CN101574539A - Gelatin sponge and preparation method thereof - Google Patents
Gelatin sponge and preparation method thereof Download PDFInfo
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- CN101574539A CN101574539A CNA2009100872748A CN200910087274A CN101574539A CN 101574539 A CN101574539 A CN 101574539A CN A2009100872748 A CNA2009100872748 A CN A2009100872748A CN 200910087274 A CN200910087274 A CN 200910087274A CN 101574539 A CN101574539 A CN 101574539A
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- gelfoam
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- 108010010803 Gelatin Proteins 0.000 title claims abstract description 57
- 239000008273 gelatin Substances 0.000 title claims abstract description 57
- 235000019322 gelatine Nutrition 0.000 title claims abstract description 57
- 235000011852 gelatine desserts Nutrition 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000004132 cross linking Methods 0.000 claims abstract description 25
- 239000000017 hydrogel Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000007864 aqueous solution Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 229920001661 Chitosan Polymers 0.000 claims description 16
- 230000005855 radiation Effects 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 15
- 230000008961 swelling Effects 0.000 claims description 13
- 238000004108 freeze drying Methods 0.000 claims description 11
- 150000004676 glycans Chemical class 0.000 claims description 8
- 229920001282 polysaccharide Polymers 0.000 claims description 8
- 239000005017 polysaccharide Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-OUBTZVSYSA-N Cobalt-60 Chemical compound [60Co] GUTLYIVDDKVIGB-OUBTZVSYSA-N 0.000 claims description 7
- -1 hydroxypropyl Chemical group 0.000 claims description 6
- 108090000723 Insulin-Like Growth Factor I Proteins 0.000 claims description 5
- 102000013275 Somatomedins Human genes 0.000 claims description 5
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims description 5
- 235000010409 propane-1,2-diol alginate Nutrition 0.000 claims description 5
- HDSBZMRLPLPFLQ-UHFFFAOYSA-N Propylene glycol alginate Chemical compound OC1C(O)C(OC)OC(C(O)=O)C1OC1C(O)C(O)C(C)C(C(=O)OCC(C)O)O1 HDSBZMRLPLPFLQ-UHFFFAOYSA-N 0.000 claims description 4
- 229940054190 hydroxypropyl chitosan Drugs 0.000 claims description 4
- 239000000770 propane-1,2-diol alginate Substances 0.000 claims description 4
- 239000003814 drug Substances 0.000 claims description 3
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 2
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 2
- 229940006091 aloe polysaccharide Drugs 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 229940045110 chitosan Drugs 0.000 claims description 2
- 238000010894 electron beam technology Methods 0.000 claims description 2
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 2
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 2
- 235000010413 sodium alginate Nutrition 0.000 claims description 2
- 239000000661 sodium alginate Substances 0.000 claims description 2
- 229940005550 sodium alginate Drugs 0.000 claims description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 2
- 238000009098 adjuvant therapy Methods 0.000 claims 1
- 230000001954 sterilising effect Effects 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 5
- 238000010382 chemical cross-linking Methods 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 18
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 15
- 239000011148 porous material Substances 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
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- 238000012216 screening Methods 0.000 description 4
- 238000004659 sterilization and disinfection Methods 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 208000032843 Hemorrhage Diseases 0.000 description 3
- 239000013043 chemical agent Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 230000010102 embolization Effects 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000017423 tissue regeneration Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
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- 235000005956 Cosmos caudatus Nutrition 0.000 description 2
- 244000293323 Cosmos caudatus Species 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 239000001828 Gelatine Substances 0.000 description 2
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
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- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- 208000005189 Embolism Diseases 0.000 description 1
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- 229930195725 Mannitol Natural products 0.000 description 1
- 206010040880 Skin irritation Diseases 0.000 description 1
- 206010053615 Thermal burn Diseases 0.000 description 1
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- RRGUKTPIGVIEKM-UHFFFAOYSA-N cilostazol Chemical compound C=1C=C2NC(=O)CCC2=CC=1OCCCCC1=NN=NN1C1CCCCC1 RRGUKTPIGVIEKM-UHFFFAOYSA-N 0.000 description 1
- 231100000433 cytotoxic Toxicity 0.000 description 1
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- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical group O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides gelatin sponge, gelatin aqueous solution is irradiated to crosslink to form gelatin hydrogel, and then the gelatin hydrogel is swollen, frozen and dried to obtain the gelatin sponge. The invention also provides a preparation method of the gelatin sponge by an irradiation crosslinking way, the whole process flow is finished in a pure water system, the irradiation and crosslinking processes have sterilizing function and good controllability, the obtained product has better structural uniformity compared with a chemical crosslinking method, and the gelatin sponge has unique advantages as biomedical materials.
