CN114133593A - Cellulose-polyethylene glycol-layered silicon dioxide composite hydrogel and application thereof - Google Patents
Cellulose-polyethylene glycol-layered silicon dioxide composite hydrogel and application thereof Download PDFInfo
- Publication number
- CN114133593A CN114133593A CN202111405230.2A CN202111405230A CN114133593A CN 114133593 A CN114133593 A CN 114133593A CN 202111405230 A CN202111405230 A CN 202111405230A CN 114133593 A CN114133593 A CN 114133593A
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- Prior art keywords
- cellulose
- polyethylene glycol
- composite hydrogel
- hydrogel
- molecular weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000017 hydrogel Substances 0.000 title claims abstract description 93
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 46
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 26
- 239000004698 Polyethylene Substances 0.000 title abstract description 6
- 229920000573 polyethylene Polymers 0.000 title abstract description 6
- 229920002678 cellulose Polymers 0.000 claims abstract description 51
- 239000001913 cellulose Substances 0.000 claims abstract description 50
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 42
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910001868 water Inorganic materials 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 9
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 74
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 71
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 70
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 70
- 235000010980 cellulose Nutrition 0.000 claims description 48
- 238000006467 substitution reaction Methods 0.000 claims description 22
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 20
- -1 hydroxyethyl carboxymethyl Chemical group 0.000 claims description 13
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 10
- 239000001110 calcium chloride Substances 0.000 claims description 10
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 10
- 239000011780 sodium chloride Substances 0.000 claims description 10
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 4
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 229920003086 cellulose ether Polymers 0.000 claims description 3
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 3
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 3
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 3
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 3
- 239000011812 mixed powder Substances 0.000 claims description 3
- KXJGSNRAQWDDJT-UHFFFAOYSA-N 1-acetyl-5-bromo-2h-indol-3-one Chemical compound BrC1=CC=C2N(C(=O)C)CC(=O)C2=C1 KXJGSNRAQWDDJT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 229920003090 carboxymethyl hydroxyethyl cellulose Polymers 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000000565 sealant Substances 0.000 claims description 2
- 229920000896 Ethulose Polymers 0.000 claims 1
- 239000001859 Ethyl hydroxyethyl cellulose Substances 0.000 claims 1
- 229920001479 Hydroxyethyl methyl cellulose Polymers 0.000 claims 1
- 230000003073 embolic effect Effects 0.000 claims 1
- 235000019326 ethyl hydroxyethyl cellulose Nutrition 0.000 claims 1
- 229920000609 methyl cellulose Polymers 0.000 claims 1
- 239000001923 methylcellulose Substances 0.000 claims 1
- 235000010981 methylcellulose Nutrition 0.000 claims 1
- 239000003431 cross linking reagent Substances 0.000 abstract description 4
- 238000010382 chemical cross-linking Methods 0.000 abstract description 3
- 238000002347 injection Methods 0.000 abstract description 2
- 239000007924 injection Substances 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- 229940094522 laponite Drugs 0.000 description 14
- XCOBTUNSZUJCDH-UHFFFAOYSA-B lithium magnesium sodium silicate Chemical compound [Li+].[Li+].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 XCOBTUNSZUJCDH-UHFFFAOYSA-B 0.000 description 14
- 230000015556 catabolic process Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- 150000002170 ethers Chemical class 0.000 description 5
- 239000000499 gel Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 4
- 235000011148 calcium chloride Nutrition 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 4
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 4
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 4
- 210000001519 tissue Anatomy 0.000 description 4
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 3
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 3
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- PTHCMJGKKRQCBF-UHFFFAOYSA-N Cellulose, microcrystalline Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC)C(CO)O1 PTHCMJGKKRQCBF-UHFFFAOYSA-N 0.000 description 1
- 125000003535 D-glucopyranosyl group Chemical group [H]OC([H])([H])[C@@]1([H])OC([H])(*)[C@]([H])(O[H])[C@@]([H])(O[H])[C@]1([H])O[H] 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 150000004781 alginic acids Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical group 0.000 description 1
