CN117417495A - Modified nano hydroxyapatite composite hydrogel and preparation method thereof - Google Patents
Modified nano hydroxyapatite composite hydrogel and preparation method thereof Download PDFInfo
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- 239000000017 hydrogel Substances 0.000 title claims abstract description 95
- 239000002131 composite material Substances 0.000 title claims abstract description 70
- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 58
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 108010010803 Gelatin Proteins 0.000 claims abstract description 53
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- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 53
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- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims abstract description 7
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- 238000002156 mixing Methods 0.000 claims description 13
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- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
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- 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 claims description 9
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 8
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- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 5
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Classifications
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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
- 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
- C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
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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
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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- 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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/325—Calcium, strontium or barium phosphate
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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Abstract
The application relates to the technical field of composite hydrogels, in particular to a modified nano hydroxyapatite composite hydrogel and a preparation method thereof. The modified nano hydroxyapatite composite hydrogel comprises the following raw materials in parts by weight: 4-6 parts of gelatin composite hydrogel, 1-3 parts of gamma-methacryloxypropyl trimethoxy silane, 2-4 parts of nano hydroxyapatite, 1-3 parts of acrylic acid, 0.1-0.3 part of N, N-methylene bisacrylamide, 0.1-0.2 part of potassium persulfate and 0.1-0.3 part of N, N, N, N-tetramethyl ethylenediamine. The modified nano hydroxyapatite composite hydrogel has excellent mechanical property and antibacterial property.
Description
Technical Field
The application relates to the technical field of composite hydrogels, in particular to a modified nano hydroxyapatite composite hydrogel and a preparation method thereof.
Background
The hydrogel is a novel polymer material with a three-dimensional reticular structure, takes an aqueous medium as a dispersion medium, has better permeability to low-molecular substances, high water content, quick swelling, good biocompatibility and drug slow release performance, and can be used as a sensor, artificial muscle, cell fixation and memory material, a drug carrier and a tissue engineering matrix material.
The hydrogel is prepared from water-soluble or hydrophilic polymer materials through certain chemical crosslinking or physical crosslinking. Among them, the polymer materials can be classified into natural and synthetic materials according to the source, and natural polymers are attracting more and more attention from students because of their better biocompatibility, sensitivity to environment, abundant sources and low price.
However, the natural polymer material has poor stability and is easy to degrade, and a large amount of water exists in the hydrogel, so that the molecular weight of the hydrogel is easy to slip in the stretching process, and meanwhile, a large amount of water can also compete with the molecular chain of the hydrogel by hydrogen bonds, so that the hydrogel has low mechanical property and is easy to deform and permanently break.
Disclosure of Invention
In order to overcome the defect of poor mechanical property of the hydrogel, the application provides a modified nano hydroxyapatite composite hydrogel and a preparation method thereof.
In a first aspect, the present application provides a modified nano hydroxyapatite composite hydrogel, which adopts the following technical scheme:
the modified nano hydroxyapatite composite hydrogel comprises the following raw materials in parts by weight: 4-6 parts of gelatin composite hydrogel, 1-3 parts of gamma-methacryloxypropyl trimethoxy silane, 2-4 parts of nano hydroxyapatite, 1-3 parts of acrylic acid, 0.1-0.3 part of N, N-methylene bisacrylamide, 0.1-0.2 part of potassium persulfate and 0.1-0.3 part of N, N, N, N-tetramethyl ethylenediamine.
Gelatin is a single-chain molecule obtained by decomposing a triple helix structure of collagen, is a partial denatured product of collagen, has good biocompatibility, biodegradability and skin affinity, but the hydrogel formed by the gelatin per se has poor mechanical properties.
When nano hydroxyapatite is added into the gelatin composite hydrogel, the gelatin composite hydrogel can take the nano hydroxyapatite as a physical crosslinking point to perform non-covalent bond action with the polysaccharide chain segment, so that the crosslinking of the polysaccharide chain segment is realized, and the mechanical property of the gelatin composite hydrogel is improved.