Description
Technical field
The present invention relates to a kind of gelfoam and preparation method thereof, specifically, relate to a kind of gelfoam that adopts the preparation of crosslinking with radiation method.
Background technology
Gelatin has good biological activity, has purposes extremely widely at biomedical sector.Gelfoam has very strong anastalsis, but a large amount of moisture and the transudates of fast Absorption can be used as the dressing of operative incision, various wound surface, and the suppository of various interventional therapys.Use chitin modified gelfoam, then can further improve the anthemorrhagic speed of sponge, the ability of absorption transudate, and can improve the pliability of sponge.
Mostly traditional gelfoam or gelatine-chitosan sponge are with hydrochloric acid, acetate dissolution chitosan, make gelatin or gelatin/chitosan mixed liquor crosslinked with cross-linking agent such as formaldehyde, glutaraldehydes, at last with the freeze-drying dehydration, sterilizing obtains foam product.But a large amount of cytotoxic materials have been used in these technologies, as: hydrochloric acid, acetic acid, formaldehyde, glutaraldehyde etc., sterilization process adopts epoxyethane fumigation mostly, and the residual toxicity of these chemical agents can have a strong impact on cell growth and tissue regeneration, thereby influences therapeutic effect.
Chinese invention patent CN1097980A provides a kind of preparation method of chitose-gelatine sponge, is intended to make adhesive bandage, hemostasis subsides.This invention is gelatin, chitosan, hydrochloric acid, sodium hydroxide, formaldehyde, distilled water wiring solution-forming, through get blisters, freezing, dry, sterilize and to make mandruka.But the very big chemical reagent of cytotoxicity such as formaldehyde, hydrochloric acid, sodium hydroxide have been used in this technology, sterilization process adopts epoxyethane fumigation, these technologies are gradually by relevant regulation limitations or ban use of, and are very poor as the biological safety that adhesive bandage, hemostasis are pasted.
Chinese invention patent CN1775302A provides a kind of preparation method of chitose-gelatine sponge wound dressing.This invention is dissolved chitosan with dilute hydrochloric acid, acetic acid, formic acid solution, the gelatin water dissolution, add materials such as plasticizers such as cross-linking agent, glycerol, Margarita powder such as formaldehyde or Biformyl, after these components are mixed, obtain the spongy wound dressing of 1-2 millimeters thick with freeze-drying.But this technology has used formaldehyde, Biformyl, hydrochloric acid, acetic acid, formic acid etc. that the chemical reagent of bio-toxicity is arranged equally, and has used the Margarita powder of nonbiodegradability, and its granule may remain in the wound tissue, becomes foreign body in vivo.
It is the technology of feedstock production absorbable gelatin sponge particle suppository with the gelatin that Chinese invention patent CN101161298A provides a kind of.This is invented after aqueous gelatin solution and the formalin mixing, the freezing crosslinked porous spongy sample that obtains.Thaw after scouring, drying of spongy sample obtained gelfoam.Gelfoam is freezing, pulverize, screening obtains absorbable gelatin sponge particle suppository.This invention uses formaldehyde to make cross-linking agent, though washing step is arranged, the reagent in the porous material is difficult to eliminate by simple washing, and the formaldehyde residue problem can influence the histocompatibility of end article inevitably.
The present invention is intended to adopt green synthesis process, obtains that biocompatibility is better, the better gelfoam of structural homogeneity.
