CN116804091A - Water-retaining gleditsia sinensis polysaccharide-based hydrogel and preparation and application thereof - Google Patents
Water-retaining gleditsia sinensis polysaccharide-based hydrogel and preparation and application thereof Download PDFInfo
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- 150000004676 glycans Chemical class 0.000 title claims abstract description 103
- 229920001282 polysaccharide Polymers 0.000 title claims abstract description 102
- 239000005017 polysaccharide Substances 0.000 title claims abstract description 102
- 241000931143 Gleditsia sinensis Species 0.000 title claims abstract description 91
- 239000000017 hydrogel Substances 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 27
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims abstract description 20
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical group C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 claims abstract description 17
- KIUKXJAPPMFGSW-DNGZLQJQSA-N (2S,3S,4S,5R,6R)-6-[(2S,3R,4R,5S,6R)-3-Acetamido-2-[(2S,3S,4R,5R,6R)-6-[(2R,3R,4R,5S,6R)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 KIUKXJAPPMFGSW-DNGZLQJQSA-N 0.000 claims abstract description 11
- 229920002674 hyaluronan Polymers 0.000 claims abstract description 11
- 229960003160 hyaluronic acid Drugs 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002537 cosmetic Substances 0.000 claims abstract description 4
- 239000003814 drug Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 19
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 claims description 15
- 229960002218 sodium chlorite Drugs 0.000 claims description 15
- 230000004048 modification Effects 0.000 claims description 9
- 238000012986 modification Methods 0.000 claims description 9
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 8
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 2
- 238000000502 dialysis Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 239000000499 gel Substances 0.000 abstract description 19
- 238000003860 storage Methods 0.000 abstract description 4
- 239000003937 drug carrier Substances 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 206010016807 Fluid retention Diseases 0.000 description 16
- 230000006641 stabilisation Effects 0.000 description 13
- 238000011105 stabilization Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000012086 standard solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000000679 carrageenan Substances 0.000 description 2
- 229920001525 carrageenan Polymers 0.000 description 2
- 235000010418 carrageenan Nutrition 0.000 description 2
- 229940113118 carrageenan Drugs 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 2
- LGZDNJBUAAXEMN-UHFFFAOYSA-N 1,2,2,3-tetramethyl-1-oxidopiperidin-1-ium Chemical compound CC1CCC[N+](C)([O-])C1(C)C LGZDNJBUAAXEMN-UHFFFAOYSA-N 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- CUGZWHZWSVUSBE-UHFFFAOYSA-N 2-(oxiran-2-ylmethoxy)ethanol Chemical compound OCCOCC1CO1 CUGZWHZWSVUSBE-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000004113 cell culture Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- LJWKFGGDMBPPAZ-UHFFFAOYSA-N ethoxyethane;toluene Chemical compound CCOCC.CC1=CC=CC=C1 LJWKFGGDMBPPAZ-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- 238000000954 titration curve Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention relates to the technical field of hydrogels, and provides a water-retaining gleditsia sinensis polysaccharide-based hydrogel and preparation and application thereof, wherein the method comprises the following steps: 5 parts of gleditsia sinensis polysaccharide is activated under alkaline condition, then mixed with 0.5-1.5 parts of hyaluronic acid, and further added with 2-3 parts of glycidyl ether for reaction, so as to prepare the gleditsia sinensis polysaccharide-based hydrogel; the glycidyl ether is 1, 6-hexanediol diglycidyl ether and/or 1, 4-butanediol diglycidyl ether. The whole preparation process is simple, green and environment-friendly, the gel forming is quick, the prepared gleditsia sinensis polysaccharide-based hydrogel can give consideration to both water retention and mechanical properties, the water retention rate is more than 86%, the storage modulus is more than 208Pa, the loss modulus is more than 58Pa, and the gel forming method is wide in application range, and can be used in the fields of cosmetics and biological medicine as a drug carrier.
Description
Technical Field
The invention relates to the technical field of hydrogels, in particular to a water-retaining gleditsia sinensis polysaccharide-based hydrogel and preparation and application thereof.
