CN101864046B - Glucosamine modified poly (ethylene glycol) diacrylate (PEGDA) hydrogel, preparation method and application thereof - Google Patents
Glucosamine modified poly (ethylene glycol) diacrylate (PEGDA) hydrogel, preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a glucosamine modified poly (ethylene glycol) diacrylate (PEGDA) hydrogel, a preparation method and application thereof. The glucosamine modified poly (ethylene glycol) diacrylate hydrogel contains 10-30 percent of poly (ethylene glycol) diacrylate, 1.0-10mM of acryloyl or propenyl glucosamine and 0.03-0.1 percent of initiating agent I2959. The preparation method comprises the steps of: preparing the PEGDA by using polyethyleneglycol as a basic material; preparing the acryloyl or propenyl glucosamine by using glucosamine hydrochloride as a raw material; and preparing a water solution or PBS (Poly (Butadiene-Styrene) solution by using the acryloyl or propenyl glucosamine and the initiating agent I2959 in a certain proportion, and can be cured into the hydrogel after being irradiated by ultraviolet with 365nm wavelength. The hydrogel can be used for tissue repair of clinical medicine, has simple preparation process, can realize in situ injection forming, meet the requirement on minimally invasive procedure, and has better application prospect and scientific significance.
Description
Technical field
The present invention relates to a kind of modified biological material and technology of preparing thereof, particularly a kind ofly have good biocompatibility and bioactive glucosamine modified poly (ethylene glycol) diacrylate (PEGDA) hydrogel and preparation method thereof and application concurrently.
Background technology
GS is to form cartilage cell epimatrix TGSS C3, hyaluronic structural unit.Glucosamine hydrochloride or vitriol are as a kind of medicine of clinical treatment osteoarthritis, and the pain of ability reduction of patient can reduce joint cavity and narrow down.Though its pharmacological action is not clear, experiment in vitro shows that finite concentration (adding 2mM in the substratum) GS can promote the chondrocyte's secretory protein glycan and the II collagen of dimensional culture, can raise the expression of TGFb-1 among the chondrocyte mRNA; Can promote the embryonic stem cell differentiating cartilage-forming cell of dimensional culture.The gel of covalent attachment GS can promote wound healing, can mediate host cell and grow into, and improves the biocompatibility of material greatly.
Gel be owing to can let the chondrocyte keep its phenotype, and nutritive substance and metabolic waste can spread and become cartilage tissue engineered ideal support.The PEG drugs approved by FDA is used for clinical bio-medical material, though PEG double methacrylate gel is a biocompatible materials, lacks biological activity and cell recognition signal, is unfavorable for the cell-specific gene activation.It is the effective means of preparation biologically active functional gel that the biological activity small molecules is attached in the support.
Summary of the invention
The objective of the invention is to biological activity small molecules GS is attached in the PEGDA gel, a kind of glucosamine modified poly (ethylene glycol) diacrylate (PEGDA) hydrogel that has good biocompatibility concurrently and can promote chondrocyte's secretory protein glycan is provided.
Another object of the present invention is to provide the preparation method of above-mentioned GS modified poly (ethylene glycol) double methacrylate (PEGDA) hydrogel.
The present invention also has a purpose to be to provide GS modified PE GDA preparing gel Application of Biomaterial.
The object of the invention is realized through following technical proposals:
A kind of glucosamine modified poly (ethylene glycol) diacrylate (PEGDA) hydrogel has following structure:
Where R is
or
n is 45 to 230.
A kind of preparation method of glucosamine modified poly (ethylene glycol) diacrylate (PEGDA) hydrogel comprises the steps:
(1) GS acryloyl verivate or GS propenyl derivatives and polyoxyethylene glycol double methacrylate are dissolved in the aqueous solution or the PBS (phosphate buffer solution) that weight fraction is 0.03%～0.08% I2959 (2-hydroxyl-4-(2-hydroxy ethoxy)-2-methyl phenyl ketone); The ultimate density of GS acryloyl or propenyl derivatives is 1.0mM～10.0mM in the mixed solution that obtains, and the ultimate density of polyoxyethylene glycol double methacrylate is 10%～30wt%;
(2) mixed solution is shone 4～10min under the 365nm wavelength, the irradiates light light intensity is 5～10mW/cm
2, promptly get glucosamine modified poly (ethylene glycol) diacrylate (PEGDA) hydrogel of the present invention.
