CN113666632A - Medical bioactive glass and preparation method and application thereof - Google Patents
Medical bioactive glass and preparation method and application thereof Download PDFInfo
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- CN113666632A CN113666632A CN202111144492.8A CN202111144492A CN113666632A CN 113666632 A CN113666632 A CN 113666632A CN 202111144492 A CN202111144492 A CN 202111144492A CN 113666632 A CN113666632 A CN 113666632A
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- Prior art keywords
- bioactive glass
- medical
- mol
- metal oxide
- glass
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- 239000005313 bioactive glass Substances 0.000 title claims abstract description 178
- 238000002360 preparation method Methods 0.000 title abstract description 9
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 230000001105 regulatory effect Effects 0.000 claims abstract description 13
- 239000001110 calcium chloride Substances 0.000 claims abstract description 11
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 10
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims abstract description 9
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims abstract description 9
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims abstract description 9
- 229910001637 strontium fluoride Inorganic materials 0.000 claims abstract description 9
- 229910001634 calcium fluoride Inorganic materials 0.000 claims abstract description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 8
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 8
- 239000003607 modifier Substances 0.000 claims abstract description 8
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical group [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229910001631 strontium chloride Inorganic materials 0.000 claims abstract description 7
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229910002319 LaF3 Inorganic materials 0.000 claims abstract description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910001510 metal chloride Inorganic materials 0.000 claims abstract description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 5
- 229910002249 LaCl3 Inorganic materials 0.000 claims abstract description 5
- 229910001626 barium chloride Inorganic materials 0.000 claims abstract description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011592 zinc chloride Substances 0.000 claims abstract description 5
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 claims abstract description 4
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(II) oxide Inorganic materials [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 claims abstract description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 4
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims abstract description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 27
- 210000000988 bone and bone Anatomy 0.000 claims description 25
- 238000002844 melting Methods 0.000 claims description 20
- 230000008018 melting Effects 0.000 claims description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 18
- 229910052681 coesite Inorganic materials 0.000 claims description 14
- 229910052906 cristobalite Inorganic materials 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- 229910052682 stishovite Inorganic materials 0.000 claims description 14
- 229910052905 tridymite Inorganic materials 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 239000000606 toothpaste Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- 239000002324 mouth wash Substances 0.000 claims description 7
- 229940051866 mouthwash Drugs 0.000 claims description 7
- 229940034610 toothpaste Drugs 0.000 claims description 7
- 239000000919 ceramic Substances 0.000 claims description 6
- -1 dental desensitizers Substances 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 239000000805 composite resin Substances 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 239000002631 root canal filling material Substances 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 230000002087 whitening effect Effects 0.000 claims description 3
- 229940124380 dental desensitizing agent Drugs 0.000 claims description 2
- 239000003814 drug Substances 0.000 claims description 2
- 229940127554 medical product Drugs 0.000 claims description 2
- 239000003973 paint Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 150000001805 chlorine compounds Chemical class 0.000 abstract 1
- 239000011521 glass Substances 0.000 description 41
- 238000010791 quenching Methods 0.000 description 20
- 238000007578 melt-quenching technique Methods 0.000 description 18
- 230000000171 quenching effect Effects 0.000 description 18
- 239000007983 Tris buffer Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- 238000002791 soaking Methods 0.000 description 14
- 230000015556 catabolic process Effects 0.000 description 11
- 238000006731 degradation reaction Methods 0.000 description 11
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 10
- 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 10
- 239000000654 additive Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 230000007547 defect Effects 0.000 description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 7
- 238000013461 design Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 230000006870 function Effects 0.000 description 6
- 230000011164 ossification Effects 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 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 5
