CN102784414B - Preparation method of injectable double-cross-linked hydrogel for tissue engineering - Google Patents
Preparation method of injectable double-cross-linked hydrogel for tissue engineering Download PDFInfo
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Abstract
The invention relates to a preparation method of injectable double-cross-linked hydrogel for tissue engineering, which comprises the following steps that: an aqueous solution of aminated gelatin, an aqueous solution of aldehyde dextran, and an aqueous solution of terminated vinyl poly ethylene glycol are mixed according to a volume ratio of 4:4:3, then are cross-linked for 10-20 minutes at a temperature of 35 to 40 DED C, and finally are cross-linked for 3 to 8 minutes by ultraviolet irradiation. The preparation method provided by the invention has a simple operation process and mild implementation conditions; and the double-cross-linked hydrogel obtained by the invention is non-toxic and biodegradable, has good mechanical properties and biocompatibility, and can be used for injectable hydrogel scaffold in the tissue engineering.
Description
Technical field
The invention belongs to the preparation field of hydrogel, particularly a kind of preparation method of the two cross-linked hydrogels of syringeability that can be used for organizational project.
Background technology
Hydrogel is hydrophilic polymer network, and it can absorb a large amount of moisture, but due to the physical crosslinking between polymer chain and chemical crosslinking effect and can not be dissolved in the water, can only swelling and keep certain shape.Hydrogel has good biocompatibility, water permeability, and can obtain the hydrogel material of diverse microcosmic structure and performance by synthetic, and these character make hydrogel obtain a wide range of applications at biomedical sector.
Injection aquagel for organizational project is that cell/carrier complexes is injected in body, forms new tissue, repairs the damaged object of body thereby reach.The method has wound feature little and simple to operate, and repairing irregularly when damaged, injectable cartilage can directly inject defective region, carries out part moulding before solidifying, and has advantages of that plasticity is strong.In addition, hydrogel solution also can mix with various medicines, is injected directly into ad-hoc location by syringe.Therefore hydrogel that can formed in situ has wide practical use in organizational project.
At present, the molding mode of syringeability hydrogel material mainly comprises chemical crosslinking, crosslinking with radiation, four kinds of modes of light initiation polymerization and physical crosslinking.The hydrogel material adopting comprises that natural material is if alginate, collagen, hyaluronic acid, agar, chitosan, glucosan and gelatin etc. and polymeric material are as poly-fumaric acid propylene glycol ester, Polyethylene Glycol and polyethylene glycol oxide propylene oxide copolymer etc.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of the two cross-linked hydrogels of syringeability that can be used for organizational project, and the method operating procedure is simple, implementation condition gentleness, this hydrogel good biocompatibility, easily degraded, synthesized polymer material biologically inert is good, and mechanical performance is strong.
The preparation method of a kind of two cross-linked hydrogels of syringeability that can be used for organizational project of the present invention, comprising:
By the 4:4:3 mixing by volume of the aqueous solution of the aqueous solution of the aqueous solution of aminated gelatin, aldehyde radical glucosan and the vinylated wall Polyethylene Glycol of end group, then crosslinked 10-20min at 35-40 DEG C, finally carries out the crosslinked 3-8min of ultra-vioket radiation, to obtain final product.
The crosslinked middle-ultraviolet lamp generator of described ultra-vioket radiation is wavelength 365nm, power 5mW/cm
2uviol lamp.
The mass percent concentration of the aqueous solution of described aminated gelatin is 15-25%, and the mass percent concentration of the aqueous solution of aldehyde radical glucosan is 8-15%, and the mass percent concentration of the aqueous solution of the vinylated wall Polyethylene Glycol of end group is 15-25%.
The preparation method of described aminated gelatin comprises: ethylenediamine and carbodiimides are added in aqueous gelatin solution, and the mol ratio that makes carboxyl, ethylenediamine and carbodiimides on gelatin is 1:10-50:1.2-5; Then under room temperature, reaction is spent the night, and dialysis ,-60 DEG C of lyophilizations, to obtain final product.
The mass percent concentration of above-mentioned aqueous gelatin solution is 2-5%.
Saturating 3 days of above-mentioned dialysis is that to adopt molecular cut off be 3500 bag filter.
