CN101914225A - Method for preparing hyaluronic acid gel by using macromolecule photocrosslinking agent - Google Patents
Method for preparing hyaluronic acid gel by using macromolecule photocrosslinking agent Download PDFInfo
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- CN101914225A CN101914225A CN201010250802XA CN201010250802A CN101914225A CN 101914225 A CN101914225 A CN 101914225A CN 201010250802X A CN201010250802X A CN 201010250802XA CN 201010250802 A CN201010250802 A CN 201010250802A CN 101914225 A CN101914225 A CN 101914225A
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Abstract
The invention relates to a method for preparing a hyaluronic acid gel by using a macromolecule photocrosslinking agent, belonging to the technical field of preparation of polymer blends and functional polymers. In the invention, a hyaluronic acid is used as the main part of the gel, a macromolecule photocrosslinking agent is used as the crosslinking agent, photosensitive groups on the macromolecule photocrosslinking agent are subject to a photodimerization reaction to form a crosslinked network under the irradiation of ultraviolet light, thus changing the defect that toxic materials are brought in if a crosslinking agent is added in the traditional gel preparation process. The hyaluronic acid gel prepared by the macromolecule photocrosslinking agent has the characteristics of light sensitivity, pH sensitivity, temperature sensitivity, brine sensitivity and the like. The hyaluronic acid gel can be somewhat used for medicament carrying, and has a certain release control effect on medicaments.
Description
Technical field
A kind of method of preparing hyaluronic acid gel by using macromolecule photocrosslinking agent belongs to polymer blended, functional polymer preparing technical field.
Background technology
Hyaluronic acid (HA) has another name called glass acid, is a kind of macromole acidic mucopolysaccharide, is present in widely in the reticular tissue of organism, is at first separated from bovine vitreous body in 1934 by Meyer and Palmer.Hyaluronic acid is present in the animal tissues, has biocompatibility and biodegradability.
The straight chain macromolecular polysaccharide that hyaluronic acid is made up of for disaccharide unit glucuronic acid and n acetylglucosamine n, relative molecular weight is 10-200 ten thousand.Hyaluronic acid is in the aqueous solution, its numberator height stretches, and be intertwined and connected mutually, form the successive reticulated structure, water molecules then combines with hyaluronan molecule by polar link and hydrogen bond in this network, make hyaluronic acid just as " molecule sponge ", can absorb and keep the moisture of 1000 times of himself quality.Because hyaluronic acid has good water-absorbent, so be particularly suitable for doing gel.
Using macromolecule photocrosslinking agent is a kind of novel photochromics, the photosensitivity height, and only needing just can be crosslinked under ultra violet lamp, and technology is simple, the preparation condition gentleness.Behind the photo-crosslinking, form polymkeric substance with network structure.The present invention relates to a kind of using macromolecule photocrosslinking agent that utilizes and be main body for linking agent, hyaluronic acid, the method that photo-crosslinking directly forms gel after both free blend prepares hyaluronic acid derivatives.This method can prepare hyaluronic acid derivatives by the method for this simple environmental protection of ultraviolet lighting, have the blend monomer be simple and easy to, the characteristics of preparation condition gentleness.Preparation and applied research to hyaluronic acid derivatives have very profound significance.
Summary of the invention
The purpose of this invention is to provide a kind of method with preparing hyaluronic acid gel by using macromolecule photocrosslinking agent, this method technology is simple, and does not have the hazardous and noxious substances adding, and is workable.
Technical scheme of the present invention: a kind of method of preparing hyaluronic acid gel by using macromolecule photocrosslinking agent, step is as follows:
(1) hyaluronic acid is dissolved in the water, mixed 12-24 hour, make mass concentration and be 0.1%～5% hyaluronic acid aqueous solution;
(2) using macromolecule photocrosslinking agent is joined in the hyaluronic acid aqueous solution of step (1) gained, illumination under ultraviolet lamp, light application time is 50～500s, the crosslinked hyaluronic acid derivatives that gets;
Described using macromolecule photocrosslinking agent is the using macromolecule photocrosslinking agent that contains a large amount of hydrophilic radicals and photosensitive group on the molecular backbone chain;
(3) the gained hyaluronic acid derivatives was put into deionized water dialysis 3 days in the step (2), changed one time water every 5 hours;
(4) the hyaluronic acid derivatives lyophilize after dialysis is finished in the step (3) obtains the dry state hyaluronic acid derivatives;
With the hyaluronic acid with strong absorptive matter is that gel main body, using macromolecule photocrosslinking agent are linking agent, both mix the back under the condition of UV-light, utilize the photosensitive group generation light dimerization reaction on the using macromolecule photocrosslinking agent to form cross-linked network, improve the hyaluronic acid hydrophobicity; And by regulating the hyaluronic acid and the mass ratio of using macromolecule photocrosslinking agent, the swelling ratio that the ultraviolet lighting time is regulated the gained hyaluronic acid derivatives.
