CN102784414A - 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 syringeability double cross that can be used for organizational project joins the method for preparing of hydrogel.
Background technology
Hydrogel is hydrophilic polymer network, and it can absorb a large amount of moisture, but because the interchain physical crosslinking of polymer and chemical crosslinking effect and can not be dissolved in the water, can only swelling and keep certain shape.Hydrogel has excellent biological compatibility, water permeability, and can obtain the hydrogel material of diverse microcosmic structure and performance through synthetic, and these character make hydrogel obtain to use widely at biomedical sector.
The injection aquagel that is used for organizational project is that cell/carrier complexes is injected in the body, forms new tissue, repairs the damaged purpose of body thereby reach.This method has wound characteristics little and simple to operate, is repairing irregularly when damaged, and the injectable cartilage can directly inject defective region, and it is moulding before curing, to carry out the part, has the strong advantage of plasticity.In addition, hydrogel solution also can mix with various medicines, is injected directly into ad-hoc location through syringe.Therefore but the hydrogel of 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 that adopts comprises that natural material such as alginate, collagen, hyaluronic acid, agar, chitosan, glucosan and gelatin etc. and polymeric material are as gathering 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 provides the method for preparing that a kind of syringeability double cross that can be used for organizational project joins hydrogel, and this method operating procedure is simple, and implementation condition is gentle; This hydrogel good biocompatibility; Be prone to degraded, the synthesized polymer material biologically inert is good, and mechanical performance is strong.
A kind of syringeability double cross that can be used for organizational project of the present invention joins the method for preparing of hydrogel, comprising:
With the aqueous solution of aminated gelatin, the aqueous solution of aldehyde radical glucosan and the aqueous solution 4:4:3 mixing by volume of the vinylated wall Polyethylene Glycol of end group, crosslinked 10-20min under 35-40 ℃ carries out the crosslinked 3-8min of ultra-vioket radiation at last then, promptly gets.
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 method for preparing of described aminated gelatin comprises: ethylenediamine and carbodiimides are added in the aqueous gelatin solution, and the mol ratio that makes carboxyl, ethylenediamine and carbodiimides on the gelatin is 1:10-50:1.2-5; Reaction is spent the night under the room temperature then, and dialysis ,-60 ℃ of lyophilizations promptly get.
The mass percent concentration of above-mentioned aqueous gelatin solution is 2-5%.
Above-mentioned dialysis is that 3500 bag filter passed through 3 days for adopting molecular cut off.
Described aldehyde radical glucosan method for preparing comprises: sodium metaperiodate is added in the glucan aqueous solution, and the mol ratio that makes the construction unit of sodium metaperiodate and glucosan is 0.2-1:1; React 2-5h under the room temperature then, dialysis ,-60 ℃ of lyophilizations get final product.
The mass percent concentration of above-mentioned glucan aqueous solution is 0.05-2%.
Above-mentioned dialysis is 3500 bag filter dialysis 3 days for adopting molecular cut off.
The method for preparing of the vinylated wall Polyethylene Glycol of described end group comprises: the wall Polyethylene Glycol (is gone up seascape space bio tech ltd; Shanghai; China), triethylamine, acryloyl chloride be dissolved in the anhydrous methylene chloride, wherein the mol ratio of wall Polyethylene Glycol, triethylamine and acryloyl chloride is 1:1-6:1-10; Purify with excessive ether sedimentation behind the reaction 40-60h under the room temperature then, be dissolved in dichloromethane once more, use excessive ether sedimentation, triplicate, reduced vacuum is dry under the room temperature, promptly gets.
The light trigger that adopts during described ultra-vioket radiation is crosslinked is gorgeous reinforcing 2959 (Sigma company, Shanghai, a China).