Every material that contains acryloyl group all is to realize of the present inventionly in the said GS acryloyl verivate, comprises N-acryl GS.
The preparation method of said N-acryl GS comprises the steps:
(1) mixed solvent of glucosamine hydrochloride is water-soluble or water and acetone, regulating the pH value is 8～10, under the ice-water bath condition, drips acrylate chloride; Slowly be warming up to room temperature behind the reaction 2h, continue reaction 24h, add 99% (percent by volume) ethanol termination reaction; Remove by filter deposition
(2) will filtrate to concentrate and separate out white needle-like crystals, recrystallization purification crystal; The mol ratio of glucosamine hydrochloride and acrylate chloride is 1: 1.5～1: 1.
Every material that contains carbon-carbon double bond can be realized the object of the invention in the said GS propenyl derivatives, comprises the GS allyl ether.
The preparation method of said GS allyl ether is following:
The pH value of aqueous solution of regulating glucosamine hydrochloride is 8～10, adds Peng Qinghuana, under 40 ℃, dropwise adds allyl bromide 98, slowly is warming up to 60 ℃ of reaction 3h then, and solution washs to chloroform layer colourless through chloroform; With the lyophilize of aqueous solution part, ethyl alcohol recrystallization; The mol ratio of glucosamine hydrochloride and allyl bromide 98 is 1: 1.5～1: 3.
Said polyoxyethylene glycol double methacrylate can adopt the commodity on the market, also can adopt following method synthetic, and step is following:
Take by weighing the polyoxyethylene glycol of 50 grams, be dissolved in the 700ml toluene reflux; After removing the moisture in the raw material with water trap; Be cooled to room temperature, under high purity nitrogen protection, add the anhydrous triethylamine that is four times in polyoxyethylene glycol terminal hydroxy group amount of substance; Dropwise add the acrylate chloride that is four times in polyoxyethylene glycol terminal hydroxy group amount of substance, 35 ℃ of following stirred overnight; Remove by filter the deposition that reaction generates, add ether in the filtrating and place 4 ℃ of refrigerators, separate out white precipitate; Filter, will precipitate and be dissolved in the 100ml toluene adding ether again; Place 4 ℃ of refrigerators; Separate out white precipitate, repeat to filter and dissolve twice again, the gained white precipitate is in the dry 24h of 35 ℃ of vacuum drying ovens.
The number-average molecular weight of said polyoxyethylene glycol is 2000～10000.
The application of a kind of glucosamine modified poly (ethylene glycol) diacrylate (PEGDA) hydrogel in cartilage tissue engineered.
Though PEG double methacrylate gel is a biocompatible materials, lack biological activity and cell recognition signal, be unfavorable for the cell-specific gene activation.Saccharide compound plays an important role in vital movement processes such as signal identification and signal conduction.GS is a kind of amino monose, is one of structural unit of forming the cartilage cell epimatrix TGSS C3, also is the depot drug product of clinical treatment osteoarthritis.The cell in vitro experiment shows, adds chondrocyte's secretory protein glycan and II collagen that GS can promote dimensional culture, can raise the expression of TGFb-1 among the chondrocyte mRNA; Can promote the embryonic stem cell differentiating cartilage-forming cell of dimensional culture.The present invention connects two keys on GS, utilize the ultraviolet light cross-linking technology crosslinked with PEGDA, prepares the hydrogel support of a kind of biological activity small molecules GS modification, is used for cartilaginous tissue and makes up.
Principle of the present invention: GS is a kind of pyranoid ring monose; The hydroxy amino that can react is arranged on the ring; Can be through amidation, esterification or etherification reaction are introduced two keys, with PEGDA under action of ultraviolet light; Initiator I2959 produces radical with two key effects, and two key GSs of band and PEGDA are cross-linked to form hydrogel.