However, the crosslinking effect of non-covalent bond crosslinking is relatively poor, and when gamma-methacryloxypropyl trimethoxy silane is matched with nano hydroxyapatite for use, gamma-methacryloxypropyl trimethoxy silane can modify the surface of nano hydroxyapatite and obtain double bonds, so that the gelatin composite hydrogel is formed by taking natural polymer skeleton, double bond modified nano hydroxyapatite and acrylic acid as crosslinking monomers, N, N-methylene bisacrylamide as a crosslinking agent, and potassium persulfate as a covalent bond crosslinking system of an initiator, and the original non-covalent bond crosslinking system is matched to form a synergetic covalent-non-covalent crosslinking network, so that the mechanical property of the gelatin composite hydrogel is further improved.
Preferably, the gelatin composite hydrogel comprises the following raw materials in parts by weight: 80-100 parts of gelatin hydrogel, 10-20 parts of sodium carboxymethylcellulose and 30-40 parts of epsilon-polylysine grafted chitosan loaded with silver-containing organic frameworks.
Hydrogels are also required to have excellent antibacterial effects because they are often used in the field of human health. Epsilon-polylysine is a colorless and odorless natural polypeptide which is easily dissolved in water and is produced by streptomyces albus, and when epsilon-polylysine is combined with cell membranes of bacteria, holes are formed on the cell membranes of the bacteria, so that the cell membrane structure of microorganisms is destroyed, and a small amount of intracellular fluid is leaked. Meanwhile, epsilon-polylysine enters cells of the thalli through pore channels on the membrane to destroy normal physiological metabolism of the cells, cause interruption of material, energy and information transmission of the cells, destroy cell cores and finally lead to cell death.
Chitosan is a linear polysaccharide obtained by deacetylation reaction of chitin, and can inhibit enzyme activities generated by some bacteria, such as lipase, protease, etc. These enzymes play an important role in the metabolism and survival of bacteria, and inhibition of chitosan can interfere with the normal function of bacteria, thereby inhibiting their growth and reproduction.
The hydroxyl group at the 2-C position on the glucose structural formula is replaced by amino group to obtain chitosan, so that the chitosan can be crosslinked with epsilon-polylysine after being oxidized by 2, 6-tetramethyl piperidine 1-oxyl, and compared with the simple mixed use of the chitosan and epsilon-polylysine, the epsilon-polylysine grafted chitosan can promote the synergistic effect of the chitosan and the epsilon-polylysine, so that the better antibacterial effect is obtained.
The silver-containing organic framework is a novel porous material formed by self-assembly of metal ions and organic ligands, and can release silver ions through slow degradation, so that different types of antibacterial effects are obtained, and a perfect antibacterial network is formed under the coordination of epsilon-polylysine and chitosan. In addition, the mechanical property of the gelatin composite hydrogel can be effectively enhanced by adding the silver-containing organic framework, so that the mechanical property of the modified nano-hydroxyapatite composite hydrogel is further improved.
Preferably, the preparation method of the gelatin composite hydrogel comprises the following steps: stirring and mixing epsilon-polylysine grafted chitosan loaded with a silver-containing organic framework, gelatin hydrogel and sodium carboxymethyl cellulose, transferring to a temperature of minus 20 ℃ for freezing for 24 hours, thawing, repeating for three times, soaking in a sodium hydroxide solution for 30 minutes, and finally washing to obtain the gelatin composite hydrogel.
Preferably, the epsilon-polylysine grafted chitosan loaded with the silver-containing organic framework comprises the following raw materials in parts by weight: 2-4 parts of potassium bromide, 0.2-0.6 part of 2, 6-tetramethylpiperidine 1-oxyl, 10-14 parts of chitosan, 2-4 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 1.0-1.4 parts of N-hydroxysuccinimide, 4-7 parts of epsilon-polylysine and 3-6 parts of silver-containing organic frameworks.
