 3-aminophenylboronic acid or 4-aminophenylboronic acid, and the activator is 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide.

[0016] Preferably, the mass ratio of sodium oxidized alginate, aminophenylboronic acid and activator is 8:(2-3):(5-6).

[0017] Preferably, the concentration of the polyvinyl alcohol solution is 10-20% w / v.

[0018] Preferably, the volume ratio of the phenylboronic acid-based oxidized sodium alginate solution to the polyvinyl alcohol solution is 1:(0.8-1.2).

[0019] Secondly, the present invention provides a rapidly gelling sodium alginate / polyvinyl alcohol fluorescent hydrogel prepared by the above preparation method.

[0020] Thirdly, the present invention provides the application of the above-mentioned rapidly gelling oxidized sodium alginate / polyvinyl alcohol fluorescent hydrogel in the preparation of medical materials for tissue repair or fluorescent anti-counterfeiting materials.

[0021] Compared with the prior art, the present invention has achieved the following beneficial effects:

[0022] (1) The preparation method of the oxidized sodium alginate / polyvinyl alcohol fluorescent hydrogel of the present invention is simple and convenient, the gelation is very fast (within 20s), no additional catalyst or special conditions such as light are required, the equipment cost is low, and it is suitable for large-scale preparation.

[0023] (2) The rapidly gelling sodium alginate / polyvinyl alcohol fluorescent hydrogel prepared by this invention has a three-dimensional porous structure, excellent swelling performance, and a swelling ratio as high as 460%. It has the potential to load various drugs, cells, growth factors, and promote drug release and wound healing. The hydrogel of this invention emits blue light under ultraviolet light irradiation, which can realize anti-counterfeiting or imaging functions. At the same time, it is stable, has pH-responsive and reactive oxygen species-responsive properties, and can achieve self-healing, which improves the utilization rate of the hydrogel. The hydrogel of this invention has excellent comprehensive performance, which broadens its application range. Attached Figure Description

[0024] The accompanying drawings, which form part of this specification, are used to provide a further understanding of the invention. The illustrative embodiments and descriptions of the invention are used to explain the invention and do not constitute an undue limitation thereof. Obviously, those skilled in the art can obtain other drawings based on these drawings without any inventive effort.

[0025] Figure 1 This is a synthesis reaction route diagram of the sodium alginate / polyvinyl alcohol fluorescent hydrogels of Examples 1 to 3 of the present invention;

[0026] Figure 2 These are scanning electron microscope (SEM) images of the sodium alginate / polyvinyl alcohol fluorescent hydrogel prepared in Example 2 of this invention;

[0027] Figure 3 This describes the relationship between the storage modulus of the sodium alginate / polyvinyl alcohol fluorescent hydrogels in Examples 1-3 of this invention and the frequency.

[0028] Figure 4 This describes the relationship between the storage modulus of the oxidized sodium alginate / polyvinyl alcohol fluorescent hydrogels in Examples 1-3 of this invention and the change over time.

[0029] Figure 5 This is a test diagram of the adhesion performance of sodium alginate / polyvinyl alcohol fluorescent hydrogel in Example 2 of the present invention;

[0030] Figure 6 The swelling ratio of the sodium alginate / polyvinyl alcohol fluorescent hydrogels prepared in Examples 1-3 of this invention;

[0031] Figure 7 This is a digital image of the oxidized sodium alginate / polyvinyl alcohol fluorescent hydrogel of Example 2 of the present invention under ultraviolet light irradiation;

[0032] Figure 8 This is a test diagram of the self-healing performance of the sodium alginate / polyvinyl alcohol fluorescent hydrogel in Example 2 of the present invention;

[0033] Figure 9 The modulus of the sodium alginate / polyvinyl alcohol fluorescent hydrogels in Examples 1-3 of this invention varies with strain.

[0034] Figure 10 These are digital images of the oxidized sodium alginate / polyvinyl alcohol fluorescent hydrogel of Example 2 of the present invention under the influence of untreated hydrochloric acid, NaOH solution, and H2O2 solution. Detailed Implementation

[0035] It should be noted that the following detailed descriptions are exemplary and intended to provide further illustration of the invention. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains.

[0036] This invention provides a method for preparing a rapidly gelling oxidized sodium alginate / polyvinyl alcohol fluorescent hydrogel, comprising the following steps:

[0037] Sodium periodate was added to an aqueous solution of sodium alginate for oxidation. After dialysis and drying, oxidized sodium alginate was obtained.

