CN103880285A - Sol-gel prepared sodium-containing bioactive glass and its application including hemostasis - Google Patents
Sol-gel prepared sodium-containing bioactive glass and its application including hemostasis Download PDFInfo
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- CN103880285A CN103880285A CN201410084093.0A CN201410084093A CN103880285A CN 103880285 A CN103880285 A CN 103880285A CN 201410084093 A CN201410084093 A CN 201410084093A CN 103880285 A CN103880285 A CN 103880285A
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- Prior art keywords
- sol
- source
- bioactive glass
- gel
- gel bioactive
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- 239000005313 bioactive glass Substances 0.000 title claims abstract description 64
- 239000011734 sodium Substances 0.000 title claims description 63
- 229910052708 sodium Inorganic materials 0.000 title claims description 32
- 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 title claims description 22
- 230000023597 hemostasis Effects 0.000 title description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011780 sodium chloride Substances 0.000 claims abstract description 17
- 239000004317 sodium nitrate Substances 0.000 claims abstract description 9
- 235000010344 sodium nitrate Nutrition 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims description 48
- 239000011575 calcium Substances 0.000 claims description 34
- 229910052791 calcium Inorganic materials 0.000 claims description 19
- 230000032683 aging Effects 0.000 claims description 16
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 15
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical group CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 14
- 208000032843 Hemorrhage Diseases 0.000 claims description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims description 12
- 208000034158 bleeding Diseases 0.000 claims description 10
- 230000000740 bleeding effect Effects 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 229940001516 sodium nitrate Drugs 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- ZHJGWYRLJUCMRT-UHFFFAOYSA-N 5-[6-[(4-methylpiperazin-1-yl)methyl]benzimidazol-1-yl]-3-[1-[2-(trifluoromethyl)phenyl]ethoxy]thiophene-2-carboxamide Chemical group C=1C=CC=C(C(F)(F)F)C=1C(C)OC(=C(S1)C(N)=O)C=C1N(C1=C2)C=NC1=CC=C2CN1CCN(C)CC1 ZHJGWYRLJUCMRT-UHFFFAOYSA-N 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 238000011282 treatment Methods 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 210000000988 bone and bone Anatomy 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 4
- 229910052728 basic metal Inorganic materials 0.000 claims description 3
- 150000003818 basic metals Chemical class 0.000 claims description 3
- 230000023555 blood coagulation Effects 0.000 claims description 3
- 230000008439 repair process Effects 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims 1
- 150000001342 alkaline earth metals Chemical class 0.000 claims 1
- 239000011521 glass Substances 0.000 abstract description 42
- 238000003980 solgel method Methods 0.000 abstract description 7
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract 1
- 239000000499 gel Substances 0.000 description 93
- 238000012360 testing method Methods 0.000 description 13
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 12
- 230000004071 biological effect Effects 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 10
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
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- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 230000000025 haemostatic effect Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
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- 239000011777 magnesium Substances 0.000 description 6
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- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- 229910001424 calcium ion Inorganic materials 0.000 description 5
- 230000002439 hemostatic effect Effects 0.000 description 5
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 5
- 229910017053 inorganic salt Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 208000027418 Wounds and injury Diseases 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 229940085991 phosphate ion Drugs 0.000 description 4
- 108090000623 proteins and genes Proteins 0.000 description 4
- 102000004169 proteins and genes Human genes 0.000 description 4
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 4
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 210000001124 body fluid Anatomy 0.000 description 3
- 239000010839 body fluid Substances 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- 239000001506 calcium phosphate Substances 0.000 description 3
- 229910000389 calcium phosphate Inorganic materials 0.000 description 3
- 235000011010 calcium phosphates Nutrition 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 210000001519 tissue Anatomy 0.000 description 3
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 3
- 102100031162 Collagen alpha-1(XVIII) chain Human genes 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
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- 230000008901 benefit Effects 0.000 description 2
- 239000005312 bioglass Substances 0.000 description 2
- 210000001772 blood platelet Anatomy 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
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- 238000006460 hydrolysis reaction Methods 0.000 description 2
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- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 238000013059 nephrectomy Methods 0.000 description 2
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- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
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- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
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- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002792 vascular Effects 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 102400000068 Angiostatin Human genes 0.000 description 1
- 108010079709 Angiostatins Proteins 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 101000882917 Penaeus paulensis Hemolymph clottable protein Proteins 0.000 description 1
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- 239000004110 Zinc silicate Substances 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
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- FZCSTZYAHCUGEM-UHFFFAOYSA-N aspergillomarasmine B Natural products OC(=O)CNC(C(O)=O)CNC(C(O)=O)CC(O)=O FZCSTZYAHCUGEM-UHFFFAOYSA-N 0.000 description 1
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- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
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- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
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- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
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- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
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- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 1
- QGMRQYFBGABWDR-UHFFFAOYSA-N sodium;5-ethyl-5-pentan-2-yl-1,3-diazinane-2,4,6-trione Chemical compound [Na+].CCCC(C)C1(CC)C(=O)NC(=O)NC1=O QGMRQYFBGABWDR-UHFFFAOYSA-N 0.000 description 1
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- 238000007669 thermal treatment Methods 0.000 description 1
- 229960004072 thrombin Drugs 0.000 description 1
- 230000008467 tissue growth Effects 0.000 description 1
- 230000017423 tissue regeneration Effects 0.000 description 1
- 238000002054 transplantation Methods 0.000 description 1
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 1
- 238000007631 vascular surgery Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 description 1
- 235000019352 zinc silicate Nutrition 0.000 description 1
Landscapes
- Materials For Medical Uses (AREA)
Abstract
A sol-gel bioactive glass initial solution, a preparation method of the sol-gel glass and the prepared sol-gel bioactive glass. The method comprises the use of Na-ethoxide in a sol-gel process2H5ONa) or NaCl instead of sodium nitrate to remove Na2O is introduced into the glass network. Medical and industrial uses of such glasses.