Background
Gleditsia sinensis polysaccharide is a natural polymer material and has many excellent properties such as good biocompatibility, biodegradability, antibacterial property and the like, so that the Gleditsia sinensis polysaccharide is receiving more and more research attention. The Gleditsia sinensis polysaccharide hydrogel is a three-dimensional network structure formed by Gleditsia sinensis polysaccharide, and is widely applied to the fields of drug delivery, tissue engineering, cell culture and the like. When the water in the hydrogel evaporates, the hydrogel is gradually decolorized in the air, so that functions such as flexibility and elasticity of the hydrogel are gradually lost, and the hydrogel prepared from the gleditsia sinensis polysaccharide has obvious defects such as low gel forming strength, weak gel stability, unsatisfactory gel forming speed and time and the like.
Although there are a great deal of researches on how to improve the above properties of hydrogels, for example, in CN110025827B, potassium chloride is used as a cross-linking agent, and a low molecular weight gelator is blended with natural plant polysaccharide to obtain a mixed hydrogel with interpenetrating physical network structure, the process for preparing the hydrogel is complicated, and toxic reagents such as terephthaloyl chloride, triethylamine and the like are used, so that the prepared hydrogel has a certain biological toxicity, and the prepared hydrogel has a biological safety risk, so that the application of the hydrogel in the biological field is limited; in addition, in CN115073771A, bonding is realized through chemical bonds, hydrogen bonds and hydrophobic-hydrophobic interactions, and a solid hydrophobic coating and a hydrophobic oil layer double-layer coating on the surface of the gel are fixed so as to achieve the water retention effect, but the preparation process of the method has strict requirements, and after plasma/corona treatment is carried out on the surface of the gel, the gel is required to react with an aminosilane coupling agent, long-chain alkane and the like in an organic solvent such as ethyl acetate, chloroform and diethyl ether toluene so as to improve the water retention of the hydrogel. This preparation scheme uses too many organic reagents and the preparation process is too complicated, presents biosafety risks, and is not suitable for the preparation of natural polysaccharide hydrogels.
In view of this, the present invention has been proposed.
Disclosure of Invention
The invention provides a water-retaining gleditsia sinensis polysaccharide-based hydrogel and preparation and application thereof, which are used for solving the defects of unsatisfactory gel forming speed, low gel forming strength, weak colloid stability and insufficient water retaining property of the prepared gleditsia sinensis polysaccharide hydrogel in the prior art when the gel is prepared from the gleditsia sinensis polysaccharide.
Specifically, the invention provides a preparation method of a gleditsia sinensis polysaccharide-based hydrogel, which comprises the following steps: 5 parts of gleditsia sinensis polysaccharide is activated under alkaline condition, then mixed with more than 0.5 part of hyaluronic acid, and further added with 2-3 parts of glycidyl ether for reaction, so as to prepare the gleditsia sinensis polysaccharide-based hydrogel; the glycidyl ether is 1, 6-hexanediol diglycidyl ether and/or 1, 4-butanediol diglycidyl ether.
The Gleditsia sinensis polysaccharide has the advantages of safety, no toxicity, biodegradability, good biocompatibility and good self-repairing performance, and in order to fully and high-value utilize the Gleditsia sinensis polysaccharide, a great amount of experimental researches show that after hyaluronic acid is introduced into the Gleditsia sinensis polysaccharide, the Gleditsia sinensis polysaccharide further reacts with glycidyl ether with a specific structure to obtain gel with an interpenetrating network structure, the gel forms a compact unordered cross-linking structure through covalent bonds, hydrogen bonds and electrostatic attraction acting force, and the water-retaining property (the syneresis phenomenon is obviously improved), the stability, the mechanical property and the like of the Gleditsia sinensis polysaccharide-based hydrogel are all improved to different degrees. The glycidyl ether is mainly used for adjusting the crosslinking degree of covalent bonds in the hydrogel material, and in experiments, the glycidyl ether with different chain lengths has different bonding effects, if the glycidyl ether chain is too long, if polyethylene glycol diglycidyl ether is adopted, the strength of the obtained gleditsia sinensis polysaccharide-based hydrogel is too high, the water retention performance is poor, and if the glycidyl ether chain is too short, if ethylene glycol glycidyl ether is adopted, the strength of the obtained gleditsia sinensis polysaccharide-based hydrogel is low, and the water retention performance is poor.