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 241000700159 Rattus Species 0.000 description 4
- 206010052428 Wound Diseases 0.000 description 4
- 208000027418 Wounds and injury Diseases 0.000 description 4
- 230000000844 anti-bacterial effect Effects 0.000 description 4
- 239000002519 antifouling agent Substances 0.000 description 4
- 229910052586 apatite Inorganic materials 0.000 description 4
- 229910001424 calcium ion Inorganic materials 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000002609 medium Substances 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 230000008439 repair process Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 210000001519 tissue Anatomy 0.000 description 4
- 229940090898 Desensitizer Drugs 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 241000194017 Streptococcus Species 0.000 description 3
- 230000000259 anti-tumor effect Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 238000010603 microCT Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 210000003625 skull Anatomy 0.000 description 3
- 229910052712 strontium Inorganic materials 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 239000000120 Artificial Saliva Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000004071 biological effect Effects 0.000 description 2
- 230000008827 biological function Effects 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 239000001963 growth medium Substances 0.000 description 2
- 238000002513 implantation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 210000000963 osteoblast Anatomy 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000000371 solid-state nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 230000006820 DNA synthesis Effects 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000009098 adjuvant therapy Methods 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000033115 angiogenesis Effects 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 230000010478 bone regeneration Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000005115 demineralization Methods 0.000 description 1
- 230000002328 demineralizing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 229910052587 fluorapatite Inorganic materials 0.000 description 1
- 229940077441 fluorapatite Drugs 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 239000003102 growth factor Substances 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000000395 remineralizing effect Effects 0.000 description 1
- 210000003296 saliva Anatomy 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000012890 simulated body fluid Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 210000004872 soft tissue Anatomy 0.000 description 1
Images
Classifications
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- C03C3/00—Glass compositions
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- A61K6/50—Preparations specially adapted for dental root treatment
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- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/831—Preparations for artificial teeth, for filling teeth or for capping teeth comprising non-metallic elements or compounds thereof, e.g. carbon
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- A61L27/58—Materials at least partially resorbable by the body
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
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- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
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- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
Abstract
Discloses medical bioactive glass and a preparation method and application thereof, and the medical bioactive glass comprises the following raw material components in parts by weight: SiO 2220‑60mol％；P2O53-8 mol%; 0.5-56 mol% of metal chloride or crystalline hydrate thereof; 20-60 mol% of the network modifying body; 0.1-20 mol% of functional regulating metal oxide; fluoride 0.1-9 mol%, and network modifier comprising alkali metal oxide and/or alkaline earth metal oxide, specifically K2One or more of O, MgO, CaO, BaO and SrO; the function-adjusting metal oxide is CuO, ZnO or Fe2O3、SnO、CeO2CoO and MnO2Fluoride is CaF2、SrF2、MgF2And LaF3One or more of the chlorides is CaCl2、SrCl2、BaCl2、ZnCl2、LaCl3And KCl.
Description
Technical Field
The invention belongs to the technical field of biomedical materials, and particularly relates to medical bioactive glass and a preparation method and application thereof.
Background
Bioactive glass (BAG) is an inorganic non-metallic material which can repair, replace and regenerate body tissues and can form bonding action between tissues and materials. The first bioactive glass 45S5 was discovered by Hench in 1969 as SiO2，Na2O, CaO and P2O5And the like. The bioactive glass can be degraded in body fluid to release active ion (Ca)2+、Si4+、PO4 3-Etc.) can produce hydroxyapatite (HAP, Ca) having the same composition as main bone component5(PO4)3OH) can form close bonding with host bones, induce bone regeneration, promote osteoblast gene expression, increase DNA synthesis amount, stimulate angiogenesis, and accelerate the repair of soft and hard tissues. Has wide application prospect in dentistry and orthopaedics. The degradation product of the bioactive glass can promote the generation of growth factors, promote the multiplication of cells, enhance the gene expression of osteoblasts and the growth of bone tissues, and is the only artificial biomaterial which can be bonded with the bone tissues and connected with soft tissues so far.