Described aldehyde radical glucosan preparation method comprises: sodium metaperiodate is added in glucan aqueous solution, and the mol ratio that makes the construction unit of sodium metaperiodate and glucosan is 0.2-1:1; Then under room temperature, react 2-5h, dialysis ,-60 DEG C of lyophilizations.
The mass percent concentration of above-mentioned glucan aqueous solution is 0.05-2%.
Above-mentioned dialysis is to adopt the bag filter that molecular cut off is 3500 to dialyse 3 days.
The preparation method of the vinylated wall Polyethylene Glycol of described end group comprises: by wall Polyethylene Glycol (upper seascape space bio tech ltd, Shanghai, China), triethylamine, acryloyl chloride be dissolved in anhydrous methylene chloride, wherein the mol ratio of wall Polyethylene Glycol, triethylamine and acryloyl chloride is 1:1-6:1-10; Then after reacting 40-60h under room temperature, purify with excessive ether sedimentation, be again dissolved in dichloromethane, use excessive ether sedimentation, in triplicate, under room temperature, reduced vacuum is dry, to obtain final product.
The light trigger adopting during described ultra-vioket radiation is crosslinked is gorgeous reinforcing 2959(Sigma company, Shanghai, China).
In the preparation method of the two cross-linked hydrogels of syringeability of the present invention, glucosan is by NaIO
4be oxidized adjacent hydroxyl and form aldehyde radical; Gelatin forms amination gelatin with ethylenediamine condensation under carbodiimides exists; Wall Polyethylene Glycol reacts with acryloyl chloride and forms the vinylated wall Polyethylene Glycol of end group under the existence of triethylamine.First, aldehyde radical glucosan and aminated gelatin are cross-linked to form first network hydrogel by the schiff base reaction between aldehyde radical and amino.Then, the vinylated wall Polyethylene Glycol of end group utilizes 365nm ultraviolet photo-initiated crosslinking under the existence of the gorgeous reinforcing 2959 of light trigger (I 2959), forms second network hydrogel.
The design of of the present invention pair of cross-linked hydrogel can make in practical operation, and the incipient stage can spontaneous fast accelerated gum, can prevent moving of solution everywhere.
The design of of the present invention pair of cross-linked hydrogel can make the gel finally obtaining have stronger mechanical property, in actual test, soaks hydrogel after 12h and still have the compression molding value of 20kPa in water.
The design of of the present invention pair of cross-linked hydrogel makes hydrogel support to reach controlled degradation property by the content that regulates component.
Beneficial effect:
(1) the inventive method operating procedure is simple, implementation condition gentleness;
(2) the natural material good biocompatibility of of the present invention pair of cross-linked hydrogel, easily degraded, synthesized polymer material biologically inert is good, and mechanical performance is strong, is expected to be applied to the injection aquagel support in organizational project.
Brief description of the drawings
Fig. 1 a is the schematic diagram of preparing of aldehyde radical glucosan;
Fig. 1 b is the schematic diagram of preparing of aminated gelatin;
Fig. 1 c is the schematic diagram of preparing of the vinylated wall Polyethylene Glycol of end group;
Fig. 2 is the plastic process schematic diagram of two cross-linked hydrogels;
Fig. 3 is the degraded schematic diagrams of two cross-linked hydrogels in PBS;
Fig. 4 is that skeletonization prerequisite cell is cultivated the growing state schematic diagram after 24h in double cross connection hydrogel surface;
Fig. 5 is that skeletonization prerequisite cell is cultivated the growing state schematic diagram after 4 days and 8 days in two cross-linked hydrogels;
Wherein, the I2959 in Fig. 1 and Fig. 2 represents gorgeous reinforcing 2959, and ODex represents aldehyde radical glucosan, and MGel represents aminated gelatin, and 4A-PEGDA represents the vinylated wall Polyethylene Glycol of end group.
Detailed description of the invention
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
As shown in Figure 1a, get glucosan and add in deionized water, magnetic agitation, until glucosan dissolves completely, is made into the glucan aqueous solution of mass percent concentration 1%.Add sodium metaperiodate (NaIO
4), wherein the mol ratio of the construction unit of sodium metaperiodate and glucosan is 1:2, after the lower lucifuge stirring reaction 4h of room temperature (25 DEG C), adds 5ml ethylene glycol, continues to stir 15min for cessation reaction.Product is packed in bag filter (molecular cut off is 3500) and dialysed 3 days, change water every day 4 times.Then product is taken out and is placed in plastic culture dish, pre-freeze 12h in cryogenic refrigerator, and by the lyophilization of pre-freeze thing, finally obtain part aldehyde radical glucosan white product.