According to the preparation method of the Gleditsia sinensis polysaccharide-based hydrogel, the mass ratio of the Gleditsia sinensis polysaccharide to the hyaluronic acid is 5:0.5-1.5;
and/or the mass ratio of the oxidized polysaccharide to the glycidyl ether is 5:1-3.
The invention can realize the remarkable improvement of the performance of the gleditsia sinensis polysaccharide-based hydrogel, in particular to the flexibility and the water-retaining property of the gleditsia sinensis polysaccharide-based hydrogel by introducing a small amount of hyaluronic acid.
The preparation method of the Gleditsia sinensis polysaccharide-based hydrogel provided by the invention comprises the following steps: 5 parts of Gleditsia sinensis polysaccharide is activated under alkaline condition, then mixed with 1 part of hyaluronic acid, and 2 parts of 1, 6-hexanediol diglycidyl ether is further added for reaction. In the test, the combination property of the gleditsia sinensis polysaccharide-based hydrogel obtained by the method is found to be optimal.
According to the preparation method of the Gleditsia sinensis polysaccharide-based hydrogel, the Gleditsia sinensis polysaccharide comprises the following steps before activation: the gleditsia sinensis polysaccharide is subjected to oxidation modification, and the carboxyl content of the oxidized gleditsia sinensis polysaccharide is within 0.5mmol/g, preferably 0.2 mmol/g-0.5 mmol/g. In experiments, the oxidation modification of the gleditsia sinensis polysaccharide can improve the dissolution performance of the gleditsia sinensis polysaccharide, not only can improve the utilization rate of the gleditsia sinensis polysaccharide, but also can obtain the gleditsia sinensis polysaccharide-based hydrogel without weakening the performance by controlling the oxidation degree of the gleditsia sinensis polysaccharide. Wherein, the oxidation degree is represented by the carboxyl content, and the method for testing the carboxyl content comprises the following steps: the extent of oxidative modification of the polysaccharide was determined by conductivity titration. Accurately weighing 0.2g of sample, dispersing the sample in 450mL of NaCl solution with the concentration of 0.001mol/L, fully stirring the solution to uniformly disperse the sample, and dropwise adding 0.1mol/L of HCl solution to ensure that the pH of the system is 2.5-3.0. The sample was stirred for 1h to fully acidify. Then, a 0.1mol/L NaOH standard solution was added dropwise at a rate of 0.1mL per minute for titration, and a titration curve was recorded with a conductivity meter. The carboxyl content was calculated by the following formula:
wherein C is COOH The content of carboxylic acid groups in a sample to be detected, mmol/g; c (C) 2 : concentration, mol/L of NaOH standard solution; v (V) 1 : the first equivalent consumes the volume of NaOH standard solution, mL; v (V) 2 : the second equivalent consumes the volume of NaOH standard solution, mL; m: sample dry mass, g.
According to the preparation method of the Gleditsia sinensis polysaccharide-based hydrogel, tempo (tetramethyl piperidine oxide), sodium chlorite and sodium hypochlorite are adopted as modifiers for oxidative modification.
According to the preparation method of the Gleditsia sinensis polysaccharide-based hydrogel, the mass ratio of the Tempo to the sodium chlorite is 0.015:1-3, and the mass ratio of the sodium chlorite to the sodium hypochlorite is 2:0.1-4.
The mass ratio of the Tempo to the sodium chlorite is more than or less than 0.015:1-3, and when the mass ratio of the sodium chlorite to the sodium hypochlorite is more than or less than 2:0.1-4, the oxidation degree of oxidized polysaccharide is lower, and the mechanical strength of the prepared Gleditsia sinensis polysaccharide-based hydrogel is lower.
According to the preparation method of the gleditsia sinensis polysaccharide-based hydrogel provided by the invention, the oxidative modification comprises the following steps:
dissolving gleditsia sinensis polysaccharide in phosphate buffer salt solution, adding Tempo and sodium chlorite, and dissolving to obtain a first product;
adding sodium hypochlorite PBS solution into the first product to react to obtain a second product;
dialyzing the second product, and freeze-drying to obtain the oxidized polysaccharide;
preferably, the molecular weight cut-off at dialysis is 8000kDa.
According to the preparation method of the Gleditsia sinensis polysaccharide-based hydrogel, the reaction by adding glycidyl ether comprises the following steps: the mixed solution obtained after adding the glycidyl ether is reacted for more than 6 hours at the temperature of 35-45 ℃.