Summary of the invention
The present invention is intended to abandon the traditional handicraft of using a large amount of poisonous chemical agents, and a kind of gelfoam that adopts the crosslinking with radiation method to obtain is provided, and its good biocompatibility, structural homogeneity are good.
Another object of the present invention is to provide a kind of preparation method of gelfoam, this method adopts crosslinking with radiation and radiation sterilization to carry out simultaneously, can obtain that biocompatibility is better, the better gelfoam of structural homogeneity.
The object of the invention to solve the technical problems realizes by the following technical solutions.
A kind of gelfoam of the present invention, it becomes gelatin hydrogel by earlier aqueous gelatin solution being carried out crosslinking with radiation, carries out swelling then, lyophilization forms.
Described crosslinking with radiation adopts cobalt-60 or electron beam to carry out crosslinking with radiation, and irradiation is 1～50kGy, is preferably 10～30kGy.
The concentration expressed in percentage by weight of described aqueous gelatin solution is 3～50%, is preferably 10～30%.
Also can contain the poly-polysaccharide of water-soluble natural in the described aqueous gelatin solution.The ratio of the poly-polysaccharide of gelatin and water-soluble natural is 10: 0～1: 9, is preferably 4: 6～8: 2.
The poly-polysaccharide of described water-soluble natural is selected from one or more in Aloe polysaccharide, carboxymethyl chitosan, hydroxypropyl chitosan, sodium alginate, propylene glycol alginate, sodium carboxymethyl cellulose, hydroxypropyl emthylcellulose, the carboxymethyl hydroxypropyl cellulose.
The swelling of described gelatin hydrogel is by carrying out in the pharmaceutical aqueous solution that is immersed in sterilized water, somatomedin aqueous solution or auxiliary treatment.Swelling time is 2～72 hours, is preferably 6～24 hours.Swelling process carries out in sterilizing room.
Described somatomedin aqueous solution can select fibroblast growth factor that those skilled in the art use always or hEGF etc. can promote the somatomedin aqueous solution that skin tissue regeneration is repaired.
Can select pharmaceutical aqueous solutions such as this area disinfectant commonly used, antibiotic, burn-scald medicine, Pletaal for pharmaceutical aqueous solution, make it to have corresponding auxiliary treatment effect, its consumption can adopt this area conventional amount used.
The gelatin hydrogel degree of cross linking by the present invention preparation is in 70～99% scopes, and water absorption rate is adjustable in 5～500 times of scopes.
The preparation method of gelfoam of the present invention, it carries out crosslinking with radiation to aqueous gelatin solution earlier and becomes gelatin hydrogel, carries out swelling, lyophilization then.
Described cryodesiccated temperature is at-10～-80 ℃, preferred-20～-60 ℃.
Adopt the good porous gelfoam of crosslinking with radiation method availability of the present invention.The aperture has excellent absorptive tissue liquid and hemostatic capability, preferred 20～70 micrometer ranges in 5～100 microns scope.
If necessary, can the porous gelfoam is freezing, pulverize, screening, obtain the graininess gelfoam of different-grain diameter.
By the gelfoam that the present invention obtains, can be used as bleeding-stopping dressing, burn wound dressing, ulcer dressing etc.; Absorbable gelatin sponge particle can be used as suppository and is used for various interventional therapys, as artery embolization for treatment of hysteromyoma, hemangioma, arteriovenous malformotion, malignant tumor and various massive hemorrhage etc.
The gelfoam that utilizes method provided by the invention to obtain does not have chemical agent residual, has better biocompatibility and structural homogeneity.Fibroblast growing state on gelatin/carboxymethyl chitosan hydrogel of the present invention is good, and the rate of increase was greater than 100% in 5 days; And on hydrogel, cultivate fibroblast with acetic acid dissolving Preparation of Chitosan, 7 days rates of increase are between 82～97%; Do not find cell culture data, but formaldehyde toxicity is higher than acetic acid, estimates that its cell proliferation rate is lower with formaldehyde crosslinking gelatin and/or chitosan gel rubber material.