Embodiment 2
As shown in Figure 1 b, get gelatin and be dissolved in 0.1M phosphate solution (pH5.0), obtain mass percent concentration and be 4% aqueous gelatin solution, after dissolving (solution is transparency liquid) completely, add ethylenediamine (ED).Magnetic agitation mix homogeneously, is adjusted to pH=5.0 with the HCl of 6M, then adds carbodiimides (EDC), under room temperature, reacts 4h; Wherein the mol ratio of the carboxyl on gelatin, ethylenediamine and carbodiimides is 1:40:2.Product is packed in bag filter (cut off Mw=3500) and dialysed 3 days, change water every day 3 ~ 4 times.After dialysis completely, dialysis solution is poured in frosting ware, put into cryogenic refrigerator pre-freeze 24h, by the lyophilization of pre-freeze thing, finally obtain the white product of modified gelatin.
Embodiment 3
As shown in Fig. 1 c; getting 8g wall Polyethylene Glycol is dissolved in the anhydrous methylene chloride of 200ml; the minor amount of water of going out in wall Polyethylene Glycol by azeotropic distillation; be cooled to room temperature; add triethylamine; then under nitrogen protection, drip acryloyl chloride, under room temperature, react 48h, wherein the mol ratio of wall Polyethylene Glycol, triethylamine and acryloyl chloride is 1:4:8.Purify with excessive ether sedimentation afterwards, be again dissolved in dichloromethane, use excessive ether sedimentation, in triplicate, under room temperature, reduced vacuum is dry for purification process, has both obtained white product.
Embodiment 4
As shown in Figure 2, the aminated aqueous gelatin solution that is first 20% by mass percent concentration, mass percent concentration is the vinylated wall Aqueous Solutions of Polyethylene Glycol of the end group 4:4:3 mixing by volume that 10% aldehyde radical glucan aqueous solution and mass percent concentration are 20%, then add gorgeous reinforcing 2595 photo-crosslinking initiator (Sigma companies, Shanghai, China) and to make its ultimate density be 0.1% (w/v).At 37 DEG C, be cross-linked 15 minutes, then at 365nm wavelength, 5mW/cm
2under the uviol lamp of power, irradiate and be cross-linked for 5 minutes, both obtained two cross-linked hydrogels.
Embodiment 5
According to method shown in embodiment 4, prepare cylindrical pair of cross-linked hydrogel piece, after soaking 24h under room temperature in phosphate buffer (pH=7.4), use universal testing machine (Dejie DXLL-20000) to carry out compression test to hydrogel, the modulus of compressibility that draws hydrogel is 19.84kPa.
Embodiment 6
According to method shown in embodiment 4, the two cross-linked hydrogel pieces of preparation, and the content by changing the vinylated wall Polyethylene Glycol of end group wherein as a control group, then be immersed in the phosphate buffer (pH=7.4) of 37 DEG C, regularly take out, lyophilization, weighs, and calculates degradation curve.As shown in Figure 3, two cross-linked hydrogels decompose 60% quality in two initial week, and mass loss subsequently slows down, and still keep about 30% quality in the time of the 5th week.
Embodiment 7
(400 μ l) in centrifuge tube, to add the aldehyde radical glucan aqueous solution using respectively after 0.22 μ m membrane filtration sterilizing, (l), (300 μ l) for the vinylated wall Polyethylene Glycol of end group and gorgeous reinforcing 2595 light trigger mixed aqueous solutions for 400 μ for aminated aqueous gelatin solution.After mix homogeneously, inject 48 porocyte culture plates with pipettor, then according to method shown in embodiment 4, prepare cylindrical pair of cross-linked hydrogel piece.By in skeletonization prerequisite cell seeding and hydrogel surface, cell density is set as 10,000/ml.Cultivate after 24h, utilize cell reagent box dyeing anyway, observation of cell form under fluorescence microscope.As shown in Figure 4, skeletonization prerequisite cell can well adhere on two cross-linked hydrogels, sprawls, and keeps surviving.Prove that two cross-linked hydrogels have the good surface biological compatibility.