In experiments, it is unexpectedly found that when the method is adopted to prepare the gleditsia sinensis polysaccharide-based hydrogel, gel can be efficiently formed at 35-45 ℃, and the obtained hydrogel has excellent performance, can be prolonged for gel forming time, and can not obviously improve the performance of the hydrogel.
The invention also provides the gleditsia sinensis polysaccharide-based hydrogel prepared by the preparation method of the gleditsia sinensis polysaccharide-based hydrogel; the gleditsia sinensis polysaccharide-based hydrogel has good mechanical strength, a structural network has a rich void structure, and the structure is compact, so that the gel state can be always presented; meanwhile, the hydrogel also has excellent water retention performance, can still keep the water content of almost 90% after being stored for 21 days, and also has good stability.
The invention also provides application of the gleditsia sinensis polysaccharide-based hydrogel in the fields of cosmetics and biological medicines, such as the field of cosmetic water retention; as a drug carrier applied to the field of biological medicine.
According to the water-retaining gleditsia sinensis polysaccharide-based hydrogel and the preparation and application thereof, 5 parts of gleditsia sinensis polysaccharide is activated under alkaline conditions and then mixed with 0.5-1.5 parts of hyaluronic acid, and 2-3 parts of 1, 6-hexanediol diglycidyl ether and/or 1, 4-butanediol diglycidyl ether are further added for reaction, so that the preparation of the novel gleditsia sinensis polysaccharide-based hydrogel is realized, the whole preparation process is simple, green and environment-friendly, the gel formation is quick, the strength and stability of the prepared gleditsia sinensis polysaccharide-based hydrogel are obviously improved, the water retention is also greatly improved, and the application range is wide
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The specific techniques or conditions are not identified in the examples and are described in the literature in this field or are carried out in accordance with the product specifications. The reagents or equipment used were conventional products available for purchase by regular vendors without the manufacturer's attention.
The test method of the invention comprises the following steps:
rheology test (rheologic test), the present invention evaluates storage modulus (G'), loss modulus (G ") at different oscillations, strains or shear rates using a rheometer (MCR 302, anton Paar Shanghai Trading co., ltd). The strain frequency of the frequency sweep is 1%, the oscillation frequency is 0.1-100Hz, and the oscillation frequency of the strain sweep is fixed to 1Hz, and the applied strain frequency is 0.01-100.
The water retention test method comprises the following steps: the hydrogels to be tested were placed in a 50% RH environment at 25℃and the water retention capacity of the hydrogels of the present invention was measured by the following formula:
wherein m is t Indicating the quality of the hydrogel at different moments, m 0 Indicating the initial mass of the hydrogel.
Example 1
The preparation method of the water-retaining gleditsia sinensis polysaccharide-based hydrogel comprises the following steps:
(1) 1g of Gleditsia sinensis polysaccharide was dissolved in 0.1M sodium Phosphate (PBS) solution (200 mL, pH 6.8), and then 0.015g of Tempo and 2g of sodium chlorite were added thereto and dissolved with stirring.
(2) 10mL of 0.1M sodium hypochlorite PBS solution is weighed, added into the solution prepared in the step (1), and kept stand at 60 ℃ for reaction for 48 hours.
(3) Dialyzing (molecular weight cut-off: 8000) the solution of step (2) for 48 hours, and freeze-drying to obtain Tempo oxidized polysaccharide (TGM) as white powder.
(4) Weighing 0.5g of TGM obtained in the step (3), dissolving in distilled water (300 mL), continuously stirring for 2h at 40 ℃, and then adding 4mL of sodium hydroxide solution (0.2 g/mL) to activate for 30min.
(5) 0.1g of HA was weighed and added to the solution prepared in step (4), and after stirring at 40℃for 10min, a uniform solution was formed.
(6) 0.2g of HDE (1, 6-hexanediol diglycidyl ether) was weighed into the solution prepared in step (5), and stirred at 40℃for 10min.
(7) And (3) taking out the magnetons in the solution in the step (6), adding the magnetons into a mould (glass tube), sealing the glass tube, and continuously reacting for 6 hours at the temperature of 40 ℃.