- 229920003064 carboxyethyl cellulose Polymers 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- LOKCTEFSRHRXRJ-UHFFFAOYSA-I dipotassium trisodium dihydrogen phosphate hydrogen phosphate dichloride Chemical compound P(=O)(O)(O)[O-].[K+].P(=O)(O)([O-])[O-].[Na+].[Na+].[Cl-].[K+].[Cl-].[Na+] LOKCTEFSRHRXRJ-UHFFFAOYSA-I 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000010102 embolization Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- 230000036046 immunoreaction Effects 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000002953 phosphate buffered saline Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
Classifications
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/08—Cellulose derivatives
- C08J2401/26—Cellulose ethers
- C08J2401/28—Alkyl ethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/02—Polyalkylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
Abstract
The invention discloses a cellulose-polyethylene glycol-layered silicon dioxide composite hydrogel which comprises modified water-soluble cellulose and/or salt thereof, layered silicon dioxide, polyethylene glycol, inorganic salt and water. According to the invention, the stability of the cellulose hydrogel is improved by using the lamellar silicon dioxide, and meanwhile, the polyethylene glycol is added into the system, so that the problem that the viscosity of the system is greatly increased due to the lamellar silicon dioxide is remarkably improved, and the method is suitable for injection or treatment of introducing the cellulose hydrogel through a thin catheter. Compared with a chemical crosslinking method, the composite hydrogel disclosed by the invention has the advantages of no introduction of a crosslinking agent and simplicity in use, and has a wide application prospect.
Description
Technical Field
The invention belongs to the field of biomedical materials, and particularly relates to injectable cellulose-polyethylene glycol-layered silicon dioxide composite hydrogel and application thereof.
Technical Field
Cellulose is a linear polymer formed by connecting D-glucopyranose units (AGU) by beta-1, 4 glycosidic bonds, is the most abundant organic polymer in the nature, has the properties of regeneration, green and biocompatibility, and is an important basic raw material for chemical engineering. Cellulose molecules have a large number of hydrogen bonds, complex intermolecular and intramolecular hydrogen bond actions are easily formed, and the cellulose is insoluble in water and common organic solvents due to high crystallinity. The current cellulose modification technology mainly comprises two aspects of etherification and esterification. The cellulose ether is a cellulose derivative prepared by etherifying and modifying cellulose, is soluble in water and an organic solvent, has the functions of thickening, film forming and the like in an aqueous solution, has good biocompatibility and biodegradability, is safe and non-toxic, has no irritation to skin and mucous membrane, has no immunoreaction, and is widely applied in the medical field.
However, although the modified cellulose has the advantages of good biocompatibility and biodegradability and has extremely high application value as a biological material, the modified cellulose has the disadvantages of rapid absorption in the human body and short residence time in tissues, so that the application is limited, and the degradation time of the cellulose hydrogel is generally improved in the form of physical crosslinking, chemical crosslinking or a composite material.
Patent US10052408B2 reports that an anti-blocking material based on carboxymethyl cellulose can improve the stability of the system by physically crosslinking carboxymethyl cellulose and polyethylene glycol with calcium ions. Patent CN104327307A discloses a method for preparing cellulose-based biodegradable hydrogel, which uses polyethylene glycol diglycidyl ether as a cross-linking agent to obtain biodegradable carboxymethyl cellulose hydrogel, and the degradation rate of the hydrogel can be adjusted by adjusting the ratio of carboxymethyl cellulose to the cross-linking agent.
In addition, the physical properties of the hydrogel can be regulated by adding inorganic nanomaterials. Silica layered materials have been widely used as active ingredients or viscosity modifiers in pharmaceuticals, cosmetics and foods due to their unique electrostatic properties, uniform size and biological activity. For example, the stability of hydrogel can be improved by adding silica layered material into gelatin, and the degradation rate in 48 hours is improved from 50% to nearly 90%. (Biotechnol. J.2020,1900456) the Laponite silica layered material was added to alginic acid hydrogel to make a shear-thinning non-Newtonian fluid that could be injected through a syringe to form a solid gel in vivo. (adv.Sci.2019,6,1901041)
Disclosure of Invention
Aiming at the problem that cellulose derivative hydrogel in the prior art is easy to degrade, the lamellar silicon dioxide is added into the cellulose derivative hydrogel to improve the stability of the gel, and the problem that the viscosity of the gel is greatly increased after the lamellar silicon dioxide is added is solved by using polyethylene glycol, so that the injectable stable cellulose composite hydrogel is obtained.