Preferably, the preparation method of the epsilon-polylysine grafted chitosan loaded with the silver-containing organic framework comprises the following steps of;
a1, dissolving potassium bromide and 2, 6-tetramethyl piperidine 1-oxyl in deionized water, then adding chitosan and dropwise adding sodium hypochlorite, adjusting the pH value of the mixed solution to 10-11 through hydrochloric acid, mixing and stirring fully, finally adding ethanol to stop the reaction, and finally centrifugally washing to obtain oxidized chitosan;
a2, dissolving oxidized chitosan in deionized water, then adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide, then reacting at 25 ℃ for 10min, centrifuging and washing to remove impurities, finally adding epsilon-polylysine, reacting at 25 ℃ for 24h, then adding a silver-containing organic framework, stirring and mixing, and finally washing, precipitating and freezing to obtain the epsilon-polylysine grafted chitosan loaded with the silver-containing organic framework.
Preferably, the silver-containing organic framework is a reactant of silver nitrate and pyridine-3, 5-dicarboxylic acid.
Preferably, the molar ratio of silver nitrate to pyridine-3, 5-dicarboxylic acid is (1.5-2.0): (0.5-1).
When the molar ratio of the silver nitrate to the pyridine-3, 5-dicarboxylic acid is adopted, the prepared silver-containing organic framework has better slow release effect on the premise of obtaining excellent antibacterial effect.
Preferably, the preparation method of the silver-containing organic framework comprises the following steps: adding silver nitrate and pyridine-3, 5-dicarboxylic acid into deionized water, stirring and dispersing at room temperature to obtain a suspension, reacting the suspension at 200 ℃ for 8 hours, and finally separating, washing and drying to obtain the silver-containing organic framework.
In a second aspect, the present application provides a method for preparing a modified nano hydroxyapatite composite hydrogel, which adopts the following technical scheme:
the preparation method of the modified nano hydroxyapatite composite hydrogel comprises the following steps:
adding gamma-methacryloxypropyl trimethoxy silane into an ethanol solution, uniformly mixing until complete hydrolysis, adding nano hydroxyapatite, slowly heating to 60 ℃ and continuously stirring, cooling the solution to room temperature, and washing and drying to obtain double bond modified nano hydroxyapatite;
dissolving gelatin composite hydrogel in deionized water, then adding double bond modified nano-hydroxyapatite, acrylic acid and N, N-methylene bisacrylamide, fully stirring, then adding potassium persulfate, stirring and reacting for 4 hours, then adding N, N, N, N-tetramethyl ethylenediamine, and finally reacting for 6 hours at 50 ℃ to obtain the modified nano-hydroxyapatite composite hydrogel.
In summary, the present application has the following beneficial effects:
1. when nano-hydroxyapatite is added into the gelatin composite hydrogel, the gelatin composite hydrogel can take the nano-hydroxyapatite as a physical crosslinking point to perform non-covalent bond action with the polysaccharide chain segment, so that the crosslinking of the polysaccharide chain segment is realized, and the mechanical property of the gelatin composite hydrogel is improved.
2. The gamma-methacryloxypropyl trimethoxy silane can modify the surface of nano hydroxyapatite to obtain double bonds, so that a covalent bond crosslinking system is formed, the original non-covalent bond crosslinking is matched, a synergetic covalent-non-covalent crosslinking network is formed, and the mechanical property of the gelatin composite hydrogel is further improved.
3. The silver-containing organic framework, epsilon-polylysine and chitosan can form a more perfect antibacterial network, and meanwhile, the mechanical property of the gelatin composite hydrogel can be effectively enhanced by adding the silver-containing organic framework, so that the mechanical property of the modified nano hydroxyapatite composite hydrogel is improved.
Detailed Description
The present application is described in further detail below in connection with examples 1-9 and comparative examples 1-6.