Embodiment 8
In centrifuge tube, add high concentration cell suspension after counting, then (400 μ l) to add the aldehyde radical glucan aqueous solution using respectively after 0.22 μ m membrane filtration sterilizing, (400 μ l) for aminated aqueous gelatin solution, (l), make final cell density dilution is 5 × 10 to 300 μ for the vinylated wall Polyethylene Glycol of end group and gorgeous reinforcing 2595 light trigger mixed aqueous solutions
6.Mixed solution is injected in 48 orifice plates, prepare two cross-linked hydrogel pieces of internal package cell according to method shown in embodiment 4.Afterwards, rapidly, toward the α-MEM that adds 1ml to contain 10% bovine serum albumin in 48 orifice plates, put into incubator cultivation.After 30min, change liquid once, change liquid once after 60min, change liquid once later every day.At the 4th day, ((Fig. 5 b) carried out after immunofluorescence dyeing with phalloidin-Alexa568 and DAPI cell, observes shooting with laser confocal microscope for Fig. 5 a) He eight day respectively.As shown in Figure 5, skeletonization precursor can survive and sprawl in two cross-linked hydrogels, increases and becomes large with incubation time.Prove that prepared two cross-linked hydrogels have good biocompatibility, and can support osteoblast to grow therein.
Claims (6)
1. a preparation method that can be used for the two cross-linked hydrogels of syringeability of organizational project, comprising:
By the 4:4:3 mixing by volume of the aqueous solution of the aqueous solution of the aqueous solution of aminated gelatin, aldehyde radical glucosan and the vinylated four arm Polyethylene Glycol of end group, then crosslinked 10-20min at 35-40 DEG C, finally carries out the crosslinked 3-8min of ultra-vioket radiation, to obtain final product;
The mass percent concentration of the aqueous solution of described aminated gelatin is 15-25%, and the mass percent concentration of the aqueous solution of aldehyde radical glucosan is 8-15%, and the mass percent concentration of the aqueous solution of the vinylated four arm Polyethylene Glycol of end group is 15-25%;
The preparation method of described aminated gelatin comprises: ethylenediamine and carbodiimides are added in aqueous gelatin solution, and the mol ratio that makes carboxyl, ethylenediamine and carbodiimides on gelatin is 1:10-50:1.2-5; Then under room temperature, reaction is spent the night, and dialysis, lyophilization, to obtain final product;
Described aldehyde radical glucosan preparation method comprises: sodium metaperiodate is added in glucan aqueous solution, and the mol ratio that makes the construction unit of sodium metaperiodate and glucosan is 0.2-1:1; Then under room temperature, react, dialysis, lyophilization;
The preparation method of the vinylated four arm Polyethylene Glycol of described end group comprises: four arm Polyethylene Glycol, triethylamine, acryloyl chloride are dissolved in anhydrous methylene chloride, and wherein the mol ratio of four arm Polyethylene Glycol, triethylamine and acryloyl chloride is 1:1-6:1-10; Then under room temperature, after reaction, purify with excessive ether sedimentation, be again dissolved in dichloromethane, use excessive ether sedimentation, in triplicate, under room temperature, reduced vacuum is dry, to obtain final product.
2. the preparation method of a kind of two cross-linked hydrogels of syringeability that can be used for organizational project according to claim 1, is characterized in that: the crosslinked middle-ultraviolet lamp generator of described ultra-vioket radiation is the uviol lamp of wavelength 365nm, power 5mW/cm2.
3. the preparation method of a kind of two cross-linked hydrogels of syringeability that can be used for organizational project according to claim 1, is characterized in that: the mass percent concentration of described aqueous gelatin solution is 2-5%.
4. the preparation method of a kind of two cross-linked hydrogels of syringeability that can be used for organizational project according to claim 1, is characterized in that: the mass percent concentration of described glucan aqueous solution is 0.05-2%.
5. the preparation method of the two cross-linked hydrogels of a kind of syringeability that can be used for organizational project according to claim 1, is characterized in that: described dialysis is to adopt saturating 3 days of the bag filter that molecular cut off is 3500.
6. the preparation method of a kind of two cross-linked hydrogels of syringeability that can be used for organizational project according to claim 1, is characterized in that: the light trigger adopting during described ultra-vioket radiation is crosslinked is gorgeous reinforcing 2959.
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CN101716366A (en) * | 2009-12-17 | 2010-06-02 | 天津大学 | Biocolloid hemostatic prepared by aldehyde-modified sodium alginate and amine-modified gelatine |
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