The specific technical scheme of the invention is as follows:
a modified cellulose composite hydrogel comprises modified water-soluble cellulose and/or salts thereof, layered silicon dioxide, polyethylene glycol, inorganic salts and water.
Preferably, the modified water-soluble cellulose is polyanionic cellulose, and more preferably etherified cellulose (cellulose ether), including single ethers and mixed ethers. The single ethers include alkyl ethers (e.g., ethyl cellulose, propyl cellulose, benzyl cellulose, phenyl cellulose, cyanoethyl cellulose, etc.), hydroxyalkyl ethers (e.g., hydroxymethyl cellulose, hydroxyethyl cellulose (HEC), hydroxypropyl cellulose (HPC), etc.), carboxyalkyl ethers (e.g., carboxymethyl cellulose (CMC), carboxyethyl cellulose, etc.), mixed ethers refer to ethers having two or more groups attached to the molecular structure, such as benzyl cyanoethyl cellulose, carboxymethyl hydroxyethyl cellulose, carboxymethyl hydroxypropyl cellulose, hydroxypropyl methyl cellulose (HPMC), 2-hydroxy-3-butoxypropyl hydroxyethyl cellulose (HBPEC), etc. the etherified cellulose of the present invention may be selected from one or more of single ether and mixed ether celluloses.
The molecular weight of the modified water-soluble cellulose is 2000-2000000Da, and the substitution degree is 0.6-0.9. The molecular weight is preferably 90000-700000Da and the degree of substitution is preferably 0.7-0.9.
The molecular weight of the polyethylene glycol is 300-4000000 Da. Preferably 4000-10000 Da.
The layered silica material of the present invention is natural or synthetic, and in one specific example of the present invention, the layered silica is commercially available from Laponite XLG, BYK, germany.
The inorganic salt of the present invention is an alkali metal salt and/or an alkaline earth metal salt. The inorganic salt as electrolyte competes for water molecules with cellulose molecules in aqueous solution to achieve the effect of thickening. Preferably, the inorganic salt is a calcium salt and/or a sodium salt. One specific example is calcium chloride and sodium chloride.
Preferably, the mass ratio of the modified water-soluble cellulose to the layered silicon dioxide to the polyethylene glycol in the composite hydrogel is 0.05-5: 0.05-5: 0.05-10. Preferably 0.5 to 3: 0.5-3: 0.5-5.
Preferably, the mass percentages of the modified water-soluble cellulose, the layered silicon dioxide and the polyethylene glycol in the composite hydrogel are respectively 0.05-5%, 0.05-5% and 0.05-10%. Preferably 0.5-3%, 0.5-3% and 0.5-5%, more preferably, the composite hydrogel comprises carboxymethyl cellulose/sodium carboxymethyl cellulose, layered silicon dioxide, polyethylene glycol, calcium chloride, sodium chloride and water, wherein the molecular weight of the carboxymethyl cellulose is 90000-700000Da, the substitution degree is 0.7-0.9, the molecular weight of the polyethylene glycol is 4000-10000Da, and the mass ratio of the carboxymethyl cellulose to the layered silicon dioxide to the polyethylene glycol is 0.5-3: 0.5-3: 0.5-5.
According to a specific scheme, the composite hydrogel comprises carboxymethylcellulose/sodium carboxymethylcellulose, layered silicon dioxide, polyethylene glycol, calcium chloride, sodium chloride and water, wherein the molecular weight of the carboxymethylcellulose/sodium carboxymethylcellulose is 70000Da0, the substitution degree is 0.9, the molecular weight of the polyethylene glycol is 6000Da, and the mass percentage content of the carboxymethylcellulose/sodium carboxymethylcellulose, the layered silicon dioxide and the polyethylene glycol is 1.5%, 1.5% and 1.5%.
The invention also aims to provide application of the composite hydrogel in preparation of tissue fillers, tissue anti-adhesion agents, tissue engineering scaffolds, sealants or embolization agents.