Raw materials
Gamma-methacryloxypropyl trimethoxysilane CAS:2530-85-0; hydroxyapatite, hubei Langbowan organism; acrylic CAS:79-10-7; n, N-methylenebisacrylamide CAS:110-26-9; potassium persulfate CAS:7727-21-1; n, N-tetramethyl ethylenediamine CAS:110-18-9; gelatin hydrogel methacryloylated gelatin north family nanometer; potassium bromide CAS:7758-02-3; chitosan CAS:9012-76-4; sodium hypochlorite CAS:7681-52-9; hydrochloric acid CAS:7647-01-0; ethanol CAS:64-17-5; sodium carboxymethyl cellulose CAS:9004-32-4;2, 6-tetramethylpiperidine 1-oxyl, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide Shanghai Relong; epsilon-polylysine with an average molecular weight of 5000Da Solarbio; silver nitrate CAS:7761-88-8; pyridine-3, 5-dicarboxylic acid CAS:499-81-0.
Examples
Example 1
The modified nano hydroxyapatite composite hydrogel comprises the following raw materials in mass: 5kg of gelatin composite hydrogel, 2kg of gamma-methacryloxypropyl trimethoxysilane, 3kg of nano hydroxyapatite, 2kg of acrylic acid, 0.2kg of N, N-methylenebisacrylamide, 0.15kg of potassium persulfate and 0.2kg of N, N-tetramethyl ethylenediamine.
The preparation method of the modified nano hydroxyapatite composite hydrogel comprises the following steps:
adding 2kg of gamma-methacryloxypropyl trimethoxysilane into 10L of 25wt% ethanol aqueous solution, uniformly mixing until complete hydrolysis, adding 3kg of nano hydroxyapatite, slowly heating to 60 ℃ and continuously stirring, cooling the solution to room temperature, washing and drying to obtain double bond modified nano hydroxyapatite;
dissolving 0.3kg of gelatin composite hydrogel in 10L of deionized water, adding 2kg of acrylic acid and 0.2kg of N, N-methylene bisacrylamide which are prepared in the step one, fully stirring, adding 0.15kg of potassium persulfate, stirring and reacting for 4 hours, adding 0.2kg of N, N-tetramethyl ethylenediamine, and reacting for 6 hours at the temperature of 50 ℃ to obtain the modified nano hydroxyapatite composite hydrogel.
Wherein the gelatin composite hydrogel comprises the following raw materials by mass: 900g of gelatin hydrogel, 150g of sodium carboxymethyl cellulose and 350g of epsilon-polylysine grafted chitosan loaded with a silver-containing organic framework.
The preparation method of the gelatin composite hydrogel comprises the following steps: 350g of epsilon-polylysine grafted chitosan loaded with a silver-containing organic framework, 900g of gelatin hydrogel and 150g of sodium carboxymethyl cellulose are stirred and mixed, then the mixture is transferred to a temperature of minus 20 ℃ for freezing for 24 hours, then the mixture is thawed and repeated three times, then the mixture is soaked in 2L of 30wt% sodium hydroxide solution for 30 minutes, and finally the gelatin composite hydrogel is obtained through washing.
The epsilon-polylysine grafted chitosan loaded with the silver-containing organic framework comprises the following raw materials by mass: 30g of potassium bromide, 4g of 2, 6-tetramethylpiperidine 1-oxyl, 120g of chitosan, 30g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 12g N-hydroxysuccinimide, 55g of epsilon-polylysine and 45g of silver-containing organic frameworks.
The preparation method of the epsilon-polylysine grafted chitosan loaded with the silver-containing organic framework comprises the following steps:
a1, dissolving 30g of potassium bromide and 4g of 2, 6-tetramethylpiperidine 1-oxyl in 4.6L of deionized water, then adding 120g of chitosan, dropwise adding 300ml of 14wt% sodium hypochlorite aqueous solution, adjusting the pH value of the mixed solution to 10 through hydrochloric acid, fully mixing and stirring, finally adding 400ml of ethanol to stop the reaction, and finally centrifugally washing to obtain oxidized chitosan;
a2, dissolving 50g of oxidized chitosan in 600ml of deionized water, then adding 30g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 12g N-hydroxysuccinimide, then reacting at 25 ℃ for 10min, centrifuging, washing to remove impurities, finally adding 55g of epsilon-polylysine, reacting at 25 ℃ for 24h, then adding 45g of silver-containing organic framework, stirring and mixing, and finally washing, precipitating and freezing to obtain the epsilon-polylysine grafted chitosan loaded with the silver-containing organic framework.
