CN109821067A - A kind of polycaprolactone diacrylate/polyethylene glycol hydrogel bracket and its preparation method and application - Google Patents
A kind of polycaprolactone diacrylate/polyethylene glycol hydrogel bracket and its preparation method and application Download PDFInfo
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- CN109821067A CN109821067A CN201910269970.4A CN201910269970A CN109821067A CN 109821067 A CN109821067 A CN 109821067A CN 201910269970 A CN201910269970 A CN 201910269970A CN 109821067 A CN109821067 A CN 109821067A
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- polyethylene glycol
- polycaprolactone
- diacrylate
- polycaprolactone diacrylate
- hydrogel
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- 229920001610 polycaprolactone Polymers 0.000 title claims abstract description 91
- 239000004632 polycaprolactone Substances 0.000 title claims abstract description 89
- 239000002202 Polyethylene glycol Substances 0.000 title claims abstract description 78
- 229920001223 polyethylene glycol Polymers 0.000 title claims abstract description 78
- 125000004386 diacrylate group Chemical group 0.000 title claims abstract description 72
- 239000000017 hydrogel Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 9
- 239000011148 porous material Substances 0.000 claims abstract description 8
- 238000012377 drug delivery Methods 0.000 claims abstract description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 33
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 24
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 239000011780 sodium chloride Substances 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 11
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000012153 distilled water Substances 0.000 claims description 11
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 11
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- 239000012065 filter cake Substances 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 230000010148 water-pollination Effects 0.000 claims 1
- 239000000243 solution Substances 0.000 description 19
- 210000003321 cartilage cell Anatomy 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 5
- 238000011081 inoculation Methods 0.000 description 5
- 239000008055 phosphate buffer solution Substances 0.000 description 5
- 210000004027 cell Anatomy 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- -1 diacrylate Ester Chemical class 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 210000001612 chondrocyte Anatomy 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000001963 growth medium Substances 0.000 description 2
- AZKSAVLVSZKNRD-UHFFFAOYSA-M 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide Chemical compound [Br-].S1C(C)=C(C)N=C1[N+]1=NC(C=2C=CC=CC=2)=NN1C1=CC=CC=C1 AZKSAVLVSZKNRD-UHFFFAOYSA-M 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 1
- 239000006144 Dulbecco’s modified Eagle's medium Substances 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 229920000375 Poly(ethylene glycol)-block-poly(ε−caprolactone) methyl ether Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004113 cell culture Methods 0.000 description 1
- 230000003833 cell viability Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012894 fetal calf serum Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
Landscapes
- Medicinal Preparation (AREA)
Abstract
The present invention discloses a kind of polycaprolactone diacrylate/polyethylene glycol hydrogel bracket and its preparation method and application, and using polyethylene glycol as hydrophilic block, polycaprolactone diacrylate is hydrophobic block；The mass ratio of polyethylene glycol and polycaprolactone diacrylate is 3~7:3~7；It is porous structure inside polycaprolactone diacrylate/polyethylene glycol hydrogel, pore size is 40~110 μm；There are porous inside hydrogel scaffold, with preferable elasticity, degradability and biocompatibility, and porous structure can be used for drug delivery and organizational project, and cell can uniformly be inoculated into internal stent without being pre-processed in cell is embedded in and grows；A kind of polycaprolactone diacrylate/polyethylene glycol hydrogel bracket of the invention improves the strong crystallinity and hydrophobicity of polyethylene glycol segment due to the addition of polycaprolactone diacrylate, viscosity of the hydrogel under collosol state is reduced, is had a good application prospect.
Description
Technical field
The present invention relates to technical field of hydrogel, specifically a kind of polycaprolactone diacrylate/polyethylene glycol water-setting
Glue bracket and its preparation method and application.
Background technique
Polyethylene glycol is nontoxic, nonirritant, has good water solubility, and has with gas chromatography component good compatible
Property, there is excellent moisture retention, dispersibility and biocompatibility etc., have in fields such as cosmetics, pharmacy and food processings wide
General application；Polycaprolactone diols is a kind of typical biodegradable thermoplastic material, can voluntarily be dropped in vivo
Solution has good biocompatibility at carbon dioxide and water, is widely used in field of biomedicine.