Gelfoam of the present invention and radiation preparation method thereof have following advantage and beneficial effect at least:
(1) the present invention adopts the poly-polysaccharide of water-soluble natural to replace chitosan, so solvent has substituted the material that acetic acid, formic acid etc. have skin irritation by water.
(2) the poly-polysaccharide of water-soluble natural is compared with chitosan, has the ability of better promotion tissue growth.
(3) with the poly-polysaccharide-modified gelatin of water-soluble natural, can increase the water solublity and the pliability of gelatin, and can promote the granulation growth, use very crucial as dressing it.
(4) replace crosslinking technologicals such as formaldehyde, glutaraldehyde with the crosslinking with radiation technology generation, can avoid the chemical residual toxicity of product, play the effect of sterilization simultaneously.
(5) porous material that obtains with the crosslinking with radiation technology has better structural homogeneity, helps the adhesion and the skin tissue regeneration of skin tissue cell.
(6) controllability of this process is fine, and the structural homogeneity that obtains product is good than chemical crosslink technique also, has special advantages as bio-medical material.
The specific embodiment
Following examples are used to illustrate the present invention, but are not used for limiting the scope of the invention.
Embodiment 1
30 gram gelatin are dissolved in the 70 gram water, are heated to 80 ℃, stir, obtain 30% aqueous gelatin solution.Pour aqueous gelatin solution into plate,, obtain the degree of cross linking and be 99% gelatin hydrogel with cobalt-60 irradiation 20kGy.Hydrogel is soaked 24 hours to swelling equilibrium in sterilized water, obtain water absorption rate and be 10 times moisture porous material.Moisture porous material-80 ℃ of lyophilizations, with the classification of Universalpulverizer crushing screening, is obtained aperture and epigranular (average pore size is at 15 microns), the soft gelfoam embolization agent of quality under-20 ℃ of low temperature.
Embodiment 2
12 gram gelatin and 3 gram carboxymethyl chitosans are dissolved in the 85 gram water, are heated to 60 ℃, stir, obtain solid content and be 15% aqueous solution with the deaeration blender.Pour aqueous solution into plate,, obtain the degree of cross linking and be gelatin/carboxymethyl chitosan hydrogel of 82% with cobalt-60 irradiation 30kGy.Hydrogel is soaked 72 hours to swelling equilibrium in containing the aqueous solution of somatomedin, obtain water absorption rate and be 20 times moisture porous material.Moisture porous material-40 ℃ of lyophilizations, and is obtained aperture evenly (average pore size is at 50 microns), the soft gelatin/carboxymerhyl chitosan sponge dressing of quality.
Embodiment 3
4 gram gelatin and 6 gram hydroxypropyl chitosans are dissolved in the 90 gram water, are heated to 60 ℃, stir, obtain solid content and be 10% aqueous solution with the deaeration blender.Pour aqueous solution into plate,, obtain the degree of cross linking and be gelatin/hydroxypropyl chitosan hydrogel of 72% with cobalt-60 irradiation 10kGy.Hydrogel is soaked 36 hours to swelling equilibrium in sterilized water, obtain water absorption rate and be 90 times moisture porous material.Moisture porous material-40 ℃ of lyophilizations, is obtained aperture evenly (average pore size is at 80 microns), the soft gelatin/hydroxypropyl chitosan sponge dressing of quality.
Embodiment 4
8 gram gelatin and 12 gram propylene glycol alginates are dissolved in the 80 gram water, are heated to 60 ℃, stir, obtain solid content and be 20% aqueous solution with the deaeration blender.Pour aqueous solution into plate,, obtain the degree of cross linking and be gelatin/propylene glycol alginate hydrogel of 70% with cobalt-60 irradiation 50kGy.Hydrogel is soaked 48 hours to swelling equilibrium in the sterilized water that contains the 1mg/L basic fibroblast growth factor, obtain water absorption rate and be 220 times moisture porous material.Moisture porous material-80 ℃ of lyophilizations, is obtained aperture evenly (average pore size is at 30 microns), the soft gelatin/propylene glycol alginate sponge dressing of quality.