Description
Technical field
The present invention comprises bioactivity glass and the application thereof containing sodium of new preparation of sol-gel in general.
Background technology
Use sol-gel technique to prepare the sol-gel process of bioactivity glass normally well known.For example, United States Patent (USP) 5,074, No. 916 (" ' 916 patent "), (its purport is incorporated in to this with for referencial use), discloses for the production of based on SiO
2, CaO
2and P
2o
5the sol-gel processing technology of alkali-free bioactive glass compositions.' 916 patent discloses by changing SiO
2content, can obtain the composition of a series of production rates of hydroxylapatite in various degree.Moreover change has been expanded the SiO that can use composition to the reaction times of solution in the body of true or simulation
2ratio.Can select the composition of the preparation of sol-gel that is disclosed in ' 916 patent to obtain the target value of thermal expansivity, Young's modulus and volume specific resistance.The manufacture method of the dry Sol-gel bioactive glass of approximate equilibrium (near equilibrium) is recorded in United States Patent (USP) 6,171, in No. 986, its full content is incorporated in to this with for referencial use.
Should ' 916 patents explain the bioactivity glass that the bioactivity glass of preparation of sol-gel is better than being obtained by scorification, and can avoid using alkalimetal oxide as Na in the bioactivity glass of preparation of sol-gel
2o.Flux (flux) or auxiliary agent when this type of alkalimetal oxide is used for melting or homogenizing.Should ' 916 patents point out, the existence of basic metal oxidative ionic causes the high pH of the interface between glass and ambient body fluid or tissue in vivo, and this may bring out inflammation and close reparation.Be somebody's turn to do ' 916 patents by only using SiO
2, CaO
2and P
2o
5and eliminate traditionally to sodium or other alkali metal compound are assisted the bioactive demand of generation and avoided problems.
The patent application gazette U.S. points out for No. 2009/0208428, and basic metal, sodium and potassium exist and can reduce bioactivity glass availability in vivo with high density in bioactivity glass.The glass that is disclosed in the preferred sol-gel source in the U.S. 2009/0208428 comprises strontium and alkali metal-free.
Bio-vitric prepared by the melting of numbering 45S5 comprises 45% SiO
2(in % by weight), and 24.5% CaO, 24.5% Na
2o and 6% P
2o
5, in the time implanting in living tissue, provide biological respinse fast compared with other bioactivity glass goods, or biological activity fast in other words.
Be fully recognized that, the biological activity of bio-vitric is owing to its surface reaction.Early stage in the nineties, report the Sol-gel bioactive glass due to its pore structure with high specific surface area.Since then, report 49S, 58S, 68S, 77S, 86S sol-gel composite, correspondingly there is respectively 50%, 60%, 70%, 80% and 90% SiO in mol%
2.The 45S5 bio-vitric that the specific surface area of all these compositions is prepared than melting is high 100 times.These compositions are typically due to by Na
2o is incorporated to glass network difficulty and does not comprise Na
2o.