Glucosan is by NaIO in the method for preparing of syringeability double cross couplet hydrogel of the present invention
4The adjacent hydroxyl of oxidation forms aldehyde radical; Gelatin forms the amination gelatin with the ethylenediamine condensation in the presence of carbodiimides; The wall Polyethylene Glycol forms the vinylated wall Polyethylene Glycol of end group with the acryloyl chloride reaction in the presence of triethylamine.At first, aldehyde radical glucosan and aminated gelatin are cross-linked to form first network aqueous gel through the schiff base reaction between aldehyde radical and the amino.Then, the vinylated wall Polyethylene Glycol of end group utilizes 365nm ultraviolet photo-initiated crosslinking in the presence of the gorgeous reinforcing 2959 of light trigger (I 2959), form second network aqueous gel.
Double cross of the present invention joins the design of hydrogel can be so that in the practical operation, and the incipient stage can spontaneous fast accelerated gum, can prevent moving of solution everywhere.
The design that double cross of the present invention joins hydrogel can make the gel that finally obtains have stronger mechanical property, and in the actual test, the hydrogel in water behind the immersion 12h still has the compression molding value of 20kPa.
The design that double cross of the present invention joins hydrogel makes the hydrogel support to reach controlled degradation property through the content of regulating component.
Beneficial effect:
(1) the inventive method operating procedure is simple, and implementation condition is gentle;
(2) double cross of the present invention joins the natural material good biocompatibility of hydrogel, is prone to degraded, and the synthesized polymer material biologically inert is good, and mechanical performance is strong, is expected to be applied to the injection aquagel support in the organizational project.
Description of drawings
Fig. 1 a is the preparation sketch map of aldehyde radical glucosan;
Fig. 1 b is the preparation sketch map of aminated gelatin;
Fig. 1 c is the preparation sketch map of the vinylated wall Polyethylene Glycol of end group;
Fig. 2 is the one-tenth glue process sketch map that double cross joins hydrogel;
Fig. 3 is that double cross joins the degraded sketch map of hydrogel in PBS;
Fig. 4 is that skeletonization prerequisite cell joins the growing state sketch map after hydrogel surface is cultivated 24h in double cross;
Fig. 5 is that skeletonization prerequisite cell joins the growing state sketch map after cultivating 4 days and 8 days in the hydrogel in double cross;
Wherein, the I2959 among Fig. 1 and Fig. 2 representes gorgeous reinforcing 2959, and ODex representes the aldehyde radical glucosan, and MGel representes aminated gelatin, and 4A-PEGDA representes the vinylated wall Polyethylene Glycol of end group.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
Shown in Fig. 1 a, to get glucosan and add in the deionized water, magnetic agitation is made into the glucan aqueous solution of mass percent concentration 1% until the glucosan dissolving fully.Add sodium metaperiodate (NaIO
4), wherein the mol ratio of the construction unit of sodium metaperiodate and glucosan is 1:2, room temperature (25 ℃) adds 5ml ethylene glycol behind the lucifuge stirring reaction 4h down, continues to stir 15min and is used for cessation reaction.With the product dialysis 3 days of packing in the bag filter (molecular cut off is 3500), change water every day 4 times.Then product is taken out and place plastic culture dish, pre-freeze 12h in cryogenic refrigerator, and, finally obtain part aldehyde radical glucosan white product with the lyophilization of pre-freeze thing.
Embodiment 2
Shown in Fig. 1 b, get gelatin and be dissolved in the 0.1M phosphate solution (pH5.0), obtain mass percent concentration and be 4% aqueous gelatin solution, treat to dissolve fully (solution is transparency liquid) after, add ethylenediamine (ED).The magnetic agitation mix homogeneously transfers to pH=5.0 with the HCl of 6M, adds carbodiimides (EDC) then, and room temperature is reaction 4h down; Wherein the mol ratio of the carboxyl on the gelatin, ethylenediamine and carbodiimides is 1:40:2.With the product dialysis 3 days of packing in the bag filter (cut off Mw=3500), change water every day 3 ~ 4 times.After the dialysis fully, dialysis solution is poured in the frosting ware, put into cryogenic refrigerator pre-freeze 24h,, finally obtain the white product of modified gelatin the lyophilization of pre-freeze thing.