The silver-containing organic framework is a reactant of silver nitrate and pyridine-3, 5-dicarboxylic acid, and the molar ratio of the silver nitrate to the pyridine-3, 5-dicarboxylic acid is 1.88:0.75.
The preparation method of the silver-containing organic framework comprises the following steps: adding 1.88mol of silver nitrate and 0.75mol of pyridine-3, 5-dicarboxylic acid into 2L of deionized water, stirring and dispersing at room temperature to obtain a suspension, reacting the suspension at 200 ℃ for 8 hours, and finally separating, washing and drying to obtain the silver-containing organic framework.
Examples 2 to 3
The difference from example 1 is that the addition amounts of the components of the modified nano-hydroxyapatite composite hydrogel are different, as shown in table 1.
Table 1 examples 1-3 Each component addition amount/kg of the modified nanohydroxyapatite composite hydrogel
| Example 1 | Example 2 | Example 3 | |
| Gelatin composite hydrogel | 5 | 6 | 4 |
| Gamma-methacryloxypropyl trimethoxysilane | 2 | 1 | 3 |
| Nano hydroxyapatite | 3 | 4 | 2 |
| Acrylic acid | 2 | 1 | 3 |
| N, N-methylenebisacrylamide | 0.2 | 0.3 | 0.1 |
| Potassium persulfate | 0.15 | 0.2 | 0.1 |
| N, N, N, N-tetramethyl ethylenediamine | 0.2 | 0.1 | 0.3 |
Examples 4 to 5
The difference from example 1 is that the addition amounts of the components of the gelatin composite hydrogel are different, as shown in Table 2.
TABLE 2 addition amount of each component per gram of the gelatin composite hydrogel of example 1, examples 4-5
| Example 1 | Example 4 | Example 5 | |
| Gelatin hydrogel | 900 | 1000 | 800 |
| Sodium carboxymethyl cellulose | 150 | 200 | 100 |
| Epsilon-polylysine grafted chitosan loaded with silver-containing organic framework | 350 | 300 | 400 |
Examples 6 to 7
The difference from example 1 is that the addition amounts of the components of epsilon-polylysine grafted chitosan supporting silver-containing organic frameworks are different, as shown in Table 3.
TABLE 3 epsilon-polylysine grafted Chitosan composition tables/g for examples 1, 6-7 loaded with silver-containing organic backbone
| Example 1 | Example 6 | Example 7 | |
| Potassium bromide | 30 | 40 | 20 |
| 2, 6-tetramethylpiperidine 1-oxyl | 4 | 2 | 6 |
| Chitosan | 120 | 100 | 140 |
| 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride | 30 | 40 | 20 |
| N-hydroxysuccinimide | 12 | 10 | 14 |
| Epsilon-polylysine | 55 | 70 | 40 |
| Silver-containing organic framework | 45 | 30 | 60 |
Examples 8 to 9
The difference from example 1 is that the molar ratios of the components in the silver-containing organic frameworks of examples 8-9 are different, as shown in Table 4.
TABLE 4 molar ratios of the components of the silver-containing organic frameworks of example 1, examples 8-9
| Example 1 | Example 8 | Example 9 | |
| Silver nitrate | 1.88 | 2.0 | 1.5 |
| Pyridine-3, 5-dicarboxylic acid | 0.75 | 0.5 | 1 |
Comparative example
Comparative example 1
A hydrogel comprising only gelatin hydrogel.
Comparative example 2
A hydrogel is prepared by mixing 5kg of gelatin hydrogel and 3kg of nano hydroxyapatite.
Comparative example 3
The difference from example 1 is that the gelatin composite hydrogel is replaced with a gelatin hydrogel of the same addition amount.