Described hyaluronic molecular weight is 10～2,000,000.
Described hyaluronic acid is selected the hyaluronic acid of Production by Microorganism Fermentation for use.
The general structure of described using macromolecule photocrosslinking agent is as follows:
R in the formula
1Be hydrophilic radical, comprise hydroxyl, carboxyl, amino hydrophilic radical;
R
2Be photosensitive group, select one or more of following a few class photosensitive groups for use, its structural formula is the pyridine salt: (I) 4-(4-(N-vinyl benzyl-N-acrinyl) aminomethyl-styryl)-picoline-Methylsulfate, (II) 4-(4-(N-vinyl benzyl-N-benzyl aminomethyl)-styryl)-picoline-Methylsulfate, (III) 4-(4-(N-vinyl benzyl-N-DOPA amido-methyl)-styryl)-picoline-Methylsulfate, (IV) 4-styryl-(4-vinyl benzyl) pyridinium salt.
The number-average molecular weight of used using macromolecule photocrosslinking agent is 3000～100000, and the mol ratio that photosensitive group accounts for the repeated structural unit of using macromolecule photocrosslinking agent is 0.5%～20%.
Hyaluronic acid: the mass ratio of using macromolecule photocrosslinking agent is 7: 1～1: 7.
The gained hyaluronic acid derivatives has water-intake rate preferably, and the moisture of gel absorption reaches 10～7000 times of weight own, and along with the increase of using macromolecule photocrosslinking agent content, the water-intake rate of gel reduces.
The gained hyaluronic acid derivatives has tangible sensitivity of light, and the swelling ratio of hyaluronic acid derivatives is controlled; After the photo-crosslinking degree reached maximum, the swelling ratio of hyaluronic acid derivatives changed little.
The gained hyaluronic acid derivatives has pH susceptibility, temperature sensitivity and salt concn susceptibility, and along with the increase of using macromolecule photocrosslinking agent content, hyaluronic acid derivatives weakens the susceptibility of these three kinds of factors.
The gained hyaluronic acid derivatives is applied to drug loading, and medicine is had controlled-release effect.
The measuring method of gel swelling rate:
Recording the crosslinked hyaluronic acid derivatives dry weight of dry state is W
0, the hyaluronic acid derivatives that dry state is crosslinked is put under the different pH, under the differing temps, in the solution under the different salt concn, places 25 ℃ water-bath, and recording its weight in wet base under the different time is W
1, the swelling ratio when the equilibrium swelling rate is hyaluronic acid derivatives swelling 24h.
Swelling ratio=(W
1-W
0)/W
0
The crosslinked hyaluronic acid derivatives of gained is in different light under the time, under the different pH, under the differing temps after measured, swelling ratio under the different salt concn, can have apparent in view sensitivity of light by this hyaluronic acid derivatives, pH susceptibility, temperature sensitivity and brine sensitivity.
Beneficial effect of the present invention: the present invention is with hyaluronic acid (HA) and using macromolecule photocrosslinking agent blend, water is solvent, ultraviolet lighting is a reaction conditions, utilize the hyaluronic acid derivatives of using macromolecule photocrosslinking agent preparation, have the blend monomer be simple and easy to, polymerizing condition gentleness, advantage such as gel structure is controlled and swelling ratio is controlled.The reaction synoptic diagram as shown in Figure 1.
Description of drawings
Fig. 1. hyaluronic acid and using macromolecule photocrosslinking agent form the reaction synoptic diagram of hyaluronic acid derivatives.
The infrared spectrogram of the hyaluronic acid derivatives that Fig. 2 .PVA-SbQ is crosslinked.
The crosslinked hyaluronic acid derivatives of Fig. 3 .PVA-SbQ is at the swelling curve of different light under the time.
The equilibrium swelling rate of hyaluronic acid derivatives under different time that Fig. 4 .PVA-SbQ is crosslinked.