[0038] Sodium oxidized alginate was dissolved in water, and aminophenylboronic acid and an activator were added to react and obtain a sodium oxidized alginate solution with phenylboronic acid group.

[0039] The sodium alginate solution with phenylboronic acid group is mixed with a polyvinyl alcohol solution and stirred for 8-20 seconds to obtain the product.

[0040] This invention first utilizes sodium periodate to oxidize sodium alginate, causing the sodium alginate to undergo ring-opening oxidation. The exposed aldehyde and carboxyl groups on the monomer react with aminophenylboronic acid, allowing a single monomer to graft up to three phenylboronic acid groups. This not only accelerates the hydrogel formation rate but also immobilizes a large number of phenylboronic acid groups on the sodium alginate molecular chain, preventing the benzene ring from vibrating in situ and thus achieving aggregation-induced emission fluorescence. Therefore, the hydrogel prepared by this invention exhibits fluorescent properties. The phenylboronic acid groups react with the hydroxyl groups in polyvinyl alcohol to form borate ester bonds, thereby crosslinking to obtain an oxidized sodium alginate / polyvinyl alcohol fluorescent hydrogel.

[0041] In this invention, the concentration of the sodium alginate aqueous solution is 1-3 wt%, more preferably 1-2 wt%, and most preferably 2 wt%. Excessive concentration of the sodium alginate aqueous solution will reduce its fluidity, which is detrimental to the oxidation reaction.

[0042] In this invention, the mass ratio of sodium alginate to sodium periodate is 2:(0.8-1.2). Sodium periodate can oxidize the hydroxyl groups in sodium alginate to aldehyde groups, facilitating its reaction with aminophenylboronic acid.

[0043] In this invention, the oxidation time is 20–30 hours, more preferably 23–27 hours; the oxidation temperature is 20–30°C, and it can be carried out at room temperature. Since sodium periodate is easily decomposed by light, the oxidation process is carried out under light-protected conditions. After oxidation is complete, this invention preferably uses a terminator to terminate the reaction, preferably ethylene glycol.

[0044] This invention does not impose special limitations on the dialysis steps; commonly used dialysis methods in the art can be employed. Dialysis is used to purify oxidized sodium alginate and remove unreacted small molecules. This invention also does not impose special limitations on the drying steps following dialysis; freeze drying is preferred.

[0045] In this invention, in the step of dissolving sodium oxidized alginate in water, the concentration of sodium oxidized alginate is 1-3 wt%, more preferably 1.5-2.5 wt%.

[0046] In this invention, the aminophenylboronic acid is selected from 3-aminophenylboronic acid or 4-aminophenylboronic acid. It reacts with carboxylic acids to form amide bonds and with aldehyde groups to form Schiff bases, thereby connecting one sodium alginate repeating unit to three phenylboronic acid groups. The activator is 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide, which can promote the reaction of amino groups with carboxyl or aldehyde groups.

[0047] In this invention, the mass ratio of sodium oxidized alginate, aminophenylboronic acid and activator is 8:(2-3):(5-6).

[0048] In this invention, the concentration of the polyvinyl alcohol solution is 10-20% w / v, and the solvent is water. This invention does not impose any special restrictions on its preparation method; any commonly used method in the art for preparing polyvinyl alcohol solutions can be used. This invention does not impose any special restrictions on the type of polyvinyl alcohol; for example, polyvinyl alcohol 1799, polyvinyl alcohol 1788, polyvinyl alcohol 2088, polyvinyl alcohol 2099, polyvinyl alcohol 2488, and polyvinyl alcohol 2499 can be used.

[0049] In this invention, the volume ratio of the phenylboronic acid-based oxidized sodium alginate solution to the polyvinyl alcohol solution is 1:(0.8-1.2). The phenylboronic acid groups of the phenylboronic acid-based oxidized sodium alginate react with the hydroxyl groups of polyvinyl alcohol to form borate ester bonds. Because the phenylboronic acid-based oxidized sodium alginate has a large number of phenylboronic acid groups, it can rapidly undergo a crosslinking reaction with polyvinyl alcohol at room temperature to form a gel.