Comparative example 4
The difference from example 1 is that in the gelatin composite hydrogel, epsilon-polylysine grafted chitosan is no longer loaded with a silver-containing organic backbone.
Comparative example 5
The difference from example 1 is that in the gelatin composite hydrogel, epsilon-polylysine grafted chitosan loaded with a silver-containing organic skeleton is replaced by chitosan with the same addition amount.
Comparative example 6
The difference from comparative example 4 is that epsilon-polylysine grafted chitosan was replaced with a mixture of chitosan and epsilon-polylysine in the same addition amount, and the mass ratio of chitosan to epsilon-polylysine was 12:5.5.
Performance test
Detection method
1. Tensile Property test
Three samples were taken from examples 1-9 and comparative examples 1-6, respectively, and were subsequently prepared as test pieces having a length of 40mm, a width of 3.6mm and a thickness of 1.5mm, after which the test pieces were subjected to a tensile test at a tensile speed of 100mm/min by referring to GB/T1843-200 and using an IN-STRON-5943 type universal material tensile machine, the test calculation was conducted to obtain tensile strength and an average value was taken. 0.27MPa
2. Antibacterial property test
Three 100mg samples were taken from examples 1-9 and comparative examples 1-6, respectively, and then sterilized overnight under an ultraviolet lamp, and then immersed in a sterile PBS solutionThe gel was brought to swelling equilibrium, after which the swollen gel was transferred into 1ml of bacterial suspension (1X 10) 6 CFU/ml) at 37 ℃ for 24 hours, the bacterial suspension containing staphylococcus aureus, RN4220 strain, beijing hua yew organism; coli, cat No. B98084, minghuake; tetanus ATCC 454 Bai Ou Bo Wei organism Bio-77897. And the concentrations of the three strains are the same;
after the culture is completed, the bacterial liquid is subjected to gradient test by sterile physiological saline, 100ul of diluted sample bacterial liquid is sucked into a flat plate, then 15ml of sterile 48 ℃ liquid agar is poured into the flat plate by a pouring method, the agar is rapidly and uniformly mixed in an oscillating way, after the agar is solidified, the agar is inversely cultured for 24 hours at 37 ℃, and the number of viable bacteria on the flat plate is observed and counted. Meanwhile, a control group without hydrogel is set, and finally, the antibacterial rate is calculated and the average value is taken.
Antibacterial ratio= (CFU Control -CFU Experiment ）/CFU Control ×100%
The test data are shown in Table 5.
TABLE 5 detection data tables for examples 1-9 and comparative examples 1-6
| Tensile Strength/MPa | Antibacterial rate/% | |
| Example 1 | 0.42Mpa | 96.2% |
| Example 2 | 0.40Mpa | 96.3% |
| Example 3 | 0.39Mpa | 90.1% |
| Example 4 | 0.41Mpa | 92.4% |
| Example 5 | 0.39Mpa | 96.5% |
| Example 6 | 0.43Mpa | 95.6% |
| Example 7 | 0.42Mpa | 95.9% |
| Example 8 | 0.41MPa | 96.4% |
| Example 9 | 0.42Mpa | 95.8% |
| Comparative example 1 | 0.20MPa | 37.3% |
| Comparative example 2 | 0.26MPa | 40.9% |
| Comparative example 3 | 0.31MPa | 41.2% |
| Comparative example 4 | 0.35Mpa | 77.6% |
| Comparative example 5 | 0.32Mpa | 62.1% |
| Comparative example 6 | 0.33Mpa | 72.8% |
Referring to comparative examples 1-2 in combination with Table 5, it can be seen that the tensile strength of comparative example 2 is significantly improved compared to comparative example 1, thereby demonstrating that the addition of nano-hydroxyapatite can effectively improve the mechanical properties of gelatin hydrogels. The reason is that the nano hydroxyapatite can be used as a physical crosslinking point to perform non-covalent bond action with the polysaccharide chain segment, so that the crosslinking of the polysaccharide chain segment is realized, and the mechanical property of the gelatin composite hydrogel is improved.