Embodiment 3
Shown in Fig. 1 c; Get 8g wall Polyethylene Glycol and be dissolved in the anhydrous methylene chloride of 200ml, go out the minor amount of water in the wall Polyethylene Glycol, be cooled to room temperature through azeotropic distillation; Add triethylamine; Under nitrogen protection, drip acryloyl chloride then, react 48h under the room temperature, wherein the mol ratio of wall Polyethylene Glycol, triethylamine and acryloyl chloride is 1:4:8.Purify with excessive ether sedimentation afterwards, be dissolved in dichloromethane once more, use excessive ether sedimentation, the purification process triplicate, reduced vacuum is dry under the room temperature, has both got white product.
As shown in Figure 2; Elder generation is 20% aminated aqueous gelatin solution with mass percent concentration; Mass percent concentration is that 10% aldehyde radical glucan aqueous solution and mass percent concentration are 20% the vinylated wall Polyethylene Glycol of end group aqueous solution 4:4:3 mixing by volume; Adding gorgeous reinforcing 2595 photo-crosslinking initiators (Sigma company, Shanghai, China) then and making its ultimate density is 0.1% (w/v).Descended crosslinked 15 minutes at 37 ℃, then at the 365nm wavelength, 5mW/cm
2The uviol lamp of power down irradiation 5 minutes is crosslinked, both double cross joins hydrogel.
Embodiment 5
According to method shown in the embodiment 4; Prepare cylindrical double cross and join the water-setting blob of viscose; In phosphate buffer (pH=7.4), soak after the 24h under the room temperature, use universal testing machine (Dejie DXLL-20000) that hydrogel is carried out compression test, the modulus of compressibility that draws hydrogel is 19.84kPa.
According to method shown in the embodiment 4, the preparation double cross joins the water-setting blob of viscose, and the content through changing the vinylated wall Polyethylene Glycol of end group wherein is as matched group; Be immersed in then in 37 ℃ the phosphate buffer (pH=7.4), regularly take out lyophilization; Weigh, calculate degradation curve.As shown in Figure 3, double cross joins hydrogel in the quality that decomposes 60% two initial week, and mass loss subsequently slows down, and when the 5th week, still keeps about 30% quality.
In centrifuge tube, add the aldehyde radical glucan aqueous solution (400 μ l) that uses respectively after 0.22 μ m membrane filtration is sterilized; Aminated aqueous gelatin solution (400 μ l), the vinylated wall Polyethylene Glycol of end group and gorgeous reinforcing 2595 light trigger mixed aqueous solutions (300 μ l).Behind the mix homogeneously, inject 48 porocyte culture plates,, prepare cylindrical double cross and join the water-setting blob of viscose then according to method shown in the embodiment 4 with pipettor.On skeletonization prerequisite cell seeding and hydrogel surface, cell density is set at 10,000/ml.After cultivating 24h, utilize cell reagent box dyeing anyway, observation of cell form under fluorescence microscope.As shown in Figure 4, skeletonization prerequisite cell can well join on the hydrogel in double cross and adheres to, and sprawls, and is held in work.Proved that double cross joins hydrogel and has the good surface biological compatibility.
Embodiment 8
In centrifuge tube, add through counting back high concentration cell suspension; Add the aldehyde radical glucan aqueous solution (400 μ l) that uses respectively after 0.22 μ m membrane filtration is sterilized then; Aminated aqueous gelatin solution (400 μ l); Vinylated wall Polyethylene Glycol of end group and gorgeous reinforcing 2595 light trigger mixed aqueous solutions (300 μ l) make that final cell density dilution is 5 * 10
6Mixed solution is injected in 48 orifice plates, and the double cross of preparing the internal package cell according to method shown in the embodiment 4 joins the water-setting blob of viscose.Afterwards, in 48 orifice plates, add α-MEM that 1ml contains 10% bovine serum albumin rapidly, put into incubator and cultivate.Change liquid behind the 30min once, change liquid once after 60min, change liquid once later every day.(Fig. 5 a) with after the 8th day (Fig. 5 b) pair cell carry out immunofluorescence dyeing with phalloidin-Alexa568 and DAPI, observed shooting with laser confocal microscope at the 4th day respectively.As shown in Figure 5, the skeletonization precursor can join in the hydrogel to become to live and sprawl in double cross, increases change greatly with incubation time.Proved that prepared double cross joins hydrogel and has good biocompatibility, and can support osteoblast portion's growth within it.