The present invention compared with prior art has following advantage:
(1) hydrogel material of the present invention contains biological activity small molecules GS, makes it have specific biological function and excellent biological compatibility.
(2) the present invention can regulate mechanical property, the swelling ratio of gel through changing molecular weight and the consumption of PEGDA.
(3) material package bone marrow interstital stem cell of the present invention can promote it to be divided into cartilage, improves the TGSS C3 secretory volume.
(4) technology of the present invention's employing is simple, helps large-scale production.
Description of drawings
Fig. 1 be before and after the material gelization proton nuclear magnetic resonance spectroscopy figure (
1H-NMR).
Fig. 2 is the total reflection Fourier infrared spectrogram (ATR-FTIR) of gelatinous material.
Fig. 3 is the chemical structural formula of gelatinous material.
Fig. 4 is the fluorescent microscope photo that the gel of embodiment 2 preparations encapsulates the bone marrow interstital stem cell of green fluorescent protein mark.
Fig. 5 is the bone marrow interstital stem cell (GFP-BMSCs) of the gel encapsulation green fluorescent protein mark of embodiment 3 preparations, cultivates 28 days TGSS C3 result.
Fig. 6 is the structural formula of embodiment 4 gels
Embodiment
For better understanding the present invention, below in conjunction with embodiment the present invention is done explanation further, but the scope that the present invention requires to protect is not limited to the scope that embodiment representes.
Embodiment 1
Preparation GS modified PE GDA hydrogel comprises the steps:
(1) the polyoxyethylene glycol double methacrylate is synthetic
Take by weighing the polyoxyethylene glycol (number-average molecular weight 4000) of 50 grams, be dissolved in the 700ml toluene reflux; After removing the moisture content in the raw material with water trap; Be cooled to room temperature, under high purity nitrogen protection, add 0.1 mole of anhydrous triethylamine; Dropwise add 0.1 mol propylene acyl chlorides, stirred 24 hours down at 35 ℃.Remove by filter the deposition that reaction generates, add 300 milliliters of ether in the filtrating and place 4 ℃ of refrigerators, separate out white precipitate; Filter; To precipitate and be dissolved in again in the 100ml benzene, add 200 milliliters of ether, separate out white precipitate in 4 ℃ of refrigerators; Repeat to filter and dissolve twice, the gained white precipitate was in dry 24 hours of 35 ℃ of vacuum drying ovens again.
(2) N-acryl GS (AGA) is synthetic: 8.6 gram glucosamine hydrochlorides are dissolved in 40ml water, and the regulator solution pH value is 8～10, under the ice-water bath condition, drips 3.5 milliliters of acrylate chlorides; React and slowly be warming up to room temperature after 2 hours; Continue reaction 24 hours, add 200 milliliter of 99% (percent by volume) ethanol termination reaction, remove by filter the salt that reaction produces; To filtrate to concentrate and separate out white needle-like crystals, recrystallization purification crystal.
(3) preparation of N-acryl GS modified PE GDA gel
1g polyoxyethylene glycol double methacrylate and 1.2mgN-acrylamido glucose are dissolved in the I2959PBS solution of 5ml 0.03% weight; The ultimate density of N-acrylamido glucose is 1.0mM in the mixed solution that obtains, and the ultimate density of polyoxyethylene glycol double methacrylate is 20wt%; With 96 orifice plates is mould, draw the above-mentioned solution of 40ul and place orifice plate, and at 365nm, 5mW/cm
2UV-light down according to 10min gelatinous material of the present invention.Fig. 3 is embodiment 1 a gel chemical structural formula, and n is 45.
It is as shown in Figure 1,
1H-NMR analyzes confirmation, before the gelation of material prepolymer solution, end thiazolinyl CH occurs at chemical shift δ 5.5～6.5ppm place
2The absorption peak of=CH-, after the gelation, this place's absorption peak disappears, and explains that radical addition polymerization has taken place the end thiazolinyl of GS and PEGDA.1646cm on the ATR-FTIR spectrogram behind the gel refrigeration drying shown in Figure 2
-1And 1548cm
-1The charateristic avsorption band of acid amides I band and II band has appearred in the place, confirms that further GS and PEGDA under UV-irradiation radical addition polymerization have taken place, and have formed cross linked gel.