The equilibrium swelling rate of hyaluronic acid derivatives under different pH that Fig. 5 .PVA-SbQ is crosslinked.
The equilibrium swelling rate of hyaluronic acid derivatives under differing temps that Fig. 6 .PVA-SbQ is crosslinked.
The equilibrium swelling rate of hyaluronic acid derivatives under different salt concn that Fig. 7 .PVA-SbQ is crosslinked.
Embodiment
Below in conjunction with embodiment the present invention is further described in detail, but does not limit the present invention.
Embodiment 1:
(molecular weight is 6.3 * 10 to the hyaluronic acid of configuration 2% in the beaker of 100mL
5Da) the aqueous solution is placed under the room temperature to stir and hyaluronic acid was dissolved fully in 24 hours.Using macromolecule photocrosslinking agent adopts polyvinyl alcohol graft stibazole salt (PVA-SbQ).Ratio in m (HA): m (PVA-SbQ)=7: 1～1: 7 in the beaker that encases with masking foil adds two kinds of materials, stirring 30min mixes both, back the direct ultraviolet photo-crosslinking becomes hyaluronic acid derivatives with the centrifugal 5min of 3000 rev/mins rotating speed, and light application time is 50～500s.The gained hyaluronic acid derivatives changed one time water with deionized water dialysis 3 days every 5 hours; Carry out lyophilize after liquid nitrogen is directly freezing, promptly get the dry state hyaluronic acid derivatives.
Embodiment 2:
(molecular weight is 2 * 10 to the hyaluronic acid of configuration 2% in the beaker of 100mL
5Da) the aqueous solution is placed under the room temperature to stir and more than 12 hours hyaluronic acid is dissolved fully.Ratio in m (HA): m (PVA-SbQ)=7: 1～1: 7 in the beaker that encases with masking foil adds two kinds of materials, stirring 30min mixes both, back the direct ultraviolet photo-crosslinking becomes hyaluronic acid derivatives with the centrifugal 5min of 3000 rev/mins rotating speed, and light application time is 50～500s.The gained hyaluronic acid derivatives changed one time water with deionized water dialysis 3 days every 5 hours; Carry out lyophilize after liquid nitrogen is directly freezing, promptly get the dry state hyaluronic acid derivatives.
The Infrared spectroscopy of the hyaluronic acid derivatives that embodiment 3 usefulness PVA-SbQ are crosslinked
Hyaluronic charateristic avsorption band: 1619cm
-1Be the antisymmetric vibration charateristic avsorption band of carbonyl C=O, 1413cm
-1Be the vibration absorption peak of C=O, 1051cm
-1It is v (C-OH) charateristic avsorption band.The charateristic avsorption band of PVA-SbQ: 1732cm
-1Be v on the pyridine ring (C=N) absorption peak, 1377cm
-1Be chain end δ (CH3) absorption peak, 1256cm
-1Be δ (O-H) absorption peak, 849cm
-1And 760cm
-1Out-of-plane deformation vibration for phenyl ring.In the crosslinked preceding infrared spectrum of different ratios hyaluronic acid derivatives and PVA-SbQ, can find: behind the photo-crosslinking, the hyaluronic acid derivatives of three kinds of ratios is at 920cm from Fig. 2
-1C=C rocking vibration peak reduce 1256cm
-1The C=C of place scissoring vibration peak reduces, simultaneously 1256cm
-1The O-H of place flexural vibration absorption peak still exists.Photo-crosslinking has taken place in this explanation different ratios hyaluronic acid derivatives under illumination condition.
The swelling curve of the hyaluronic acid derivatives different light time that embodiment 4PVA-SbQ is crosslinked
Preparation m (HA): m (PVA-SbQ)=1: 3 hyaluronic acid and the mixing solutions of PVA-SbQ, difference illumination 50s, 150s, 300s, 450s, 500s under ultraviolet lamp, make the dry state hyaluronic acid derivatives, record the swelling curve of the hyaluronic acid derivatives of different light under the time in the aqueous solution afterwards, as shown in Figure 3.