Embodiment 5
10 gram gelatin are dissolved in the 90 gram water, are heated to 80 ℃, stir, obtain 10% aqueous gelatin solution.Pour aqueous gelatin solution into plate,, obtain the degree of cross linking and be 90% gelatin hydrogel with cobalt-60 irradiation 5kGy.Hydrogel is soaked 6 hours to swelling equilibrium in the aseptic aqueous solution that contains 10% mannitol embolism resistance medicament, obtain water absorption rate and be 50 times moisture porous material.Moisture porous material-60 ℃ of lyophilizations, with the classification of Universalpulverizer crushing screening, is obtained aperture (average pore size is at 40 microns) and epigranular, the soft gelfoam embolization agent of quality under-20 ℃ of low temperature.
During as dressing, the capacity of absorptive tissue liquid and speed, anthemorrhagic speed are better than commercially available gelfoam matched group with the gelfoam of method provided by the present invention preparation; During as sthptic sponge, the bleeding stopping period and the rate of always losing blood all are better than matched group; During as suppository, biocompatibility and immunogenicity are better than matched group.
Though above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements all belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (10)
1. a gelfoam is characterized in that, it becomes gelatin hydrogel by earlier aqueous gelatin solution being carried out crosslinking with radiation, carries out swelling then, lyophilization forms.
2. gelfoam according to claim 1 is characterized in that, described crosslinking with radiation adopts cobalt-60 or electron beam to carry out crosslinking with radiation, and irradiation is 1～50kGy.
3. gelfoam according to claim 1 and 2 is characterized in that, the described gelatin hydrogel degree of cross linking is in 70～99% scopes.
4. according to any described gelfoam of claim 1-3, it is characterized in that the concentration expressed in percentage by weight of described aqueous gelatin solution is 3～50%, is preferably 10～30%.
5. according to any described gelfoam of claim 1-4, it is characterized in that, also contain the poly-polysaccharide of water-soluble natural in the described aqueous gelatin solution.
6. gelfoam according to claim 5, it is characterized in that described natural polysaccharide is selected from one or more in Aloe polysaccharide, carboxymethyl chitosan, hydroxypropyl chitosan, sodium alginate, propylene glycol alginate, sodium carboxymethyl cellulose, hydroxypropyl emthylcellulose, the carboxymethyl hydroxypropyl cellulose.
7. according to claim 5 or 6 described gelfoam, it is characterized in that the ratio of the poly-polysaccharide of described gelatin and described water-soluble natural is 10: 0～1: 9, is preferably 4: 6～8: 2.
8. according to any described gelfoam of claim 1-7, it is characterized in that the swelling of described gelatin hydrogel is undertaken by being immersed in sterilized water, somatomedin aqueous solution or the adjuvant therapy medicaments aqueous solution.
9. prepare the method for any described gelfoam of claim 1-8, it is characterized in that, it carries out crosslinking with radiation to aqueous gelatin solution earlier and makes gelatin hydrogel, carries out swelling, lyophilization then.
10. according to the preparation method of the described gelfoam of claim 9, it is characterized in that described cryodesiccated temperature is at-10～-80 ℃, preferred-20～-60 ℃.
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| CN2009100872748A CN101574539B (en) | 2009-06-15 | 2009-06-15 | Gelatin sponge and preparation method thereof |
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| CN2009100872748A CN101574539B (en) | 2009-06-15 | 2009-06-15 | Gelatin sponge and preparation method thereof |
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| CN101574539B CN101574539B (en) | 2012-07-18 |
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Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102068714A (en) * | 2011-01-19 | 2011-05-25 | 北京大学 | Collagen sponge and preparation method thereof |
| CN102139127A (en) * | 2011-03-17 | 2011-08-03 | 杭州艾力康医药科技有限公司 | Developable gelatin sponge suppository and preparation process thereof |
| CN102139128A (en) * | 2011-03-22 | 2011-08-03 | 杭州艾力康医药科技有限公司 | Developable polyvinyl alcohol microballoon/particle embolic agent and preparation process thereof |
| CN102660045A (en) * | 2012-05-03 | 2012-09-12 | 吉林大学 | Method for preparing gelatin sponge by using wood frog wracks |
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2009
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