Referring to comparative examples 2-3 in combination with Table 5, it can be seen that the tensile strength of comparative example 3 is further improved relative to comparative example 2, thus demonstrating that the mechanical properties of gelatin hydrogels can be further improved when gamma-methacryloxypropyl trimethoxysilane is used in combination with nano-hydroxyapatite. The preparation method is characterized in that gamma-methacryloxypropyl trimethoxy silane can modify the surface of nano hydroxyapatite to obtain double bonds, so that the gelatin composite hydrogel is formed by taking natural polymer skeleton, double bond modified nano hydroxyapatite and acrylic acid as crosslinking monomers, N, N-methylene bisacrylamide as a crosslinking agent, and a covalent bond crosslinking system taking potassium persulfate as an initiator is matched with the original non-covalent bond crosslinking to form a synergetic covalent-non-covalent crosslinking network, so that the mechanical property of the gelatin composite hydrogel is further improved.
Referring to comparative examples 3 to 6 in combination with Table 5, it can be seen that the antibacterial property of comparative example 5 is significantly improved as compared with comparative example 3, since chitosan can inhibit the enzymatic activities such as lipase, protease, etc. produced by some bacteria. These enzymes play an important role in the metabolism and survival of bacteria, and inhibition of chitosan can interfere with the normal function of bacteria, thereby inhibiting their growth and reproduction.
In contrast to comparative example 5, the antibacterial property of comparative example 4 was further improved because epsilon-polylysine was able to bind to the cell membrane of the cells, thereby promoting the formation of pores in the cell membrane of the cells, and thus destroying the cell membrane structure of the microorganism, resulting in leakage of a small amount of intracellular fluid. Meanwhile, epsilon-polylysine enters cells of the thalli through pore channels on the membrane to destroy normal physiological metabolism of the cells, cause interruption of material, energy and information transmission of the cells, destroy cell cores and finally lead to cell death.
The reason why the antibacterial performance of comparative example 6 is slightly lowered compared with comparative example 4 is that chitosan can be crosslinked with epsilon-polylysine after the oxidation of 2, 6-tetramethylpiperidine 1-oxyl, and the epsilon-polylysine is grafted with chitosan in a manner that promotes the synergistic effect of the two substances compared with the simple mixing of chitosan and epsilon-polylysine, thereby obtaining more excellent antibacterial effect.
Referring to example 1 and comparative example 4 in combination with table 5, it can be seen that the mechanical properties and antibacterial properties of example 1 are significantly improved compared with those of comparative example 4, because the silver-containing organic skeleton can release silver ions through slow degradation, thereby obtaining different types of antibacterial effects, and forming a perfect antibacterial network under the coordination of epsilon-polylysine and chitosan. In addition, the mechanical property of the gelatin composite hydrogel can be effectively enhanced by adding the silver-containing organic framework, so that the mechanical property of the modified nano-hydroxyapatite composite hydrogel is further improved.
Referring to examples 1 to 9 in combination with Table 5, it can be seen that in examples 1 to 9, example 1 has relatively more excellent mechanical properties and antibacterial properties, and thus it is demonstrated that the modified nano-hydroxyapatite composite hydrogel prepared by using the addition ratio of the components of example 1 has more excellent mechanical properties and antibacterial properties.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.
Claims (9)
1. The modified nano hydroxyapatite composite hydrogel is characterized by comprising the following raw materials in parts by weight: 4-6 parts of gelatin composite hydrogel, 1-3 parts of gamma-methacryloxypropyl trimethoxy silane, 2-4 parts of nano hydroxyapatite, 1-3 parts of acrylic acid, 0.1-0.3 part of N, N-methylene bisacrylamide, 0.1-0.2 part of potassium persulfate and 0.1-0.3 part of N, N, N, N-tetramethyl ethylenediamine.