When just beginning swelling, because HA goes up the electrostatic repulsion effect of carboxyl, the quick swelling of the hyaluronic acid derivatives of different light under the time, all gel swelling curve unanimities of this stage.When swelling reaches maximum value, light application time is to occur in the gel swelling process of 50s, 150s, 300s retreating the swollen phenomenon when the gel swelling rate reaches maximum value, and when light application time continuation increase reached 450s and 500s, the gel swelling process was exactly that typical the increase earlier afterwards reaches maximum value until balance.This is when being 50s, 150s, 300s because of light application time, the gained gel is in the sol-gel intermediate state, the degree of crosslinking of PVA-SbQ wherein is not enough to stop the diffusion of HA in water, reaches maximum value and retreats the swollen phenomenon so can occur the gel swelling rate in the gel swelling process.When light application time increases to 450s, the degree of crosslinking of PVA-SbQ be enough to stop HA in water diffusion and reach certain balance, when continuing to increase light application time to 500s, the swelling curve of gel is similar to the swelling curve of 450s.This also matches with the flow curve result of different light under the time, illustrates that this ratio gel changes solid gel into by liquid colloidal sol when 450s.
The swelling ratio of hyaluronic acid derivatives under different time of embodiment 5 different crosslinked ratios
Take by weighing the hyaluronic acid derivatives of different crosslinked ratios, put into the beaker of dress water, place 25 ℃ water bath with thermostatic control, record the swelling ratio of crosslinked hyaluronic acid derivatives under different time, each ratio is done three parallel laboratory tests.Swelling ratio was mapped to the time, obtained the swelling ratio of different crosslinked ratio hyaluronic acid derivatives under different time, as shown in Figure 4.
The swelling ratio of the hyaluronic acid derivatives of different crosslinked ratios under different time all is to increase earlier afterwards to reach maximum value until balance as can be seen from Figure 4.Swelling ratio maximum when wherein the hyaluronic acid derivatives of m (HA): m (PVA-SbQ)=1: 3 reaches swelling equilibrium reaches 70.9 times of own weight, and along with the minimizing of HA and the increase of PVA-SbQ, swelling ratio sharply descends.To both ratios is that 1: 7 crosslinked hyaluronic acid derivatives swelling ratio is 12.7 times of own weight.
When hyaluronic acid derivatives has just begun swelling since HA on carboxyl static repulsive interaction, the quick swelling of gel.HA intensive hydrophilic interaction makes it enter water from gel network, and along with the increase of PVA-SbQ, formed cross-linked network degree of crosslinking is identical under the identical time of illumination, and hyaluronic content becomes the principal element of restriction swelling ratio.So along with the minimizing of HA content, the swelling ratio of the hyaluronic acid derivatives that PVA-SbQ is crosslinked reduces.
The swelling ratio of hyaluronic acid derivatives under different pH of embodiment 6 different crosslinked ratios
Dispose different pH solution, take by weighing the hyaluronic acid derivatives of different crosslinked ratios, place under the different pH solution, the swelling ratio of the hyaluronic acid derivatives of test cross connection behind the swelling 24h.Swelling ratio is mapped to pH, obtains the swelling ratio of different crosslinked ratio hyaluronic acid derivatives under different pH, as shown in Figure 5.
As can be seen from Figure 5 along with the increase of PVA-SbQ, the reducing of pH sensitive group ratio, crosslinked hyaluronic acid derivatives is subjected to the influence of pH more little, and gained gel swelling rate is influenced by pH hardly when m (HA): m (PVA-SbQ)=1: 7.
When the increase under pH=9 of the crosslinked hyaluronic acid derivatives of m (HA): m (PVA-SbQ)=1: 3 along with pH, the crosslinked hyaluronic acid derivatives swelling ratio of all proportions increases, along with the crosslinked hyaluronic acid derivatives swelling ratio of the increase of pH reduces, illustrate that crosslinked hyaluronic acid derivatives has pH susceptibility after the pH=9.This is because in the hyaluronic acid structure this pH sensitive groups of carboxyl is arranged, and acidic conditions suppresses its ionization down, and alkaline condition promotes its ionization down.Between pH=4-7, acidic conditions suppresses carboxyl ionization down, and the keying action of gel and water is weakened, and showing is that the gel swelling rate descends.So under this pH scope, along with acidity strengthens, swelling ratio descends.Between pH=7-9, alkaline condition promotes the ionization of carboxyl down, make the keying action of gel and water strengthen, showing the gel swelling rate rises, institute's gel swelling ratio under this section pH in varing proportions strengthens and increases along with alkalescence, behind pH＞9, along with the enhancing of alkalescence, the alkali resistance of gel weakens, so the swelling ratio of this stage gel descends.