[0050] This invention also provides a rapidly gelling oxidized sodium alginate / polyvinyl alcohol fluorescent hydrogel prepared by the above-described method. The oxidized sodium alginate / polyvinyl alcohol fluorescent hydrogel obtained by this invention has a three-dimensional porous structure, excellent swelling properties with a swelling ratio as high as 460%, emits blue light under ultraviolet light irradiation, exhibits pH-responsive and reactive oxygen species-responsive characteristics, and is capable of self-healing.

[0051] The present invention also provides the application of the above-mentioned rapidly gelling oxidized sodium alginate / polyvinyl alcohol fluorescent hydrogel in the preparation of medical materials for tissue repair or fluorescent anti-counterfeiting materials.

[0052] The technical solution of the present invention will be further described below with reference to specific embodiments. Figure 1 The synthesis reaction route diagrams for the oxidized sodium alginate / polyvinyl alcohol fluorescent hydrogels of Examples 1 to 3 are shown.

[0053] Example 1

[0054] This embodiment provides a method for preparing sodium alginate / polyvinyl alcohol fluorescent hydrogel, including the following steps:

[0055] (1) Weigh 1.5g of sodium alginate and dissolve it in 75mL of deionized water, stirring until completely dissolved. Weigh 0.75g of sodium periodate and dissolve it in 5mL of deionized water. Add the sodium periodate solution dropwise to the sodium alginate solution and stir in the dark for 24h. Add 1mL of ethylene glycol to the above solution to stop the oxidation for 2h, dialyze to purify for 2d, and freeze-dry to obtain oxidized sodium alginate powder.

[0056] (2) Weigh 80 mg of sodium alginate powder and dissolve it in 4 mL of deionized water, stirring until completely dissolved. Weigh 35 mg of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC), 23 mg of N-hydroxysuccinimide (NHS), and 27 mg of 3-aminophenylboronic acid and add them to the above solution. Stir for 2 h to obtain a phenylboronic acid-based sodium alginate solution.

[0057] (3) Weigh 1g of polyvinyl alcohol 1799, dissolve it in 10mL of deionized water, heat and stir at 90℃ until completely dissolved; to obtain a polyvinyl alcohol solution.

[0058] (4) Take 1 mL of the polyvinyl alcohol solution (10% w / v) from step (3), add 1 mL of the sodium phenylboronic acid oxidized alginate solution from step (2), and stir rapidly for 10 s to obtain sodium oxidized alginate / polyvinyl alcohol fluorescent hydrogel.

[0059] Example 2

[0060] This embodiment provides a method for preparing sodium alginate / polyvinyl alcohol fluorescent hydrogel, including the following steps:

[0061] (1) Weigh 1.5g of sodium alginate and dissolve it in 75mL of deionized water, stirring until completely dissolved. Weigh 0.75g of sodium periodate and dissolve it in 5mL of deionized water. Add the sodium periodate solution dropwise to the sodium alginate solution and stir in the dark for 24h. Add 1mL of ethylene glycol to the above solution to stop the oxidation for 2h, dialyze to purify for 2d, and freeze-dry to obtain oxidized sodium alginate powder.

[0062] (2) Weigh 80 mg of sodium alginate powder and dissolve it in 4 mL of deionized water, stirring until completely dissolved. Weigh 35 mg of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, 23 mg of N-hydroxysuccinimide, and 27 mg of 3-aminophenylboronic acid and add them to the above solution. Stir for 2 h to obtain a phenylboronic acid-based sodium alginate solution.

[0063] (3) Weigh 1.5g of polyvinyl alcohol 1799, dissolve it in 10mL of deionized water, heat and stir at 90℃ until completely dissolved; to obtain a polyvinyl alcohol solution.

[0064] (4) Take 1 mL of polyvinyl alcohol solution (15% w / v), add 1 mL of phenylboronic acid-based oxidized sodium alginate solution to it, stir quickly for 10 s to obtain rapid fluorescent self-healing oxidized sodium alginate / polyvinyl alcohol hydrogel.

[0065] Figure 2 The scanning electron microscope (SEM) image of the sodium alginate / polyvinyl alcohol fluorescent hydrogel prepared in this embodiment shows that the prepared hydrogel has a rich porous structure, which can store a large amount of water, making it an excellent drug carrier.