Embodiment 2
(1) the polyoxyethylene glycol double methacrylate is synthetic
Take by weighing the polyoxyethylene glycol (number-average molecular weight 10000) of 50 grams, be dissolved in the 700ml toluene reflux; After removing the moisture content in the raw material with water trap; Be cooled to room temperature, under high purity nitrogen protection, add 0.04 mole of anhydrous triethylamine; Dropwise add 0.04 mol propylene acyl chlorides, stirred 24 hours down at 35 ℃.Remove by filter the triethylamine salt that reaction generates, add 300 milliliters of ether in the filtrating and place 4 ℃ of refrigerators, separate out white precipitate; Filter; To precipitate and be dissolved in again in the 100ml benzene, add 200 milliliters of ether, separate out white precipitate in 4 ℃ of refrigerators; Repeat to filter and dissolve twice, the gained white precipitate is in the dry 24h of 35 ℃ of vacuum drying ovens again.
(2) N-acryl GS is synthetic: the 8.6g glucosamine hydrochloride is dissolved in 30ml water and the 10ml acetone mixed solvent, and the regulator solution pH value is 8～10, under the ice-water bath condition, drips acrylate chloride 3.5ml; Slowly be warming up to room temperature behind the reaction 2h; Continue reaction 24h, add 200 milliliter of 99% (percent by volume) ethanol termination reaction, remove by filter the salt that reaction produces; Filtrating concentrates the adularescent needle-like crystal and separates out recrystallization purification crystal.
(3) preparation of N-acryl GS modified PE GDA gel
Preparation GS modified PE GDA hydrogel comprises the steps: that (1) is dissolved in 1.5g polyoxyethylene glycol double methacrylate and 11.6mg N-acrylamido glucose the phosphate buffer solution of pH value 7.4 of the I2959 of 5ml 0.06%; The ultimate density of N-acrylamido glucose is 10.0mM in the mixed solution that obtains, and the ultimate density of polyoxyethylene glycol double methacrylate is that 30wt% (2) is a mould with 96 orifice plates, draw 40ul step (1) solution and place orifice plate, and at 365nm, 7mW/cm
2UV-light down according to 7min gelatinous material of the present invention.
The bone marrow interstital stem cell step of GS modified PE GDA gelinite outer package green fluorescent protein mark: (1) is with disinfectant 1.5g polyoxyethylene glycol double methacrylate and 11.6mg N-acrylamido glucose are dissolved in the I2959PBS solution of 5ml 0.06% weight; (2) draw the above-mentioned solution of 2ml, mix with the rat mesenchymal stem cells suspension of equivalent green fluorescent protein mark; (3) be mould with 96 orifice plates, draw step 2 solution 40ul in orifice plate, at 365nm, 7mW/cm
2UV-light according to 7min, places 2 orifice plates to cultivate the gel cell conjugate down.
Fig. 4 is the fluorescent microscope photo that the gel of embodiment 2 preparations encapsulates the bone marrow interstital stem cell vitro culture 7d of green fluorescent protein mark.The strong green fluorescence of cell expressing among the figure, the testimonial material biocompatibility is good.
Embodiment 3
(1) the polyoxyethylene glycol double methacrylate is synthetic
Take by weighing the polyoxyethylene glycol (number-average molecular weight 10000) of 50 grams, be dissolved in the 700ml toluene reflux; After removing the moisture content in the raw material with water trap; Be cooled to room temperature, under high purity nitrogen protection, add 0.04 mole of anhydrous triethylamine; Dropwise add 0.04 mol propylene acyl chlorides, stirred 24 hours down at 35 ℃.Remove by filter the triethylamine salt that reaction generates, add 300 milliliters of ether in the filtrating and place 4 ℃ of refrigerators, separate out white precipitate; Filter; To precipitate and be dissolved in again in the 100ml benzene, add 200 milliliters of ether, separate out white precipitate in 4 ℃ of refrigerators; Repeat to filter and dissolve twice, the gained white precipitate is in the dry 24h of 35 ℃ of vacuum drying ovens again.