Claims (10)
1. a syringeability double cross that can be used for organizational project joins the method for preparing of hydrogel, comprising:
With the aqueous solution of aminated gelatin, the aqueous solution of aldehyde radical glucosan and the aqueous solution 4:4:3 mixing by volume of the vinylated wall Polyethylene Glycol of end group, crosslinked 10-20min under 35-40 ℃ carries out the crosslinked 3-8min of ultra-vioket radiation at last then, promptly gets.
2. a kind of syringeability double cross that can be used for organizational project according to claim 1 joins the method for preparing of hydrogel, and it is characterized in that: the crosslinked middle-ultraviolet lamp generator of described ultra-vioket radiation is wavelength 365nm, power 5mW/cm
2Uviol lamp.
3. a kind of syringeability double cross that can be used for organizational project according to claim 1 joins the method for preparing of hydrogel; It is characterized in that: the mass percent concentration of the aqueous solution of described aminated gelatin is 15-25%; 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%.
4. a kind of syringeability double cross that can be used for organizational project according to claim 1 joins the method for preparing of hydrogel; It is characterized in that: the method for preparing of described aminated gelatin comprises: ethylenediamine and carbodiimides are added in the aqueous gelatin solution, and the mol ratio that makes carboxyl, ethylenediamine and carbodiimides on the gelatin is 1:10-50:1.2-5; Reaction is spent the night under the room temperature then, and dialysis, lyophilization promptly get.
5. a kind of syringeability double cross that can be used for organizational project according to claim 4 joins the method for preparing of hydrogel, and it is characterized in that: the mass percent concentration of said aqueous gelatin solution is 2-5%.
6. a kind of syringeability double cross that can be used for organizational project according to claim 1 joins the method for preparing of hydrogel; It is characterized in that: described aldehyde radical glucosan method for preparing comprises: sodium metaperiodate is added in the glucan aqueous solution, and the mol ratio that makes the construction unit of sodium metaperiodate and glucosan is 0.2-1:1; React under the room temperature then, dialysis, lyophilization get final product.
7. a kind of syringeability double cross that can be used for organizational project according to claim 6 joins the method for preparing of hydrogel, and it is characterized in that: the mass percent concentration of said glucan aqueous solution is 0.05-2%.
8. join the method for preparinies of hydrogel according to claim 4 or 6 described a kind of syringeability double crosses that can be used for organizational project, it is characterized in that: described dialysis is that 3500 bag filter passed through 3 days for adopting molecular cut off.
9. a kind of syringeability double cross that can be used for organizational project according to claim 1 joins the method for preparing of hydrogel; It is characterized in that: the method for preparing of the vinylated wall Polyethylene Glycol of described end group comprises: wall Polyethylene Glycol, triethylamine, acryloyl chloride are dissolved in the anhydrous methylene chloride, and wherein the mol ratio of wall Polyethylene Glycol, triethylamine and acryloyl chloride is 1:1-6:1-10; Under the room temperature purify with excessive ether sedimentation in the reaction back then, is dissolved in dichloromethane once more, uses excessive ether sedimentation, triplicate, and reduced vacuum is dry under the room temperature, promptly gets.
10. a kind of syringeability double cross that can be used for organizational project according to claim 1 joins the method for preparing of hydrogel, and it is characterized in that: the light trigger that adopts during described ultra-vioket radiation is crosslinked is gorgeous reinforcing 2959.
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| CN103146002A (en) * | 2013-03-04 | 2013-06-12 | 上海大学 | Injectable polyglutamic acid chemical crosslinking hydrogel and preparation method thereof |
| CN104910396A (en) * | 2015-06-03 | 2015-09-16 | 西安交通大学 | Injectable double-crosslinked hyaluronic acid aquagel and preparation method thereof |
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| CN107050510A (en) * | 2017-06-14 | 2017-08-18 | 东华大学 | A kind of sodium alginate/glutin injectable double-network hydrogel and its preparation and application |
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