The product in for example zeolite of some hemostasia products and starch powder source, uses in the world because they have the haemostatic effect that high-specific surface area produces.Think there is the material of high surface area can be rapidly from blood planar water, and concentrated blood coagulating protein (clotting protein) and thrombocyte, thus promote instantaneous sludged blood to form.Sol-gel bioactive glass has higher specific surface area, the generally acknowledged character such as the mouth care in the purposes such as their enhance bone growth, soft tissue growth and healing and such as desensitizing dental, antigingivitis and tooth whitening, should be desirable anastalsis material.No. 2009/0186013 and 2009/0232902, US patent application publication, introduces its full content with for referencial use at this, the biological activity silica gel that the claimed sol-gel with vesicular structure and high-specific surface area with haemostatic effect is made.But the silica gel of all reports is to be all made up of Si, Ca and P initial soln or their mineral compound, and these silica gel are not reported and are contained sodium initial soln.
Several pieces of articles are disclosed in the recent period about comprising Na
2the 45S5 bio-vitric in the sol-gel source of O.Referring to Q Z Chen, Y Lia, L Y Jina, J M W Quinnc, P A Komesaroffe, " A new sol-gel process for producing Na
2o-containing bioactive glass ceramics ", Acta Biomaterialia V6 (10), 4143-53,2010; R L Siqueira, O P Edgar and D Zanotto, " Gel-derived SiO
2– CaO – Na
2o – P
2o
5bioactive powders:Synthesis and in vitro bioactivity ", Materials Science and Engineering:C V31 (5), 983 – 91,2011; Q ZChen, G A Thouas, " Fabrication and Characterization of Sol-gel Derived45S5Bioglass – Ceramic Scaffolds ", Acta Biomaterialia, 7,3636-26,2011; I Cacciotti, M Lombardi, the people such as A Bianco, " Sol-gel Derived45S5Bioglass:Synthesis, Microstructural Evolution and Thermal Behaviour ", J Mater Sci:Mater Med, 23:1849-66,2012.All these work have been used NaNO
3(SODIUMNITRATE) in preparation of sol-gel process by Na
2o introduces bio-vitric system.As explained below, comparative experiments has been illustrated and can be visually observed precipitation in the gel surface of being prepared by SODIUMNITRATE after aging, and this can cause possible heterogeneous composition.The definite composition of the sol-gel 45S5 bioglass material of reporting is owing to not reporting that in those disclosed work data have retained problem.In addition, all these goods have been described and have been prepared sol-gel 45S5 glass with the high temperature sintering of 700 ℃-1100 ℃.High temperature sintering can make it possible to prepare homogeneous composition, but this process can reduce surface-area tempestuously, thereby produces fine and close 45S5 bio-vitric.Author does not provide the data of any porosity and specific surface area in these are open yet.
Summary of the invention
An aspect, the present invention is intended to comprise the Sol-gel bioactive glass initial soln in Si source, Ca source, P source and Na source, free NaCl and C are selected in wherein said sodium source
2h
5the group of ONa composition.
Further, the present invention is intended to by making patient contact the method that the Sol-gel bioactive glass of being made up of the Sol-gel bioactive glass initial soln that comprises Si source, Ca source, P source and Na source makes patient reach anastalsis or induces rapid blood coagulation, and wherein free NaCl and Na-ethylate (C are selected in sodium source
2h
5oNa) in the group of composition.
On the other hand, the present invention is intended to comprise the Sol-gel bioactive glass of Si, Ca, P and Na, and wherein said Sol-gel bioactive glass derives from and comprises and select free NaCl and C
2h
5the mixture in the sodium source of the group of ONa composition.
Also on the other hand, the present invention is intended to make to need the patient for the treatment of to reach anastalsis or induces the method for rapid blood coagulation, described method comprises the Sol-gel bioactive glass that patient is contacted comprise Si, Ca, P and Na, and wherein said Sol-gel bioactive glass derives from and comprises and select free NaCl and C
2h
5the mixture in the sodium source of the group of ONa composition.
Also on the other hand, the present invention is intended to the preparation method of the Sol-gel bioactive glass that comprises Si, Ca, P and Na, described method comprises mixes the Sol-gel bioactive glass initial soln that comprises Si source, Ca source, P source and Na source, and free NaCl and C are selected in wherein said sodium source
2h
5the group of ONa composition; Place aging described mixture solution; With dry described mixture, thereby form Sol-gel bioactive glass.
Consult figure below and describe in detail time, other system of the present invention, method, characteristic and advantage to those skilled in the art will, maybe will become apparent.Be intended to all these additional systems, method, characteristic and advantage within the scope of the invention, and included by following claim.
Embodiment
Unless be particularly limited, otherwise that the technician in the implication of these all technology that use and the scientific terminology field applicable with the present invention understood conventionally is identical.