Current gel rubber material is quickly grown, but still remains following problems: the response time is long, and mechanical property needs into one
Step improves and biocompatibility and biodegradability are poor；In addition, current is water in situ with PEG-PCL block copolymer
When gel rubber material, due to PCL sections of strong crystallinity and hydrophobicity, unsuitable embedding cell is easy at room temperature when solution is unstable
Gel is spontaneously formed, pharmaceutical grade protein should not be loaded, and PCL sections of strong crystallinity and hydrophobicity can also make this material institute shape
At hydrogel, viscosity very big inconvenience is injected under collosol state, and modulus is excessive, and degradation rate is excessively slow etc., serious to limit
The application of current hydrogel material.
Summary of the invention
To solve the above problems, the object of the present invention is to provide a kind of polycaprolactone diacrylate/polyethylene glycol water-settings
Glue bracket and its preparation method and application.
The present invention to achieve the above object, is achieved through the following technical solutions:
A kind of polycaprolactone diacrylate/polyethylene glycol hydrogel bracket gathers oneself using polyethylene glycol as hydrophilic block
Lactone diacrylate is hydrophobic block；The mass ratio of polyethylene glycol and polycaprolactone diacrylate is 3~7:3~7；It is poly-
It is porous structure inside caprolactone diacrylate/polyethylene glycol hydrogel, pore size is 40~110 μm.
Preferably, the mass ratio of polyethylene glycol and polycaprolactone diacrylate is 4:5.
The invention also includes a kind of preparation methods of polycaprolactone diacrylate/polyethylene glycol hydrogel bracket, including
Following steps:
1. in a solvent by polycaprolactone glycol dissolution, triethylamine, acryloyl chloride are added thereto, is stirred at 75~85 DEG C
It mixes 2~3 hours, filters, filtered after filtrate is precipitated in n-hexane, filter cake is dried, obtain polycaprolactone diacrylate；
Wherein polycaprolactone glycol, triethylamine, acryloyl chloride mass ratio be 4~6:1:0.9~1.2；The solvent be methylene chloride,
Toluene, benzene or chloroform；
2. by polyethylene glycol and step 1. gained polycaprolactone diacrylate be dissolved in dimethyl sulfoxide, thereto plus
Enter sodium chloride particle, azodiisobutyronitrile is added thereto, obtain reaction solution, places reaction liquid into 65~75 DEG C of convection constant temperature
It reacts 10~15 hours, is then successively immersed in it in distilled water and ethyl alcohol each 5~10 hours, then with distillation washing in case
It washs 3~5 times, is freeze-dried 2~3 days, obtains polycaprolactone diacrylate/polyethylene glycol hydrogel bracket；Wherein poly- second two
Alcohol, polycaprolactone diacrylate, dimethyl sulfoxide, sodium chloride and azodiisobutyronitrile mass ratio be 3~7:3~7:150
~170:1~3:0.01~0.05.
Preferred preparation method, polycaprolactone glycol, triethylamine, acryloyl chloride mass ratio be 5:1:1.0.
Preferred preparation method, the average grain diameter of sodium chloride particle are 180~400 μm.
Preferred preparation method, polyethylene glycol, polycaprolactone diacrylate, dimethyl sulfoxide, sodium chloride and azo two
The mass ratio of isobutyronitrile is 4:5:160:2:0.03.
The invention also includes a kind of applications of polycaprolactone diacrylate/polyethylene glycol hydrogel bracket, are used for drug
Transmitting and organizational project.
The present invention has the advantage that compared with prior art
A kind of polycaprolactone diacrylate/polyethylene glycol hydrogel bracket gathers oneself using polyethylene glycol as hydrophilic section
Lactone has preferable elasticity, degradability and bio-compatible as hydrophobic section, and there are porous inside hydrogel scaffold
Property, and porous structure can be used for drug delivery and organizational project, and cell can uniformly connect in cell is embedded in and grows
Kind is to internal stent without being pre-processed；A kind of polycaprolactone diacrylate/polyethylene glycol hydrogel branch of the invention
Frame improves the strong crystallinity and hydrophobicity of polyethylene glycol segment due to the addition of polycaprolactone diacrylate, reduces water-setting
Viscosity of the glue under collosol state, improves its mechanical property, biocompatibility and biodegradability, has good application
Prospect.
Detailed description of the invention
Fig. 1 is the SEM picture before cartilage cell's inoculation；
Fig. 2 is the SEM picture after cartilage cell's inoculation.