[0066] Example 3

[0067] This embodiment provides a method for preparing sodium alginate / polyvinyl alcohol fluorescent hydrogel, including the following steps:

[0068] (1) Weigh 1.5g of sodium alginate and dissolve it in 75mL of deionized water, stirring until completely dissolved. Weigh 0.75g of sodium periodate and dissolve it in 5mL of deionized water. Add the sodium periodate solution dropwise to the sodium alginate solution and stir in the dark for 24h. Add 1mL of ethylene glycol to the above solution to stop the oxidation for 2h, dialyze to purify for 2d, and freeze-dry to obtain oxidized sodium alginate powder.

[0069] (2) Weigh 80 mg of sodium alginate powder and dissolve it in 4 mL of deionized water, stirring until completely dissolved. Weigh 35 mg of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, 23 mg of N-hydroxysuccinimide, and 27 mg of 3-aminophenylboronic acid and add them to the above solution. Stir for 2 h to obtain a phenylboronic acid-based sodium alginate solution.

[0070] (3) Weigh 2g of polyvinyl alcohol 1799, dissolve it in 10mL of deionized water, heat and stir at 90℃ until completely dissolved; to obtain a polyvinyl alcohol solution.

[0071] (4) Take 1 mL of the polyvinyl alcohol solution (20% w / v) from step (3), add 1 mL of phenylboronic acid-based oxidized sodium alginate solution to it, stir rapidly for 10 s to obtain rapid fluorescent self-healing oxidized sodium alginate / polyvinyl alcohol hydrogel.

[0072] Test case

[0073] 1. Rheological test:

[0074] The rheometer strain parameters were set to 1%, the temperature to 25℃, and the scanning frequency range to 0.1-40Hz. The storage modulus of the oxidized sodium alginate / polyvinyl alcohol fluorescent hydrogels in Examples 1-3 as a function of frequency was obtained, as follows: Figure 3 As shown. Figure 3 In the study, the storage modulus of hydrogels at various concentrations remained stable with frequency changes, indicating the completion of internal cross-linking of the hydrogels; the storage modulus of the hydrogels increased with increasing polyvinyl alcohol solution concentration, indicating that modulus control can be achieved in material preparation.

[0075] The rheometer strain parameters were set to 1%, the temperature to 25℃, and the scanning frequency range to 1Hz. Rheological tests were performed on the mixing process of phenylboronic acid-based oxidized sodium alginate solution and polyvinyl alcohol solution. The storage modulus of the oxidized sodium alginate / polyvinyl alcohol fluorescent hydrogels in Examples 1-3 as a function of time were obtained, as follows: Figure 4 As shown. Figure 4In the experiment, it was observed that G′ gradually increased to G″ over time, indicating that both solutions transitioned to a solid gel state. Furthermore, as the polyvinyl alcohol concentration decreased, the moment when G′ exceeded G″ occurred even earlier. The reaction time for the 10% w / v polyvinyl alcohol solution (Example 1) was even shorter than the instrument reaction time, and the data directly showed that G′ was greater than G″ in the gel state.

[0076] 2. Adhesion performance test:

[0077] Example 2 shows the adhesion performance test of sodium alginate / polyvinyl alcohol fluorescent hydrogel. Figure 5 As shown, Figure 5 In this process, the prepared hydrogel is adhered to the finger joints, and as the fingers bend, the hydrogel adheres tightly to the skin surface.

[0078] 3. Swelling performance test:

[0079] The sodium alginate / polyvinyl alcohol fluorescent hydrogels prepared in Examples 1-3 were freeze-dried to constant weight and then weighed. The dried gel was then immersed in 10 mL of phosphate buffer (pH = 7.2). Every so often, the gel was removed, the surface moisture was carefully blotted with filter paper, and the wet weight was weighed. The swelling ratio was calculated. Figure 6 As shown in the figure, the swelling ratio of the hydrogel decreases with increasing crosslinking agent concentration, but can still reach over 400%, indicating that the prepared hydrogel has excellent swelling properties.

[0080] 4. Fluorescence performance determination:

[0081] The sodium alginate / polyvinyl alcohol fluorescent hydrogel prepared in Example 2 was used as the test object and irradiated with a 365nm ultraviolet lamp. Figure 7 As shown, the hydrogel itself is yellow, emits blue light under ultraviolet light, and eventually turns green.