The preparation method of Sol-gel bioactive glass initial soln, sol-gel glass and gained Sol-gel bioactive glass are disclosed in this, comprising in sol-gel process by by Na-ethylate or NaCl rather than SODIUMNITRATE by Na
2o introduces glass network.Described initial soln comprises that element is as organo-metallic or the inorganic salt of for example Si, Ca, Na, P, Ca and/or B, and described element is converted to their corresponding oxide compounds after heat treated.Gained gel provides homogeneous material.This gel can the relative low temperature below 100 ℃ under thermal treatment, thereby preserve the pore structure of high-specific surface area, and then avoid sintering step and for example possibility of disclosed biologically active molecules in 5,830,480 (its content is incorporated in to this with for referencial use with entirety) of interpolation is provided.Sol-gel glass at 500-1000 ℃ or preferred sintering at 550-650 ℃ alternatively.Biological activity sol-gel prepared in accordance with the present invention provides significantly improved hemostatic properties compared with the 45S5 bio-vitric in melting source and other sol-gel composite.In addition, biological activity sol-gel prepared in accordance with the present invention shows suitable compared with the anastalsis product being obtained commercially at present with some or better hemostatic properties.
Sol-gel bioactive glass initial soln according to the present invention is for providing the mixture of composition in Si source, Ca source, P source and Na source.Organometallic compound or the inorganic salt (except SODIUMNITRATE) in many Si of providing source, Ca source, P source or Na source can be provided.For example, organoalkoxysilane can be used as the source of silicon as tetraethoxysilane (tetraethoxysilane), and calcium methylate can be used as calcium source, and triethyl phosphate (triethylphoshpate) can be used as phosphorus source.Sodium-chlor or sodium ethylate can be used as sodium source.Sol-gel bioactive glass initial soln and sol-gel prepared therefrom can further comprise K, Mg, Zn, B, F, Ag, Cu, Fe, Mn, Mo, Sr and Zn.
Silicon oxide typically exists with the amount of the biological activity sol-gel glass of 20-86 % by weight or 30-60 % by weight or 30-45 % by weight.Many organosilicons or silicon salt can be used as initial soln, and can be enough to produce the SiO of 0-86 % by weight in bioactivity glass
2amount exist.Also can use colloid silica or contain silicic acid.
Sol-gel bioactive glass can further comprise sodium.Much organic sodium or inorganic sodium can be used as initial soln, include but not limited to sodium-chlor or sodium ethylate.This type of initial soln can be to be enough to produce the Na of 0-40 % by weight, 1-55 % by weight, 5-15 % by weight, 25-30 % by weight or approximately 10 % by weight in biological activity sol-gel glass
2the amount of O is used.
Sol-gel bioactive glass can further comprise potassium.Potassium initial soln can include but not limited to that organic potassium compound or inorganic potassium salt are as saltpetre (KNO
3), potassium sulfate (K
2sO
4) and potassium silicate.The wherein low bioactive glass compositions of potassium content is advantageously provided.If comprise potassium initial soln, it can be to be enough to produce the K of 0-8 % by weight in bioactivity glass
2the amount of O exists.
Bioactivity glass of the present invention preferably includes calcium.Calcium initial soln includes but not limited to that the inorganic salt of organic calcium compound or calcium are as nitrocalcite (Ca (NO
3)
2), calcium nitrate tetrahydrate (CaNo
34H
2o), calcium sulfate (CaSO
4), the source of Calucium Silicate powder or calcium oxide.The source of calcium oxide comprises any compound of decomposing to form calcium oxide.Ca
2+ion is assisted at glass surface and is formed the layer that is rich in calcium phosphate from the release of bioactive glass surface.By bioactivity glass supply calcium ion can increase be rich in calcium phosphate layer form speed.However, it should be understood that the layer that is rich in calcium phosphate can form in the situation that not providing calcium ion by bioactivity glass, because body fluid itself comprises calcium ion.Therefore, for purposes of the present invention, can use the bioactivity glass that does not comprise calcium.The introducing of calcium initial soln can be is enough in gained sol-gel glass to produce at least 5%, the amount of 0-40%, 10-20%, 20-30% or approximately 25% CaO.
Bioactivity glass of the present invention preferably includes P
2o
5.Phosphoric acid ester (salt) initial soln comprises many organophosphates (salt) and inorganic phosphate, includes but not limited to triethyl phosphate.Phosphate ion is from the auxiliary formation containing carbonate hydroxyapatite (hydroxycarbonated apatite) of release of bioactive glass surface.But can provide under phosphate ion and form can't help bioactivity glass containing carbonate hydroxyapatite, because body fluid itself comprises phosphate ion, provide phosphate ion to increase the speed that forms containing carbonate hydroxyapatite by bioactivity glass.The introducing of phosphoric acid ester (salt) initial soln can be the P that is enough to produce 0-80%, 0-50%, 20-70%, 20-30%, 25-30% or approximately 25% in gained glass
2o
5amount.