(2) N-acryl GS is synthetic: the 8.6g glucosamine hydrochloride is dissolved in 30ml water and the 10ml acetone mixed solvent, and the regulator solution pH value is 8～10, under the ice-water bath condition, drips acrylate chloride 3.5ml; Slowly be warming up to room temperature behind the reaction 2h; Continue reaction 24h, add 99% ethanol termination reaction, remove by filter the salt that reaction produces; Filtrating concentrates the adularescent needle-like crystal and separates out recrystallization purification crystal.
(3) preparation of N-acryl GS modified PE GDA gel
Preparation GS modified PE GDA hydrogel comprises the steps: that (1) is dissolved in 0.5g polyoxyethylene glycol double methacrylate and 5.8mg N-acrylamido glucose the phosphate buffer solution of pH value 7.4 of the I2959 of 5ml 0.08%; The ultimate density of N-acrylamido glucose is 5.0mM in the mixed solution that obtains, and the ultimate density of polyoxyethylene glycol double methacrylate is that 10wt% (2) is a mould with 96 orifice plates, draw 40ul step (1) solution and place orifice plate, and at 365nm, 8mW/cm
2UV-light down according to 5min gelatinous material of the present invention.
GS modified PE GDA gelinite outer package GFP-BMSCs step: (1) is with disinfectant 1.0g polyoxyethylene glycol double methacrylate and 11.6mg N-acrylamido glucose are dissolved in the I2959PBS solution of 5ml 0.08%; (2) draw the above-mentioned solution of 2ml, mix with the bone marrow interstital stem cell suspension of equivalent green fluorescent protein mark; (3) be mould with 96 orifice plates, draw step 2 solution 40ul in orifice plate, at 365nm, 8mW/cm
2UV-light according to 5min, places 24 orifice plates to cultivate the gel cell conjugate down.
Control group: the bone marrow interstital stem cell step of PEGDA gelinite outer package green fluorescent protein mark: (1) disinfectant 1.0g polyoxyethylene glycol double methacrylate is dissolved in the I2959PBS solution of 5ml 0.08%; (2) draw the above-mentioned solution of 2ml, mix with the bone marrow interstital stem cell suspension of equivalent green fluorescent protein mark; (3) be mould with 96 orifice plates, draw step 2 solution 40ul in orifice plate, at 365nm, 8mW/cm
2UV-light according to 5min, places 24 orifice plates to cultivate the gel cell conjugate down.
Fig. 5 is the bone marrow interstital stem cell of the gel encapsulation green fluorescent protein mark of embodiment 3 preparations, cultivates 28 days TGSS C3 result.The result shows that GS modified PE GDA can promote the bone marrow interstital stem cell of green fluorescent protein mark to be divided into cartilage, improves the secretory volume of extracellular matrix TGSS C3.
Embodiment 4
(1) the polyoxyethylene glycol double methacrylate is synthetic
Take by weighing the polyoxyethylene glycol (number-average molecular weight 10000) of 50 grams, be dissolved in the 700ml toluene reflux; After removing the moisture content in the raw material with water trap; Be cooled to room temperature, under high purity nitrogen protection, add 0.04 mole of anhydrous triethylamine; Dropwise add 0.04 mol propylene acyl chlorides, stirred 24 hours down at 35 ℃.Remove by filter the triethylamine salt that reaction generates, add 300 milliliters of ether in the filtrating and place 4 ℃ of refrigerators, separate out white precipitate; Filter; To precipitate and be dissolved in again in the 100ml benzene, add 200 milliliters of ether, separate out white precipitate in 4 ℃ of refrigerators; Repeat to filter and dissolve twice, the gained white precipitate is in the dry 24h of 35 ℃ of vacuum drying ovens again.
(2) the GS allyl ether is synthetic:
It is in 8～10 the aqueous solution, to be catalyzer with the Peng Qinghuana that the 20g glucosamine hydrochloride is dissolved in pH value, under 40 ℃, dropwise adds allyl bromide 98 30g, slowly is warming up to 60 ℃ of reaction 3h then, and solution washs to chloroform layer colourless through chloroform.The lyophilize of aqueous solution part, ethyl alcohol recrystallization.The feed ratio of glucosamine hydrochloride and allyl bromide 98 (ratio of amount of substance) is: 1: 3.