The swelling ratio of hyaluronic acid derivatives under differing temps of embodiment 7 different crosslinked ratios
Take by weighing the hyaluronic acid derivatives of different crosslinked ratios, place the water-bath of differing temps, the swelling ratio of the hyaluronic acid derivatives of test cross connection behind the swelling 24h, each ratio is done three parallel laboratory tests.Swelling ratio is mapped to temperature, obtains the swelling ratio of hyaluronic acid derivatives under differing temps of different crosslinked ratios, as shown in Figure 6.
As can be seen from Figure 6 the swelling ratio of the hyaluronic acid derivatives of different crosslinked ratios presents the trend that reduces with the rising of temperature, this is because the hydrophilic radical-OH that exists on the hydrophilic molecules chain in the PVA-SbQ/HA system at low temperatures,-COOH easily associates by hydrogen bond and water molecules, make the hydrogen bond rupture between the molecule, Van der Waals force weakens relatively, Intermolecular Forces weakens, molecular chain is opened, cause the gel swelling suction to strengthen, and when temperature rises, the hydrogen bond action of its macromolecular chain and water weakens, and hydrophobic interaction strengthens, and causes the gel swelling suction to weaken.
The swelling ratio of hyaluronic acid derivatives under different salt concn of embodiment 8 different crosslinked ratios
Dispose the solution of different salt concn, take by weighing the hyaluronic acid derivatives of different crosslinked ratios, place different salt concn solution, the swelling ratio of the hyaluronic acid derivatives of test cross connection behind the swelling 24h, each ratio is done three parallel laboratory tests.Swelling ratio is mapped to salt concn, obtains the swelling ratio of different crosslinked ratio hyaluronic acid derivatives under different salt concn, as shown in Figure 7.
As can be seen from Figure 7 when salt concn is 0.01mol/L, the hyaluronic acid derivatives of different crosslinked ratios is compared swelling ratio with not with salt the time and is sharply reduced, but when salt concn reaches 0.1mol/L, the swelling ratio increase, further increase salt concn, swelling ratio reduces with smaller amplitude.Sharply reducing with salt 0.01mol/L gel swelling rate is because hyaluronic acid is electronegative in the aqueous solution, PVA-SbQ is positively charged, they can be owing to sodium positive ion and the chlorine negative ion in the electrostatic interaction difference planar water, make the keying action of hyaluronic acid derivatives and water weaken, so crosslinked hyaluronic acid derivatives swelling ratio sharply reduces when salt concn is 0.01mol/L, it is because the increase of salt concn that salt concn rises to swelling ratio between the 0.1mol/L at 0.01mol/L, and gel surface is being assembled negative ions can be made the keying action of gel and water increase to cause the water-intake rate increase.Increase swelling ratio along with salt concn reduces slightly afterwards, and the 0.1mol/L that acts on of salt concn reaches maximum, and it is less to the influence of gel swelling rate to increase salt concn afterwards.
Claims (10)
1. the method for a preparing hyaluronic acid gel by using macromolecule photocrosslinking agent is characterized in that, step is as follows:
(1) hyaluronic acid is dissolved in the water, mixed 12-24 hour, make mass concentration and be 0.1%～5% hyaluronic acid aqueous solution;
(2) using macromolecule photocrosslinking agent is joined in the hyaluronic acid aqueous solution of step (1) gained, illumination under ultraviolet lamp, light application time is 50～500s, the crosslinked hyaluronic acid derivatives that gets;
Described using macromolecule photocrosslinking agent is the using macromolecule photocrosslinking agent that contains a large amount of hydrophilic radicals and photosensitive group on the molecular backbone chain;
(3) step (2) gained hyaluronic acid derivatives is put into deionized water dialysis 3 days, changed one time water every 5 hours;
(4) the hyaluronic acid derivatives lyophilize that step (3) is dialysed after finishing obtains the dry state hyaluronic acid derivatives;
With the hyaluronic acid with strong absorptive matter is that gel main body, using macromolecule photocrosslinking agent are linking agent, both mix the back under the condition of UV-light, utilize the photosensitive group generation light dimerization reaction on the using macromolecule photocrosslinking agent to form cross-linked network, improve the hyaluronic acid hydrophobicity; And by regulating the hyaluronic acid and the mass ratio of using macromolecule photocrosslinking agent, the swelling ratio that the ultraviolet lighting time is regulated the gained hyaluronic acid derivatives.