2. The modified nano-hydroxyapatite composite hydrogel according to claim 1, wherein the gelatin composite hydrogel comprises the following raw materials in parts by weight: 80-100 parts of gelatin hydrogel, 10-20 parts of sodium carboxymethylcellulose and 30-40 parts of epsilon-polylysine grafted chitosan loaded with silver-containing organic frameworks.
3. The modified nano-hydroxyapatite composite hydrogel according to claim 2, wherein the preparation method of the gelatin composite hydrogel is as follows: stirring and mixing epsilon-polylysine grafted chitosan loaded with a silver-containing organic framework, gelatin hydrogel and sodium carboxymethyl cellulose, transferring to a temperature of minus 20 ℃ for freezing for 24 hours, thawing, repeating for three times, soaking in a sodium hydroxide solution for 30 minutes, and finally washing to obtain the gelatin composite hydrogel.
4. The modified nano-hydroxyapatite composite hydrogel according to claim 2, wherein the epsilon-polylysine grafted chitosan loaded with the silver-containing organic framework comprises the following raw materials in parts by weight: 2-4 parts of potassium bromide, 0.2-0.6 part of 2, 6-tetramethylpiperidine 1-oxyl, 10-14 parts of chitosan, 2-4 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 1.0-1.4 parts of N-hydroxysuccinimide, 4-7 parts of epsilon-polylysine and 3-6 parts of silver-containing organic frameworks.
5. The modified nano-hydroxyapatite composite hydrogel according to claim 4, wherein the preparation method of the epsilon-polylysine grafted chitosan loaded with the silver-containing organic framework comprises the following steps of;
a1, dissolving potassium bromide and 2, 6-tetramethyl piperidine 1-oxyl in deionized water, then adding chitosan and dropwise adding sodium hypochlorite, adjusting the pH value of the mixed solution to 10-11 through hydrochloric acid, mixing and stirring fully, finally adding ethanol to stop the reaction, and finally centrifugally washing to obtain oxidized chitosan;
a2, dissolving oxidized chitosan in deionized water, then adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide, then reacting at 25 ℃ for 10min, centrifuging and washing to remove impurities, finally adding epsilon-polylysine, reacting at 25 ℃ for 24h, then adding a silver-containing organic framework, stirring and mixing, and finally washing, precipitating and freezing to obtain the epsilon-polylysine grafted chitosan loaded with the silver-containing organic framework.
6. The modified nano-hydroxyapatite composite hydrogel according to claim 5, wherein: the silver-containing organic framework is a reactant of silver nitrate and pyridine-3, 5-dicarboxylic acid.
7. The modified nano-hydroxyapatite composite hydrogel according to claim 6, wherein: the molar ratio of the silver nitrate to the pyridine-3, 5-dicarboxylic acid is (1.5-2.0): (0.5-1).
8. The modified nano-hydroxyapatite composite hydrogel according to claim 7, wherein the preparation method of the silver-containing organic skeleton is as follows: adding silver nitrate and pyridine-3, 5-dicarboxylic acid into deionized water, stirring and dispersing at room temperature to obtain a suspension, reacting the suspension at 200 ℃ for 8 hours, and finally separating, washing and drying to obtain the silver-containing organic framework.
9. A method for preparing the modified nano-hydroxyapatite composite hydrogel according to any one of claims 1 to 8, comprising the following steps:
adding gamma-methacryloxypropyl trimethoxy silane into an ethanol solution, uniformly mixing until complete hydrolysis, adding nano hydroxyapatite, slowly heating to 60 ℃ and continuously stirring, cooling the solution to room temperature, and washing and drying to obtain double bond modified nano hydroxyapatite;
dissolving gelatin composite hydrogel in deionized water, then adding double bond modified nano-hydroxyapatite, acrylic acid and N, N-methylene bisacrylamide, fully stirring, then adding potassium persulfate, stirring and reacting for 4 hours, then adding N, N, N, N-tetramethyl ethylenediamine, and finally reacting for 6 hours at 50 ℃ to obtain the modified nano-hydroxyapatite composite hydrogel.
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