(3) preparation of GS modified PE GDA gel
Preparation GS modified PE GDA hydrogel comprises the steps: that (1) is dissolved in 1.0g polyoxyethylene glycol double methacrylate and 1.1mg GS allyl ether the phosphate buffer solution of pH value 7.4 of the I2959 of 5ml 0.08%; The ultimate density of GS allyl ether is 1.0mM in the mixed solution that obtains, and the ultimate density of polyoxyethylene glycol double methacrylate is that 20wt% (2) is a mould with 96 orifice plates, draw 40ul step (1) solution and place orifice plate, and at 365nm, 10mW/cm
2UV-light down according to 4min gelatinous material of the present invention.
Fig. 6 is the structural formula of embodiment 4 gels, and n is 230.
Claims (4)
1. glucosamine modified poly (ethylene glycol) diacrylate (PEGDA) hydrogel is characterized in that: have following structure:
Wherein R is 45～230 for
n.
2. the preparation method of the described a kind of glucosamine modified poly (ethylene glycol) diacrylate (PEGDA) hydrogel of claim 1 is characterized in that, comprises the steps:
(1) GS acryloyl verivate and polyoxyethylene glycol double methacrylate are dissolved in the aqueous solution or the phosphate buffer solution that weight fraction is 2-hydroxyl-4-(2-hydroxy ethoxy)-2-methyl phenyl ketone of 0.03%～0.08%; The ultimate density of GS acryloyl verivate is 1.0mM～10.0mM in the mixed solution that obtains, and the ultimate density of polyoxyethylene glycol double methacrylate is 10%～30wt%;
(2) mixed solution is shone 4～10min under the 365nm wavelength, the irradiates light light intensity is 5～10mW/cm
2, promptly get glucosamine modified poly (ethylene glycol) diacrylate (PEGDA) hydrogel.
3. preparation method according to claim 2 is characterized in that, said GS acryloyl verivate comprises N-acryl GS.
4. preparation method according to claim 3 is characterized in that, the preparation method of said N-acryl GS comprises the steps:
(1) mixed solvent of glucosamine hydrochloride is water-soluble or water and acetone, regulating the pH value is 8～10, under the ice-water bath condition, drips acrylate chloride; Slowly be warming up to room temperature behind the reaction 2h, continue reaction 24h, add 99% volume ethanol termination reaction; Remove by filter deposition
(2) will filtrate to concentrate and separate out white needle-like crystals, recrystallization purification crystal; The mol ratio of glucosamine hydrochloride and acrylate chloride is 1: 1.5～1: 1.
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| CN108841776B (en) * | 2018-06-13 | 2022-05-10 | 河海大学常州校区 | Preparation method and application of 3D gel with adjustable components |
| CN108906007B (en) * | 2018-07-20 | 2021-04-13 | 河南中医药大学 | Preparation method and application of glycosyl hydrophilic magnetic composite microspheres |
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| CN1895773A (en) * | 2006-06-15 | 2007-01-17 | 南开大学 | Chromatographic fixed-phase for modified glycan substrate, its preparation and use |
| EP2149581A1 (en) * | 2007-04-20 | 2010-02-03 | Institut Molekulyarnoi Biologii Im. V.A. Engelgardta Rossiiskoi Akademii Nauk | Monomer and composition for producing low-percentage hydrogel and/or hydrogel having a low cross linkage content, a hydrogel and a biochip based thereon |
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| CN1895773A (en) * | 2006-06-15 | 2007-01-17 | 南开大学 | Chromatographic fixed-phase for modified glycan substrate, its preparation and use |
| EP2149581A1 (en) * | 2007-04-20 | 2010-02-03 | Institut Molekulyarnoi Biologii Im. V.A. Engelgardta Rossiiskoi Akademii Nauk | Monomer and composition for producing low-percentage hydrogel and/or hydrogel having a low cross linkage content, a hydrogel and a biochip based thereon |
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