Sol-gel bioactive glass of the present invention can comprise zinc.For example zinc nitrate of the inorganic salt (Zn (NO that zinc initial soln includes but not limited to organic zinc compound or comprises zinc
3)
2), zinc phosphate (ZnSO
4) and zinc silicate, and decompose any this compounds to form zinc oxide.If existed, zinc initial soln can be the amount that is enough to the ZnO that produces 0.01-5% in glass.
Bioactivity glass of the present invention can comprise magnesium.Magnesium initial soln includes but not limited to that organo-magnesium compound or inorganic magnesium salt are as magnesium nitrate (Mg (NO
3)
2), magnesium sulfate (MgSO
4), Magnesium Silicate q-agent, and decompose to form magnesian any this compounds.In the time comprising magnesium source, magnesium source can be the amount that is enough to the MgO that produces 0.01-5% in bioactivity glass.
Sol-gel bioactive glass of the present invention also comprises boron.Boron initial soln includes but not limited to organic boric acid ester (salt) compound, inorganic borate, boric acid and trimethyl borate.Thereby the boron initial soln that can use q.s is enough to provide the B of the amount of at least 25% in glass, 30%-50%, 35-45% or as many as 80 % by weight
2o
3.
Bioactivity glass of the present invention can comprise fluorine.Fluorine initial soln includes but not limited to that organofluorine compound or inorganic fluoride salt are as Calcium Fluoride (Fluorspan) (CaF
2), strontium fluoride (SrF
2), magnesium fluoride (MgF
2), Sodium Fluoride (NaF) or Potassium monofluoride (KF).Fluorochemical stimulating osteoblast also increases the speed of carbon containing precipitation of hydroxyapatite.If existed, the amount of fluorine initial soln is for providing the Calcium Fluoride (Fluorspan) of 0-35% or 0.01-5%.
Biological activity sol-gel can further comprise Cu source, Fe source, Mn source, Mo source or Sr source.If existed, this type of source comprises its organic metal salt and inorganic salt.Can in glass, have to provide corresponding oxide compound more than 0.01-5 % by weight separately.
According to the present invention, biological activity sol-gel is the hemostatic material of biological absorbable (bioabsorbable), and excellent anastalsis is provided, and can be made into various forms and be applicable to control the hemorrhage of various exterior skins and the inner wound of body.Biological activity sol-gel glass can be in particulate state or powder-form, netted (matt) or fibers form, styptic sponge, introducing foam materials, the form of paste or paste.They also can be made into coagulable (settable) and the non-carrier solidifying.
Sol-gel bioactive glass be applicable to the to perform the operation site disposal of purposes and wound.For example, at vascular surgery, hemorrhage problem is particularly serious.In cardiac operation, the blood coagulation disorders that cause because of external circulation of blood (extracorporeal bypass) in addition multiple vascular anastomosiss and needle tubing insertion point, can cause carrying out Bleeding control by local hemostatic.During spinal operation, be difficult for controlling by sewing up or burning as its bone, epidural and/or subdural hemorrhage or from myelapoplexy, hemostasis so fast and effectively can make the minimizing possibility that nerve root (nerve root) sustains damage and reduce operating time.In for example LD liver transplantation operation of liver surgery or tumor removal, there is the material risk of bleeding profusely.Effectively hemostatic material can fully strengthen patient at the successful result (outcome) of accepting in this type of operation.Even in those situations of not bleeding profusely, as being also supposed to as the effective hemostasis in the treatments such as tooth extraction and scratch and burn in dentistry.In neurosurgery, wound oozes out be common and be difficult to process.
Biological activity sol-gel can further combine with biologically active agent.Biologically active agent comprises antibody, antigen, and microbiotic, wound disinfecting substance, zymoplasm, thrombin, conventional chemical and radiation therapy medicine, VEGF, antineoplastic agent is as angiostatin, Endostatin, biological response modifier, and various combination.Biological activity sol-gel also can combine with high molecular polymer, thereby further structural strength support is provided.For example, porous bioglass hemostatic agent can be prepared by further using the multipolymer of some oxyethane and propylene oxide in described sol-gel process.
Other purposes of sol-gel composite of the present invention comprise filling bone defects, bone repair/regeneration, protect limb art, medicament slow release is sent, cartilage defect repair, dentin hypersensitiveness desensitization, tooth whitening and guided tissue regeneration.