Specific embodiment
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1
A kind of polycaprolactone diacrylate/polyethylene glycol hydrogel bracket gathers oneself using polyethylene glycol as hydrophilic block
Lactone diacrylate is hydrophobic block；The mass ratio of polyethylene glycol and polycaprolactone diacrylate is 3:7；Polycaprolactone
It is porous structure inside diacrylate/polyethylene glycol hydrogel, pore size is 40~110 μm.
Embodiment 2
A kind of polycaprolactone diacrylate/polyethylene glycol hydrogel bracket gathers oneself using polyethylene glycol as hydrophilic block
Lactone diacrylate is hydrophobic block；The mass ratio of polyethylene glycol and polycaprolactone diacrylate is 7:3；Polycaprolactone
It is porous structure inside diacrylate/polyethylene glycol hydrogel, pore size is 40~110 μm.
Embodiment 3
A kind of polycaprolactone diacrylate/polyethylene glycol hydrogel bracket gathers oneself using polyethylene glycol as hydrophilic block
Lactone diacrylate is hydrophobic block；The mass ratio of polyethylene glycol and polycaprolactone diacrylate is 1:1；Polycaprolactone
It is porous structure inside diacrylate/polyethylene glycol hydrogel, pore size is 40~110 μm.
Embodiment 4
A kind of polycaprolactone diacrylate/polyethylene glycol hydrogel bracket gathers oneself using polyethylene glycol as hydrophilic block
Lactone diacrylate is hydrophobic block；The mass ratio of polyethylene glycol and polycaprolactone diacrylate is 4:6；Polycaprolactone
It is porous structure inside diacrylate/polyethylene glycol hydrogel, pore size is 40~110 μm.
Embodiment 5
A kind of polycaprolactone diacrylate/polyethylene glycol hydrogel bracket gathers oneself using polyethylene glycol as hydrophilic block
Lactone diacrylate is hydrophobic block；The mass ratio of polyethylene glycol and polycaprolactone diacrylate is 4:5；Polycaprolactone
It is porous structure inside diacrylate/polyethylene glycol hydrogel, pore size is 40~110 μm.
Embodiment 6
Polycaprolactone diacrylate/polyethylene glycol hydrogel bracket preparation method of embodiment 1, including following step
It is rapid:
1. 8kg polycaprolactone glycol dissolves in a solvent, 2kg triethylamine, 1.8kg acryloyl chloride are added thereto, 75
It is stirred 2 hours at DEG C, filters, filtered after filtrate is precipitated in n-hexane, filter cake is dried, obtain polycaprolactone diacrylate
Ester；The solvent is methylene chloride；
2. 1. gained polycaprolactone diacrylate is dissolved in 150kg dimethyl sulfoxide for 3kg polyethylene glycol and 7kg step
In, 1kg sodium chloride particle is added thereto, 0.01kg azodiisobutyronitrile is added thereto, obtains reaction solution, reaction solution is set
It is reacted 10 hours in 65 DEG C of convection constant temperature case, then it is successively immersed in distilled water and ethyl alcohol each 5 hours, is then used
Distillation water washing 3 times is freeze-dried 2 days, obtains polycaprolactone diacrylate/polyethylene glycol hydrogel bracket.
Embodiment 7
Polycaprolactone diacrylate/polyethylene glycol hydrogel bracket preparation method of embodiment 2, including following step
It is rapid:
1. 6kg polycaprolactone glycol dissolves in a solvent, 1kg triethylamine, 1.2kg acryloyl chloride are added thereto, 85
It is stirred 3 hours at DEG C, filters, filtered after filtrate is precipitated in n-hexane, filter cake is dried, obtain polycaprolactone diacrylate
Ester；The solvent is toluene；
2. 1. gained polycaprolactone diacrylate is dissolved in 170kg dimethyl sulfoxide for 7kg polyethylene glycol and 3kg step
In, 3kg sodium chloride particle is added thereto, 0.05kg azodiisobutyronitrile is added thereto, obtains reaction solution, reaction solution is set
It is reacted 15 hours in 75 DEG C of convection constant temperature case, then it is successively immersed in in distilled water and ethyl alcohol each 10 hours, then
It is washed with distilled water 5 times, is freeze-dried 3 days, obtains polycaprolactone diacrylate/polyethylene glycol hydrogel bracket.