The invention also provides a preparation method of the composite hydrogel, which comprises the steps of adding the modified water-soluble cellulose into water, uniformly stirring, continuously adding the layered silicon dioxide, uniformly stirring, further adding the mixed powder of the inorganic salt and the polyethylene glycol, and uniformly stirring to obtain the composite hydrogel.
The invention has the advantages that:
in the process of improving the stability of the cellulose hydrogel by using the lamellar silicon dioxide, the invention finds that although the lamellar silicon dioxide can improve the stability of the cellulose hydrogel, the viscosity of the system is greatly increased, which brings great problems to injection or intervention of the cellulose hydrogel through a thin catheter. In the process of solving the problems, the research of the invention unexpectedly discovers that the problem of high system viscosity can be obviously improved after polyethylene glycol is added into the system, and the stability of the cellulose hydrogel is ensured. Compared with a chemical crosslinking method, the technical scheme of the invention has the advantages of no introduction of a crosslinking agent and simple use, and has wide application prospect.
Detailed Description
The invention is described in further detail below with reference to specific examples and data, it being understood that these examples are intended to illustrate the invention and are not intended to limit the scope of the invention in any way.
Terms used in the present invention generally have meanings commonly understood by those of ordinary skill in the art, unless otherwise specified. In the following examples, various procedures and methods not described in detail are conventional methods well known in the art.
Example 1 preparation of CMC composite hydrogel
The effect of adding lamellar silicon dioxide and polyethylene glycol on the hydrogel viscosity was examined using CMC having a molecular weight of 70 ten thousand and a substitution rate of 0.9 as an example.
CMC hydrogel No. 1 sample: adding 0.5g of CMC with the molecular weight of 70 ten thousand Da and the substitution rate of 0.9 into 100mL of deionized water, and mechanically stirring uniformly to obtain a CMC hydrogel No. 1 sample.
CMC hydrogel No. 2 sample: adding 0.5g of CMC with the molecular weight of 70 ten thousand Da and the substitution rate of 0.9 into 100mL of deionized water, mechanically stirring uniformly, continuously adding 0.5g of layered silicon dioxide Laponite, and stirring uniformly to obtain a CMC hydrogel No. 2 sample.
CMC hydrogel No. 3 sample: 0.5g of CMC with the molecular weight of 70 ten thousand Da and the substitution rate of 0.9 is added into 100mL of deionized water and is mechanically stirred uniformly. 0.5g of Laponite was added and stirred well. Further adding 0.235g of CaCl2·2H2And O, 0.215g of NaCl and 1g of polyethylene glycol with the molecular weight of 6000Da are mixed and stirred uniformly to obtain a CMC hydrogel No. 3 sample.
CMC hydrogel No. 4 sample: adding 1.5g of CMC with the molecular weight of 70 ten thousand Da and the substitution rate of 0.9 into 100mL of deionized water, and mechanically stirring uniformly to obtain a CMC hydrogel No. 4 sample.
CMC hydrogel No. 5 sample: adding 1.5g of CMC with the molecular weight of 70 ten thousand Da and the substitution rate of 0.9 into 100mL of deionized water, mechanically stirring uniformly, continuously adding 0.5g of layered silicon dioxide Laponite, and stirring uniformly to obtain a CMC hydrogel No. 5 sample.
CMC hydrogel No. 6 sample: 1.5g of CMC with the molecular weight of 70 ten thousand Da and the substitution rate of 0.9 is added into 100mL of deionized water and is mechanically stirred uniformly. 0.5g of Laponite was added and stirred well. Further adding 0.235g of CaCl2·2H2O, 0.215g of NaCl and 0.25g of polyethylene glycol with the molecular weight of 6000Da are mixed and stirred uniformly to obtain a CMC hydrogel No. 6 sample.
CMC hydrogel sample No. 7: adding 5g of CMC with the molecular weight of 70 ten thousand Da and the substitution rate of 0.9 into 100mL of deionized water, and mechanically stirring uniformly to obtain a CMC hydrogel No. 7 sample.
CMC hydrogel No. 8 sample: adding 5g of CMC with the molecular weight of 70 ten thousand Da and the substitution rate of 0.9 into 100mL of deionized water, mechanically stirring uniformly, continuously adding 0.25g of layered silicon dioxide Laponite, and stirring uniformly to obtain a CMC hydrogel No. 8 sample.