(8) Immersing the hydrogel obtained in the step (7) into deionized water to remove residual sodium hydroxide and HDE, thereby obtaining the water-retaining gleditsia sinensis polysaccharide-based hydrogel.
Example 2
The procedure for the preparation of the water-retaining polysaccharide-based hydrogel of gleditsia sinensis was essentially the same as in example 1, except that: 0.2g of 1, 6-hexanediol diglycidyl ether was replaced by 0.2g of 1, 4-butanediol diglycidyl ether.
Example 3
The procedure for the preparation of the water-retaining polysaccharide-based hydrogel of gleditsia sinensis was essentially the same as in example 1, except that: 0.1g of HA was replaced with 0.05g of HA.
Example 4
The preparation procedure of the gleditsia sinensis polysaccharide-based hydrogel was essentially the same as in example 1, except that: instead of steps (1) - (3), 0.5g of TGM in step (4) was replaced with 0.5g of Gleditsiae Abnormalis polysaccharide.
Example 5
The procedure for the preparation of the water-retaining polysaccharide-based hydrogel of gleditsia sinensis was essentially the same as in example 1, except that: 0.2g of HDE was replaced with 0.3g of HDE.
Example 6
The procedure for the preparation of the water-retaining polysaccharide-based hydrogel of gleditsia sinensis was essentially the same as in example 1, except that: 2g of sodium chlorite was replaced with 1g of sodium chlorite.
Example 7
The procedure for the preparation of the water-retaining polysaccharide-based hydrogel of gleditsia sinensis was essentially the same as in example 1, except that: 2g of sodium chlorite was replaced with 3g of sodium chlorite.
Example 8
The procedure for the preparation of the water-retaining polysaccharide-based hydrogel of gleditsia sinensis was essentially the same as in example 1, except that: the reaction was continued for 6 hours at 40℃in step (7) to 8 hours at 40 ℃.
Comparative example 1
The preparation procedure of the gleditsia sinensis polysaccharide-based hydrogel was essentially the same as in example 1, except that: 0.2g of 1, 6-hexanediol diglycidyl ether was replaced by 0.2g of borax.
Comparative example 2
The preparation procedure of the gleditsia sinensis polysaccharide-based hydrogel was essentially the same as in example 1, except that: 0.1g of HA was replaced with 0.1g of carrageenan.
Comparative example 3
The procedure for the preparation of the water-retaining polysaccharide-based hydrogel of gleditsia sinensis was essentially the same as in example 1, except that: 0.2g of HDE was replaced with 0.1g of HDE.
Comparative example 4
The procedure for the preparation of the water-retaining polysaccharide-based hydrogel of gleditsia sinensis was essentially the same as in example 1, except that: 0.2g of 1, 6-hexanediol diglycidyl ether was replaced by 0.2g of polyethylene glycol diglycidyl ether.
Comparative example 5
The procedure for the preparation of the water-retaining polysaccharide-based hydrogel of gleditsia sinensis was essentially the same as in example 1, except that: 0.2g of 1, 6-hexanediol diglycidyl ether was substituted for 0.2g of ethylene glycol diglycidyl ether.