Embodiment 8
Polycaprolactone diacrylate/polyethylene glycol hydrogel bracket preparation method of embodiment 3, including following step
It is rapid:
1. 4kg polycaprolactone glycol dissolves in a solvent, 1kg triethylamine, 1.2kg acryloyl chloride are added thereto, 78
It is stirred 2.5 hours at DEG C, filters, filtered after filtrate is precipitated in n-hexane, filter cake is dried, obtain two propylene of polycaprolactone
Acid esters；The solvent is benzene；
2. 1. gained polycaprolactone diacrylate is dissolved in 155kg dimethyl sulfoxide for 3kg polyethylene glycol and 3kg step
In, 2.5kg sodium chloride particle is added thereto, 0.02kg azodiisobutyronitrile is added thereto, reaction solution is obtained, by reaction solution
It is placed in 68 DEG C of convection constant temperature case and reacts 12 hours, then it is successively immersed in in distilled water and ethyl alcohol each 6 hours, then
It is washed with distilled water 4 times, is freeze-dried 2.5 days, obtains polycaprolactone diacrylate/polyethylene glycol hydrogel bracket.
Embodiment 9
Polycaprolactone diacrylate/polyethylene glycol hydrogel bracket preparation method of embodiment 4, including following step
It is rapid:
1. 6kg polycaprolactone glycol dissolves in a solvent, 1kg triethylamine, 0.9kg acryloyl chloride are added thereto, 82
It is stirred 2 hours at DEG C, filters, filtered after filtrate is precipitated in n-hexane, filter cake is dried, obtain polycaprolactone diacrylate
Ester；The solvent is chloroform；
2. 1. gained polycaprolactone diacrylate is dissolved in 165kg dimethyl sulfoxide for 4kg polyethylene glycol and 6kg step
In, 2.5kg sodium chloride particle is added thereto, 0.04kg azodiisobutyronitrile is added thereto, reaction solution is obtained, by reaction solution
It is placed in 72 DEG C of convection constant temperature case and reacts 11 hours, then it is successively immersed in in distilled water and ethyl alcohol each 6 hours, then
It is washed with distilled water 4 times, is freeze-dried 3 days, obtains polycaprolactone diacrylate/polyethylene glycol hydrogel bracket.
Embodiment 10
Polycaprolactone diacrylate/polyethylene glycol hydrogel bracket preparation method of embodiment 5, including following step
It is rapid:
1. 10kg polycaprolactone glycol dissolves in a solvent, 2kg triethylamine, 2kg acryloyl chloride are added thereto, 75~
It is stirred 2~3 hours at 85 DEG C, filters, filtered after filtrate is precipitated in n-hexane, filter cake is dried, obtain polycaprolactone two
Acrylate；The solvent is methylene chloride；
2. 1. gained polycaprolactone diacrylate is dissolved in 160kg dimethyl sulfoxide for 4kg polyethylene glycol and 5kg step
In, 2kg sodium chloride particle is added thereto, 0.03kg azodiisobutyronitrile is added thereto, obtains reaction solution, reaction solution is set
It is reacted 12 hours in 70 DEG C of convection constant temperature case, then it is successively immersed in distilled water and ethyl alcohol each 6 hours, is then used
Distillation water washing 4 times is freeze-dried 2.5 days, obtains polycaprolactone diacrylate/polyethylene glycol hydrogel bracket.
The detection data such as table 1 of the resulting polycaprolactone diacrylate/polyethylene glycol hydrogel bracket of embodiment 6~10
It is shown.
The detection data of the resulting polycaprolactone diacrylate/polyethylene glycol hydrogel bracket of 1 embodiment of table 6~10
Bracket (37 DEG C, pH=7.4) are impregnated using phosphate buffer solution (PBS) in the present invention, measure the molten of porous support
Bracket after drying is cut into identical size (1 × 1 × 1cm by swollen rate3), and (the W that weighs before immersiond).Bracket is immersed into PBS
In buffer solution, bracket is taken out after 24 hours, the water suction of excess surface is wiped with filter paper, measures its weight in wet base (Ww).Pass through public affairs
Formula calculates swelling ratio: (Ww-Wd)/Wd。
MTT (thiazolyl blue) method of present invention routine has studied influence of the hydrogel to human body chondrocyte growth.It will contain
The plate for the hydrogel scaffold for having embodiment 12 to prepare impregnates (20-30 minutes each) three times in 70% ethanol solution.It will branch
Frame is rinsed with PBS solution after natural drying, and overnight incubation in the medium.For the growth of Induction of chondrocytes, by cartilage
Cell is re-dispersed into DMEM culture medium, and adds 10% fetal calf serum and 1% antibiotic.Hydrogel scaffold is impregnated again
In culture medium, cell culture test is carried out.When distinguishing 3 days, 6 days and 9 days after inoculation, surveyed with MTT solution (5mg/ml)
Determine cell survival rate.Simultaneously using tissue culturing plate as control group, according to above-mentioned steps cultured cartilage cell.The experimental results showed that this
The hydrogel scaffold of invention is more conducive to the growth of cartilage cell, has higher cell viability.