Embodiment
The preparation of sol-gel
Utilize composition shown in table 1 and as described in following 1-1 to 1-6, prepare Sol-gel bioactive glass:
Table 1: the composition of Sol-gel bioactive glass
Preparation 1-1.100S gel (control group-containing Na source, Ca source or P source): by mix deionized water (D.I.water), HCl, TEOS (tetraethoxysilane), mix subsequently within 60 minutes, carry out facilitation of hydrolysis reaction complete to prepare gel.Then, mixture is transferred in polypropylene model to aging 55 hours at 60 ℃.After aging, gel is transferred in drying receptacle for being dried to 180 ℃, then at 700 ℃ with United States Patent (USP) 5,074, identical step heating of report in No. 916 (its content is incorporated in to this with for referencial use with its full content).Heat treated gel grinds to form the powder of <300 μ m for analyzing and test.
Preparation 1-2.77S gel (Dui Zhao Zu – is not containing Na source): by mixing deionized water, HCl, TEOS (tetraethoxysilane) 30 minutes, TEP (triethyl phosphate) be added in solution and mix other 20 minutes, then adding CaNO
34H
2o (calcium nitrate tetrahydrate) mixes other 60 minutes simultaneously, thereby completes the dissolving of nitrocalcite, prepares gel.Then, mixture is transferred in polypropylene molds at 60 ℃ to aging 55 hours.After aging, gel is transferred in drying receptacle for being dried to 180 ℃, then at 700 ℃ with United States Patent (USP) 5,074, the identical step heating of report in No. 916.Heat treated gel grinds to form the powder of <300 μ m for analyzing and test.
Preparation 1-3.58S gel (Dui Zhao Zu – is not containing Na source): by mixing deionized water, HCl, TEOS (tetraethoxysilane) 30 minutes, TEP (triethyl phosphate) be added in solution and mix other 20 minutes, then adding CaNO
34H
2o (calcium nitrate tetrahydrate) mixes other 60 minutes simultaneously, thereby completes the dissolving of nitrocalcite, prepares gel.Then, mixture is transferred in polypropylene molds at 60 ℃ to aging 55 hours.After aging, gel is transferred in drying receptacle for being dried to 180 ℃, then at 700 ℃ with United States Patent (USP) 5,074, the identical step heating of report in No. 916.Heat treated gel grinds to form the powder of <300 μ m for analyzing and test.
Preparation 1-4.45S5 gel #1 (comprising that sodium ethylate is as Na source): by mixing deionized water, HCl, the TEOS (tetraethoxysilane) 30 minutes of half amount, TEP (triethyl phosphate) is added in solution and mixes other 20 minutes, then add remaining deionized water, calcium methylate and sodium ethylate, mix other 60 minutes simultaneously, thereby complete hydrolysis reaction, prepare gel.Then, mixture is transferred in polypropylene molds at 60 ℃ to aging 55 hours.After aging, gel is transferred in drying receptacle for being dried to 180 ℃, then at 550 ℃ with United States Patent (USP) 5,074, the identical step heating of report in No. 916.Heat treated gel grinds to form the powder of <300 μ m for analyzing and test.
Preparation 1-5.45S5 gel #2 (comprising that NaCl is as Na source): by mixing deionized water, HCl, TEOS (tetraethoxysilane) 30 minutes, TEP (triethyl phosphate) be added in solution and mix other 20 minutes, then adding CaNO
34H
2o (calcium nitrate tetrahydrate) and NaCl mix other 60 minutes simultaneously, thereby complete the dissolving of nitrocalcite and NaCl, prepare gel.Then, mixture is transferred in polypropylene molds at 60 ℃ to aging 55 hours.After aging, gel is transferred in drying receptacle for dry at 180 ℃, then at 550 ℃ with United States Patent (USP) 5,074, the identical step heating of report in No. 916.
Preparation 1-6.45S5 gel #3 (Dui Zhao Zu – comprises that SODIUMNITRATE is as Na source): by mixing deionized water, HCl, TEOS (tetraethoxysilane) 30 minutes, TEP (triethyl phosphate) be added in solution and mix other 20 minutes, then adding CaNO
34H
2o (calcium nitrate tetrahydrate) and NaNO
3(SODIUMNITRATE) mixes other 60 minutes simultaneously, thereby completes the dissolving of nitrocalcite and SODIUMNITRATE, prepares gel.Then, mixture is transferred in polypropylene molds at 60 ℃ to aging 55 hours.After aging, be visually observed precipitation.After aging, gel is transferred in drying receptacle for dry at 180 ℃, then at 550 ℃ with United States Patent (USP) 5,074, the identical step heating of report in No. 916.