CMC hydrogel No. 9 sample: 1.5g of CMC with the molecular weight of 70 ten thousand Da and the substitution rate of 0.9 is added into 100mL of deionized water and is mechanically stirred uniformly. 0.25g of Laponite was added and stirred well. Further adding 0.235g of CaCl2·2H2And O, 0.215g of NaCl and 5g of polyethylene glycol with the molecular weight of 6000Da are mixed and stirred uniformly to obtain a CMC hydrogel No. 9 sample.
And (3) viscosity measurement: the hydrogel sample obtained was subjected to viscosity measurement using an SNB rotary viscometer.
As shown in table 1, when the CMC was 0.5%, 1.5%, or 5% by mass, the viscosity of the CMC hydrogel system was greatly increased by adding the layered silica Laponite, and the viscosity of the system was significantly reduced by further adding PEG.
In particular, when the mass percent of CMC is 1.5%, by comparing the viscosities of samples hydrogel nos. 4-6, it was found that the viscosity of the CMC hydrogel system increased greatly by adding lamellar silica Laponite (hydrogel No. 5), increased by 37.97 times, and formed a viscous system with poor fluidity, while further adding PEG significantly reduced the system viscosity (hydrogel No. 6).
TABLE 1 Effect of layered silica and polyethylene glycol on cellulose hydrogel viscosity
Example 2
Taking CMC with molecular weight of 70 ten thousand Da and substitution rate of 0.9 as an example, the influence of adding polyethylene glycol with different molecular weight on the hydrogel viscosity is examined.
CMC hydrogel No. 10 sample: 1.5g of CMC with the molecular weight of 70 ten thousand Da and the substitution rate of 0.9 is added into 100mL of deionized water and is mechanically stirred uniformly. 1.5g of layered silica Laponite was added thereto and stirred well. Further adding 0.235g of CaCl2·2H2O, 0.215g of NaCl and 0.25g of polyethylene glycol with the molecular weight of 600Da are mixed and stirred uniformly to obtain a CMC hydrogel No. 10 sample.
CMC hydrogel No. 11 sample: 1.5g of CMC with the molecular weight of 70 ten thousand Da and the substitution rate of 0.9 is added into 100mL of deionized water and is mechanically stirred uniformly. 1.5g of layered silica Laponite was added thereto and stirred well. Further adding 0.235g of CaCl2 & 2H2O, 0.215g of NaCl and 0.25g of polyethylene glycol mixed powder with the molecular weight of 4000000Da, and uniformly stirring to obtain a CMC hydrogel No. 11 sample.
TABLE 2 Effect of different molecular weight polyethylene glycols on the viscosity of cellulose hydrogels
The results are shown in Table 2 and indicate that polyethylene glycol having a molecular weight in the range of 600-4000000 can significantly reduce the viscosity of cellulose gel to which layered silica is added.
EXAMPLE 3 polyethylene glycol Capacity to control the viscosity of cellulose hydrogels of different molecular weights
CMC hydrogel No. 12 sample: adding 1.5g of CMC with the molecular weight of 9 ten thousand Da and the substitution rate of 0.7 into 100mL of deionized water, and mechanically stirring uniformly to obtain a CMC hydrogel No. 12 sample.
CMC hydrogel No. 13 sample: adding 1.5g of CMC with the molecular weight of 9 ten thousand Da and the substitution rate of 0.7 into 100mL of deionized water, mechanically stirring uniformly, continuously adding 1.5g of layered silicon dioxide Laponite, and stirring uniformly to obtain a CMC hydrogel No. 13 sample.
CMC hydrogel No. 14 sample: 1.5g of CMC with the molecular weight of 9 ten thousand Da and the substitution rate of 0.7 is added into 100mL of deionized water and is mechanically stirred uniformly. 1.5g of layered silica Laponite was added thereto and stirred well. Further adding 0.235g of CaCl2·2H2O, 0.215g of NaCl and 1.5g of polyethylene glycol with the molecular weight of 6000Da are mixed and stirred uniformly to obtain a CMC hydrogel No. 14 sample.
As shown in Table 3, it is understood from the results of tables 1 and 2 that CMC having a molecular weight in the range of 9 to 70 ten thousand Da can form a composite gel having a desired viscosity with lamellar silica and polyethylene glycol.