[0082] 5. Self-healing performance test:

[0083] A portion of the sodium alginate / polyvinyl alcohol fluorescent hydrogel prepared in Example 2 was stained with methylene blue, and then brought into contact with the surface of another portion of the hydrogel. After standing for 10 minutes, the morphology of the hydrogel was observed. Figure 8 As shown, the two hydrogel parts become one.

[0084] Rheological tests were performed on the hydrogels to further verify their self-healing properties. The rheometer scanning frequency was set to 1 Hz, the temperature to 25 °C, and the strain parameter range to 1-300%. The modulus of the oxidized sodium alginate / polyvinyl alcohol fluorescent hydrogels in Examples 1-3 as a function of strain was obtained, as follows: Figure 9 As shown. Figure 9In the initial 1% low strain state, G′ was observed to be greater than G″, indicating a solid gel state. Subsequently, applying a 300% strain caused both G′ and G″ to decrease significantly. Furthermore, G′ became lower than G″, indicating the collapse of the network structure and the instantaneous transition of the hydrogel from a quasi-solid to a quasi-liquid state. After reducing the strain to 1%, both G′ and G″ immediately recovered to their original values, indicating that the hydrogel returned to its original solid state, which confirmed the change in the crosslinked network. During the cyclic testing, the healing process was completely repeatable and reversible, demonstrating the thixotropic and inherent self-healing properties of the hydrogel.

[0085] 6. pH response and reactive oxygen species response:

[0086] 200 μL of 1M hydrochloric acid, NaOH solution, and H2O2 solution were added dropwise to the sodium alginate / polyvinyl alcohol fluorescent hydrogel prepared in Example 2, respectively, and compared with the untreated hydrogel. After standing for 30 min, the morphology of the hydrogel was observed. Figure 10 As shown, the untreated blank hydrogel retained its original morphology. The hydrogel structure was disrupted by the addition of hydrochloric acid, the hydrogel structure remained unchanged after the addition of NaOH solution, and the hydrogel structure was also disrupted after the addition of H2O2 solution. This indicates that the prepared rapid fluorescent self-healing oxidized sodium alginate / polyvinyl alcohol hydrogel is pH sensitive, decomposing in acidic environments, with decomposition intensified in alkaline environments, and also decomposing in reactive oxygen species environments.

[0087] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing a rapidly gelling oxidized sodium alginate / polyvinyl alcohol fluorescent hydrogel, characterized in that, Includes the following steps: Sodium periodate was added to an aqueous solution of sodium alginate for oxidation. After dialysis and drying, oxidized sodium alginate was obtained. Sodium alginate oxide was dissolved in water, and 3-aminophenylboronic acid and an activator were added to react and obtain a sodium alginate oxide solution with phenylboronic acid group; the mass ratio of sodium alginate oxide, 3-aminophenylboronic acid and activator was 8:(2~3):(5~6); The sodium alginate solution with phenylboronic acid group is mixed with polyvinyl alcohol solution and stirred for 8-20 seconds to obtain the product. The mass ratio of sodium alginate to sodium periodate is 2:(0.8~1.2); The oxidation time is 20-30 hours; The concentration of the sodium alginate aqueous solution is 1~2wt%; The rapidly gelling sodium alginate / polyvinyl alcohol fluorescent hydrogel emits blue light under 365nm ultraviolet light.

2. The preparation method according to claim 1, characterized in that, The oxidation temperature is 20~30℃; the oxidation process is carried out under light-protected conditions.

3. The preparation method according to claim 1, characterized in that, In the step of dissolving sodium oxidized alginate in water, the concentration of sodium oxidized alginate is 1~3wt%.

4. The preparation method according to claim 1, characterized in that, The activator is 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide.

5. The preparation method according to claim 1, characterized in that, The concentration of the polyvinyl alcohol solution is 10~20% w / v.

6. The preparation method according to claim 1, characterized in that, The volume ratio of the phenylboronic acid-based oxidized sodium alginate solution to the polyvinyl alcohol solution is 1:(0.8~1.2).

7. The rapidly gelling sodium alginate / polyvinyl alcohol fluorescent hydrogel prepared by the preparation method according to any one of claims 1 to 6.

8. The application of the rapidly gelling oxidized sodium alginate / polyvinyl alcohol fluorescent hydrogel as described in claim 7 in the preparation of medical materials for tissue repair or fluorescent anti-counterfeiting materials.

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