Obtain following vesicular structure data by foregoing:
Anastalsis research
Male adult Vist rat (Wistar rats) is anaesthetized by intraperitoneal injection Sodital (40mg/kg).Manufacture irregular otch and separate left kidney.Thin flexible plastic disc is placed under kidney, and with the absorbent cotton parcel kidney of weighing in advance.Then intravenous injection heparin sodium (300IU/kg).After five minutes, the clamp of antisitic defect (atraumatic clamp) is placed across kidney vessel pedicle (renal vascular pedicle), the stern post (caudal pole) of kidney is extruded by the ring of approximately 4mm protruding above dish, and cuts off tissue with scalpel blade.Before unclamping, clamp applies the cut surface of hemostatic agent to kidney.Clamp unclamps record and measures bleeding time and the amount of bleeding (blood Wt).
4-1. studies #1
Test sample: 45S5 (melting), sol-gel 58S
Control group: FloSeal, starch (the two is the product that is obtained commercially using in world's market scope)
Blank: do not apply material
Each trial target is tested with 50mg, and carries out 6 tests.
Table 3: study the bleeding time of #1 and the test-results of bleeding in the rat model of partial nephrectomy
Based on the statistic data of this test, sol-gel 58S confirmed with market in be obtained commercially the comparable haemostatic effect of product F loSeal.Order is 58S> melting 45S5> starch.All test materialss are all better than non-processor contrast.
4-2. studies #2
Test sample: 45S5 (melting), 45S5 (sol-gel), 58S, 77S, 100S
Control group: NexStat (Hemostasis, LLC),
Blank: do not apply material
With 3 kinds of dosage, (5 μ l, 15 μ l and 50 μ l) test each trial target, and every kind of dosage carries out 6 tests.
Test-results
Table 4: blank
| Bleeding time (s) | The blood Wt (g) collecting |
| 647±25.57 | 5.35±0.17 |
Table 5: study the bleeding time of #2 in the rat model of partial nephrectomy and bleed
Based on the statistics of this test, sol-gel 45S5 has confirmed best haemostatic effect.Be sequentially sol-gel 45S5>NexStat>77SGreatT.GreaT .GT58S> melting 45S5>100S.
Sol-gel 45S5 has confirmed and other test materials, best haemostatic effect compared with some anastalsis product being obtained commercially even.The 45S5 bio-vitric in surface area ratio melting source with the sol-gel 45S5 of vesicular structure is high 30 times.The function of high area is also to concentrate blood coagulating protein and thrombocyte to promote instantaneous grumeleuse to form from the rapid planar water of blood.The function of the calcium ion discharging from glass in addition, is to combine to promote grumeleuse to form at the carboxylic acid functional of release and protein.Although sol-gel 45S5 specific surface area and other sol-gel material are compared and are not the highest with 100S as 58S, 77S, can imagine is the Na of sol-gel 45S5 inside
+on sol-gel 45S5 surface or the inner a large amount of silanol groups (Si-OH) that produce in hole, this will promote the physics and chemistry of water on glass surface to absorb with OH-ion-exchange meeting in liquid.
Due to its surfactivity fast, the Ca discharging from sol-gel 45S5
2+also by highly significant.As previously mentioned, calcium ion will combine with peripheral protein matter (being most importantly used as a kind of scleroproein of glue), thereby keep fibrin monomer mutually to form polymer fiber.Gained scleroproein fiber forms loose network, and its function is embedding red corpuscle, thereby forms the grumeleuse that stops blood flow.All of these factors taken together contributes to the haemostatic effect being shown by sol-gel 45S5 bio-vitric.
Run through this specification sheets, preferred and optional embodiment of the present invention is provided to various indicating.But detailed description above will be considered to illustrative and be not restrictive, and any provided embodiment is not provided in the present invention.It should be understood that the claims including all equivalents are intended to determine the spirit and scope of the present invention just.
Claims (26)
1. a Sol-gel bioactive glass initial soln, it comprises Si source, Ca source, P source and Na source, wherein said sodium source is selected in the group of free NaCl and Na-ethylate composition.
2. Sol-gel bioactive glass initial soln according to claim 1, wherein said Si source is tetraethoxysilane.
3. Sol-gel bioactive glass initial soln according to claim 1, wherein said Ca source is calcium nitrate tetrahydrate.
4. Sol-gel bioactive glass initial soln according to claim 1, wherein said Ca source is calcium methylate.
5. Sol-gel bioactive glass initial soln according to claim 1, wherein said P source is triethyl phosphate.
6. Sol-gel bioactive glass initial soln according to claim 1, wherein said Na source is NaCl.
7. Sol-gel bioactive glass initial soln according to claim 1, wherein said Na source is C
2h
5oNa, and so that the Na of 20-30 % by weight to be provided in Sol-gel bioactive glass
2the amount of O exists.