The gleditsia sinensis polysaccharide-based hydrogels prepared in examples 1 to 8 and comparative examples 1 to 5 were tested, wherein the water retention was calculated from the mass of the hydrogel after 21 days, and the results were as follows:
| water retention rate | Storage modulus (Pa) | Loss modulus (Pa) | Stability of | |
| Example 1 | 90％ | 221.67 | 58.18 | Stabilization |
| Example 2 | 86％ | 231.94 | 62.13 | Stabilization |
| Example 3 | 82％ | 238.85 | 64.67 | Stabilization |
| Example 4 | 87％ | 208.41 | 61.154 | Stabilization |
| Example 5 | 86％ | 233.49 | 67.77 | Stabilization |
| Example 6 | 89％ | 228.41 | 60.42 | Stabilization |
| Example 7 | 90％ | 221.42 | 64.29 | Stabilization |
| Example 8 | 91％ | 215.04 | 61.98 | Stabilization |
| Comparative example 1 | 80％ | 158.66 | 57.119 | Stabilization |
| Comparative example 2 | 72％ | 213.77 | 62.746 | Stabilization |
| Comparative example 3 | 92％ | 154.45 | 34.66 | Stabilization |
| Comparative example 4 | 79％ | 310.35 | 88.722 | Stabilization |
| Comparative example 5 | 70％ | 93.95 | 38.063 | Stabilization |
From the above test results, it can be seen that: the hydrogel prepared by the method can achieve both water retention and mechanical properties, the water retention after 21 days is more than 82%, the storage modulus is more than 208Pa, and the loss modulus is more than 58 Pa. The chain length of the glycidyl ether has a large influence on the mechanical property and water retention of the hydrogel, when the glycidyl ether chain is too long, the longer alkyl chain obviously improves the mechanical strength of the gel, but the large gap formed by the large molecular space occupied by the alkyl chain with the same length weakens the water retention of the gel, when the alkyl chain is too short, the strength of the obtained gleditsia sinensis polysaccharide-based hydrogel is lower, the participating groups are insufficient to form an effective gap structure, so that the water retention is poor, and when the addition amount of the glycidyl ether is too low, the mechanical property of the hydrogel is also obviously reduced. In addition, compared with other hydrogel raw materials with good water-retaining property, such as carrageenan, the hyaluronic acid is more suitable for the use of the gleditsia sinensis polysaccharide.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A method for preparing a gleditsia sinensis polysaccharide-based hydrogel, which is characterized by comprising the following steps: 5 parts of gleditsia sinensis polysaccharide is activated under alkaline condition, then mixed with 0.5-1.5 parts of hyaluronic acid, and further added with 2-3 parts of glycidyl ether for reaction, so as to prepare the gleditsia sinensis polysaccharide-based hydrogel; the glycidyl ether is 1, 6-hexanediol diglycidyl ether and/or 1, 4-butanediol diglycidyl ether.
2. The preparation method of the gleditsia sinensis polysaccharide-based hydrogel according to claim 1, wherein the mass ratio of the gleditsia sinensis polysaccharide to the hyaluronic acid is 5:0.5-1.5;
and/or the mass ratio of the oxidized polysaccharide to the glycidyl ether is 5:1-3.
3. The method for preparing the gleditsia sinensis polysaccharide-based hydrogel according to claim 1, comprising: 5 parts of Gleditsia sinensis polysaccharide is activated under alkaline condition, then mixed with 1 part of hyaluronic acid, and 2 parts of 1, 6-hexanediol diglycidyl ether is further added for reaction.
4. The method for preparing a Gleditsia sinensis polysaccharide-based hydrogel according to claim 3, wherein the Gleditsia sinensis polysaccharide comprises, prior to activation: the gleditsia sinensis polysaccharide is subjected to oxidation modification, and the carboxyl content of the oxidized gleditsia sinensis polysaccharide is within 0.5mmol/g, preferably 0.2 mmol/g-0.5 mmol/g.
5. The method for preparing the Gleditsia sinensis polysaccharide based hydrogel according to claim 4, wherein the oxidative modification uses Tempo, sodium chlorite and sodium hypochlorite as modifiers.
6. The preparation method of the gleditsia sinensis polysaccharide-based hydrogel according to claim 5, wherein the mass ratio of the Tempo to the sodium chlorite is 0.015:1-3, and the mass ratio of the sodium chlorite to the sodium hypochlorite is 2:0.1-4.
7. The method of preparing a gleditsia sinensis polysaccharide-based hydrogel according to any one of claims 4 to 6, wherein the oxidative modification comprises:
dissolving gleditsia sinensis polysaccharide in sodium phosphate solution, adding Tempo and sodium chlorite, and dissolving to obtain a first product;
adding sodium hypochlorite PBS solution into the first product to react to obtain a second product;
dialyzing the second product, and freeze-drying to obtain oxidized polysaccharide;
preferably, the molecular weight cut-off at dialysis is 8000kDa.
8. The method for preparing a gleditsia sinensis polysaccharide-based hydrogel according to any one of claims 1 to 7, wherein the adding glycidyl ether to react comprises: the mixed solution obtained after adding the glycidyl ether is reacted for more than 6 hours at the temperature of 35-45 ℃.
9. The process for producing a nigre polysaccharide-based hydrogel according to any one of claims 1 to 8.
10. Use of the gleditsia sinensis polysaccharide-based hydrogel of claim 8 or 9 in the fields of cosmetics and biological medicine.
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