TABLE 3 viscosity of 1.5% by weight CMC hydrogel samples
Example 4 stability of cellulose-polyethylene glycol-layered silica composite hydrogel according to the present invention, 1g of hydrogel sample was weighed and placed in a centrifuge tube, 10mL of phosphate buffered saline solution with pH of 7.4 was added, and stability test was performed in a constant temperature water bath shaker controlled at 37 ℃. And taking out the sample at regular intervals to observe the state, and determining the degradation endpoint when the obvious gel cannot be taken out. The stability test results of hydrogels 1-9 are shown in table 4, and compared with pure CMC hydrogel, the stability of hydrogel can be increased by adding lamellar silicon dioxide, and the stability is not affected by adding polyethylene glycol. For example, the hydrogel No. 1 is 0.5% CMC, the degradation period is 2 hours, the hydrogel No. 2 added with 0.5% lamellar silica has the degradation period prolonged to 20 hours, the hydrogel No. 3 further added with 1% polyethylene glycol and the hydrogel No. 9 added with 5% polyethylene glycol have the degradation period kept unchanged, and the degradation period of the hydrogel No. 6 is even obviously prolonged, which shows that the cellulose-polyethylene glycol-lamellar silica composite hydrogel disclosed by the invention has ideal viscosity and good stability.
TABLE 4 stability of CMC hydrogel samples
Claims (10)
1. A modified cellulose composite hydrogel is characterized by comprising modified water-soluble cellulose and/or salt thereof, layered silicon dioxide, polyethylene glycol, inorganic salt and water.
2. The composite hydrogel according to claim 1, wherein the modified water-soluble cellulose is a polyanionic cellulose.
3. The composite hydrogel according to claim 2, wherein the polyanionic cellulose is cellulose ether selected from one or more of methyl cellulose, hydroxyethyl methyl cellulose, carboxymethyl cellulose, ethyl hydroxyethyl cellulose, hydroxyethyl carboxymethyl cellulose, hydroxypropyl carboxymethyl cellulose, benzyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, hydroxybutyl cellulose, cyanoethyl cellulose, benzyl cyanoethyl cellulose, carboxymethyl hydroxyethyl cellulose, and phenyl cellulose.
4. The composite hydrogel according to claim 1, wherein the modified water-soluble cellulose has a molecular weight of 2000-2000000Da and a degree of substitution of 0.6-0.9.
5. The composite hydrogel according to claim 1, wherein the molecular weight of the polyethylene glycol is 300-.
6. The composite hydrogel according to claim 1, wherein the inorganic salt is an alkali metal salt and/or an alkaline earth metal salt.
7. The composite hydrogel according to claim 1, wherein the mass ratio of the modified water-soluble cellulose to the layered silica to the polyethylene glycol is 0.05-5: 0.05-5: 0.05-10.
8. The composite hydrogel as claimed in claim 7, which comprises carboxymethylcellulose, layered silica, polyethylene glycol, calcium chloride, sodium chloride and water, wherein the molecular weight of carboxymethylcellulose is 90000-700000Da, the degree of substitution is 0.7-0.9, the molecular weight of polyethylene glycol is 4000-10000Da, and the mass ratio of carboxymethylcellulose, layered silica and polyethylene glycol is 0.5-3: 0.5-3: 0.5-5.
9. Use of the composite hydrogel according to any one of claims 1 to 8 for the preparation of a tissue filler, a tissue anti-adhesion agent, a tissue engineering scaffold, a sealant or an embolic agent.
10. The method for preparing a composite hydrogel according to any one of claims 1 to 8, wherein the modified water-soluble cellulose is added to water and stirred uniformly, the layered silica is further added and stirred uniformly, and the mixed powder of the inorganic salt and the polyethylene glycol is further added and stirred uniformly to obtain the composite hydrogel.
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| US5538728A (en) * | 1989-10-19 | 1996-07-23 | Shiseido Company, Ltd. | Hydrophilic polymer-silicate mineral complex material and use thereof |
| JPH09187493A (en) * | 1996-01-10 | 1997-07-22 | S T Chem Co Ltd | Gel-like deodorizer |
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