8. Sol-gel bioactive glass initial soln according to claim 6, wherein said Na source is NaCl, and so that the Na of 20-30 % by weight to be provided in Sol-gel bioactive glass
2the amount of O exists.
9. Sol-gel bioactive glass initial soln according to claim 7, wherein said Na source is C
2h
5oNa.
10. Sol-gel bioactive glass initial soln according to claim 2, wherein said phosphorus source is triethyl phosphate, and so that the P of 20-30 % by weight to be provided in Sol-gel bioactive glass
2o
5amount exist.
11. 1 kinds of Sol-gel bioactive glass, it comprises Si, Ca, P and Na, wherein said Sol-gel bioactive glass derives from and comprises and select free NaCl and C
2h
5the mixture in the sodium source of the group of ONa composition.
12. Sol-gel bioactive glass according to claim 11, wherein said Na source is NaCl.
13. Sol-gel bioactive glass according to claim 11, wherein said Na source is C
2h
5oNa.
14. 1 kinds comprise the preparation method of the Sol-gel bioactive glass of Si, Ca, P and Na, and described method comprises:
Mix the Sol-gel bioactive glass initial soln that comprises Si source, Ca source, P source and Na source, free NaCl and C are selected in wherein said sodium source
2h
5the group of ONa composition;
Place aged mixture solution; With
Dry described mixture, thus described Sol-gel bioactive glass formed.
15. methods according to claim 14, the aging 40-70 hour that carries out at the temperature of 50-80 ℃ of wherein said placement.
16. methods according to claim 14, it is further included in sintering 15-50 hour at 500-800 ℃.
17. 1 kinds of patients for needs treatment reach the method for anastalsis, and it comprises makes described patient contact Sol-gel bioactive glass according to claim 11.
Induce the method for rapid blood coagulation in bleeding patients for 18. 1 kinds, it comprises makes described patient contact Sol-gel bioactive glass according to claim 11.
19. 1 kinds of patients for needs treatment reach the method for anastalsis, and it comprises makes described patient contact the Sol-gel bioactive glass of being made up of Sol-gel bioactive glass initial soln according to claim 1.
20. Sol-gel bioactive glass according to claim 11, wherein Si, Ca, P and Na are with their SiO
2, Ca
2o, P
2o
5exist with the oxide form of NaO.
21. Sol-gel bioactive glass according to claim 20, it further comprises K, Mg, Zn, B, F or Ag more than one.
22. 1 kinds comprise the preparation method of the Sol-gel bioactive glass of Si, Ca, P and Na, and described method comprises:
Mix the Sol-gel bioactive glass initial soln that comprises Si source, Ca source, P source and Na source, free NaCl and C are selected in wherein said sodium source
2h
5the group of ONa composition; With
Drying composite at temperature below 100 ℃.
23. methods according to claim 22, it further comprises interpolation biologically active molecules.
24. 1 kinds of soft methods for the treatment of of forming wound of patient, it comprises makes described patient contact Sol-gel bioactive glass according to claim 11.
Repair the damaged method of bone in patient for 25. 1 kinds, it comprises makes the bone of needs treatment contact Sol-gel bioactive glass according to claim 11.
26. 1 kinds of Sol-gel bioactive glass, it comprises Si, alkaline-earth metal, P and basic metal, wherein said Sol-gel bioactive glass derives from the mixture that comprises sodium source, and the choosing of described sodium source freely contains the group of the compound of organic sodium or the composition of the metal-salt except SODIUMNITRATE.
Applications Claiming Priority (2)
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| CN104324410A (en) * | 2014-09-26 | 2015-02-04 | 湖北华中医用材料有限公司 | Raw material composition of multi-component active wound repair material and preparation method |
| CN108863021A (en) * | 2018-07-26 | 2018-11-23 | 福州大学 | A kind of nitrogen oxides bio-vitric and preparation method thereof |
| CN108892388A (en) * | 2018-07-26 | 2018-11-27 | 福州大学 | A kind of preparation method of porous nitrogen oxides bio-vitric |
| CN110418771A (en) * | 2017-03-16 | 2019-11-05 | 尼拉伊贾扬特·拉克加 | Gel pouring prepares cellular glass and glass-ceramic particles structure |
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| CN110418771B (en) * | 2017-03-16 | 2022-07-26 | 尼拉伊贾扬特·拉克加 | Preparation of porous glass and glass ceramic particle structure by gel casting |
| CN108863021A (en) * | 2018-07-26 | 2018-11-23 | 福州大学 | A kind of nitrogen oxides bio-vitric and preparation method thereof |
| CN108892388A (en) * | 2018-07-26 | 2018-11-27 | 福州大学 | A kind of preparation method of porous nitrogen oxides bio-vitric |
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