2. method according to claim 1 is characterized in that, described hyaluronic molecular weight is 10～2,000,000.
3. method according to claim 1 is characterized in that described hyaluronic acid is selected the hyaluronic acid of Production by Microorganism Fermentation for use.
4. method according to claim 1 is characterized in that, the general structure of described using macromolecule photocrosslinking agent is as follows:
R in the formula
1Be hydrophilic radical, comprise hydroxyl, carboxyl, amino hydrophilic radical;
R
2Be photosensitive group, select one or more of following a few class photosensitive groups for use, its structural formula is the pyridine salt: (I) 4-(4-(N-vinyl benzyl-N-acrinyl) aminomethyl-styryl)-picoline-Methylsulfate, (II) 4-(4-(N-vinyl benzyl-N-benzyl aminomethyl)-styryl)-picoline-Methylsulfate, (III) 4-(4-(N-vinyl benzyl-N-DOPA amido-methyl)-styryl)-picoline-Methylsulfate, (IV) 4-styryl-(4-vinyl benzyl) pyridinium salt.
5. method according to claim 1 is characterized in that, the number-average molecular weight of used using macromolecule photocrosslinking agent is 3000～100000, and the mol ratio that photosensitive group accounts for the repeated structural unit of using macromolecule photocrosslinking agent is 0.5%～20%.
6. method according to claim 1 is characterized in that hyaluronic acid: the mass ratio of using macromolecule photocrosslinking agent is 7: 1～1: 7.
7. use the hyaluronic acid derivatives of the described method preparation of claim 1, it is characterized in that: the gained hyaluronic acid derivatives has water-intake rate preferably, the moisture of gel absorption reaches 10～7000 times of weight own, and along with the increase of using macromolecule photocrosslinking agent content, the water-intake rate of gel reduces.
8. with the hyaluronic acid derivatives of the described method preparation of claim 1, it is characterized in that: the gained hyaluronic acid derivatives has sensitivity of light, and the swelling ratio of hyaluronic acid derivatives is controlled; After the photo-crosslinking degree reached maximum, the swelling ratio of hyaluronic acid derivatives changed little.
9. use the hyaluronic acid derivatives of the described method preparation of claim 1, it is characterized in that: the gained hyaluronic acid derivatives has pH susceptibility, temperature sensitivity and salt concn susceptibility, along with the increase of using macromolecule photocrosslinking agent content, hyaluronic acid derivatives weakens the susceptibility of these three kinds of factors.
10. with the hyaluronic acid derivatives of the described method preparation of claim 1, it is characterized in that: the gained hyaluronic acid derivatives is applied to drug loading, and medicine is had controlled-release effect.
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| US20180200371A1 (en) * | 2012-05-01 | 2018-07-19 | Karen K. Brown | Hyaluronic acid stabilizer |
| CN103183833B (en) * | 2012-12-14 | 2016-02-17 | 江南大学 | The preparation method of a kind of photo-crosslinking sodium alginate and polyvinyl alcohol-styryl pyridinium condenses composite membrane |
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| CN105669923A (en) * | 2016-04-12 | 2016-06-15 | 江南大学 | Photosensitive antibacterial hydrogel and preparation method thereof |
| CN106832439A (en) * | 2017-03-26 | 2017-06-13 | 广州市芯检康生物科技有限公司 | A kind of multi-functional instant composite of new aeroge for blood components protection and preparation method thereof |
| CN107033371A (en) * | 2017-04-28 | 2017-08-11 | 江南大学 | A kind of preparation method of photo crosslinked polyethylene alcohol/nanocrystalline cellulose PVA/CNC composite aquogels |
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| CN110327056A (en) * | 2019-05-24 | 2019-10-15 | 武汉大学 | A kind of intelligent aqueous gel and preparation method thereof for visualizing blood sugar test |
| CN110327056B (en) * | 2019-05-24 | 2021-01-01 | 武汉大学 | Intelligent hydrogel for visual blood glucose detection and preparation method thereof |
| CN114249905A (en) * | 2020-09-25 | 2022-03-29 | 北京化工大学 | Photoinitiator-free 3D printing polyvinyl alcohol-based hydrogel and preparation method and application thereof |
| CN113274314A (en) * | 2021-05-07 | 2021-08-20 | 山东省药学科学院 | Application of salt sensitive hydrogel as intelligent water control and replenishing material |
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