Cartilage cell is carried out to the resulting polycaprolactone diacrylate of embodiment 12/polyethylene glycol hydrogel bracket to glue
Attached property and proliferation research.
The cartilage cell of people is inoculated on hydrogel scaffold first, then rinses bracket twice (every time with PBS solution
10min), sample solidify overnight with 2.5% glutaraldehyde solution, finally successively by sample be put into concentration be 50%,
75%, it is carried out dehydrating in 95%, 100% ethyl alcohol, impregnates 15min every time.With the growth feelings of SEM observation cartilage cell
Condition, Fig. 1 are the SEM picture before cartilage cell's inoculation, and Fig. 2 is the SEM picture after cartilage cell's inoculation, it can be seen that cartilage cell
There is good adhesiveness with hydrogel scaffold.
Claims (7)
1. a kind of polycaprolactone diacrylate/polyethylene glycol hydrogel bracket, it is characterised in that: using polyethylene glycol as hydrophily
Block, polycaprolactone diacrylate are hydrophobic block；The mass ratio of polyethylene glycol and polycaprolactone diacrylate be 3~
7:3~7；It is porous structure inside polycaprolactone diacrylate/polyethylene glycol hydrogel, pore size is 40~110 μm.
2. a kind of polycaprolactone diacrylate/polyethylene glycol hydrogel bracket according to claim 1, feature exist
In: the mass ratio of polyethylene glycol and polycaprolactone diacrylate is 4:5.
3. a kind of preparation method of polycaprolactone diacrylate/polyethylene glycol hydrogel bracket described in claim 1, special
Sign is: the following steps are included:
1. in a solvent by polycaprolactone glycol dissolution, triethylamine, acryloyl chloride are added thereto, stirs 2 at 75~85 DEG C
~3 hours, filtering filtered after precipitating filtrate in n-hexane, filter cake is dried, obtains polycaprolactone diacrylate；Its
Middle polycaprolactone glycol, triethylamine, acryloyl chloride mass ratio be 4~6:1:0.9~1.2；The solvent is methylene chloride, first
Benzene, benzene or chloroform；
2. by polyethylene glycol and step, 1. gained polycaprolactone diacrylate is dissolved in dimethyl sulfoxide, and chlorine is added thereto
Change sodium particle, azodiisobutyronitrile is added thereto, obtains reaction solution, places reaction liquid into 65~75 DEG C of convection constant temperature case
It, is then successively immersed in distilled water and ethyl alcohol each 5~10 hours, is then washed with distilled water 3 by reaction 10~15 hours
It~5 times, is freeze-dried 2~3 days, obtains polycaprolactone diacrylate/polyethylene glycol hydrogel bracket；Wherein polyethylene glycol,
Polycaprolactone diacrylate, dimethyl sulfoxide, sodium chloride and azodiisobutyronitrile mass ratio be 3~7:3~7:150~
170:1~3:0.01~0.05.
4. a kind of preparation method of polycaprolactone diacrylate/polyethylene glycol hydrogel bracket according to claim 3,
It is characterized by: the mass ratio of polycaprolactone glycol, triethylamine, acryloyl chloride is 5:1:1.0.
5. a kind of preparation method of polycaprolactone diacrylate/polyethylene glycol hydrogel bracket according to claim 3,
It is characterized by: the average grain diameter of sodium chloride particle is 180~400 μm.
6. a kind of preparation method of polycaprolactone diacrylate/polyethylene glycol hydrogel bracket according to claim 3,
It is characterized by: the quality of polyethylene glycol, polycaprolactone diacrylate, dimethyl sulfoxide, sodium chloride and azodiisobutyronitrile
Than for 4:5:160:2:0.03.
7. a kind of application of polycaprolactone diacrylate/polyethylene glycol hydrogel bracket, it is characterised in that: be used for drug delivery
And organizational project.
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