The physicochemical property and biological function of the bioactive glass can be regulated and controlled through the composition, structure and form of the bioactive glass, so as to meet different clinical requirements. By adjusting the components of the bioactive glass and introducing different chemical elements, the structure and the function can be regulated and controlled or special properties can be endowed to the glass, for example, strontium is added into the bioactive glass, and chlorine can accelerate the degradation of the bioactive glass and improve the bioactivity of the bioactive glass; adding zinc, magnesium, cobalt,Fluorine and the like can make the glass antibacterial; the addition of strontium and fluorine can enhance the osteogenesis effect of the bioactive glass, and the like. There have been related studies, such as the Chinese patent application CN200780029345.8 bioactive glass, disclosing a bioactive glass comprising Sr and Si02The mol percentage of SrO is 0.2 to 45 percent, and Na, K, Ca and P are also included205、Mg、Zn、B2O3One or more sources of F or Ag, wherein CaF is used2、SrF2、MgF2One or more of NaF or KF provides the F, and CaF2、SrF2、MgF2The total mole percentage of NaF or KF is 0% to 50%, comprises 0% to 30% of the total mole percentage of a source of Na ions and/or K ions, comprises 0% to 50% of CaO, comprises 0% to 14% of P 205Comprising 0 to 40 mole percent MgO, comprising 0 to 10 mole percent ZnO, comprising 0 to 15 mole percent B 203. Studies have also found that by modifying network formers in the glass (e.g., SiO)2Linked to other network formers by bridging oxygen ions) and network modifiers (e.g. Na)2O, CaO, etc., the content proportion of non-bridge oxygen ion oxide generated by breaking the bridge oxygen bond between the bridge oxygen and the network forming body element can change the network connectivity of the glass (i.e. the average number of bridge oxygen bonds in each glass skeleton unit), and further regulate and control the degradation rate of the material to meet different application requirements. For example, the ratio of the network forming body to the network modifying body in the glass is reduced, so that the structure of the glass can be changed from a three-dimensional network structure to a chain structure, the stability of the glass is further reduced, the degradability is improved, and the bioactive glass is formed, and vice versa. The research result shows that when the network connectivity of the bioactive glass is 1.9-2, the bioactive glass has good bioactivity, namely degradability and capability of generating apatite. When the network connectivity of the bioactive glass is greater than 2.6, the bioactive glass has little bioactivity.
In further in vitro studies, it was found that2-Na2O-CaO-P2O5Some bioactive glasses of the composition areThe formation of a small amount of mineralized hydroxyapatite can be detected only after soaking in simulated body fluid for 24 hours, and the degradation can cause the pH value of the solution to be rapidly increased. This means that the inclusion of such bioactive glasses as remineralizing toothpaste additives or desensitizers does not allow for rapid, efficient and controlled achievement of the desired mineralization. In addition, too high pH can damage cells and tissues, and when the bioactive glass is applied as a bone grafting material, the material can be degraded too fast, and the degradation rate is not coordinated with the bone repair and reconstruction rate.
Therefore, in combination with the application requirements, it is necessary to develop the personalized development and research of the novel bioactive glass.
Disclosure of Invention
The invention aims to provide medical bioactive glass, a preparation method and application thereof, and the medical bioactive glass can be used in dentistry and orthopaedics.
The purpose of the invention is realized by the following technical scheme:
the invention firstly provides medical bioactive glass, which comprises the following raw material components: SiO 22、P2O5Metal chloride or crystalline hydrate thereof, network modifier; the network modifier comprises an alkali metal oxide or/and an alkaline earth metal oxide; the network connectivity NC of the medical bioactive glass is 1.5-3.35; the calculation formula of NC is: the calculation formula of NC is:
in the formula:
is SiO in medical bioactive glass2The molar percentage of (A); mMOIs the mol percentage content of the alkaline earth metal oxide in the medical bioactive glass;
is the mol percentage content of alkali metal oxide in the medical bioactive glass;
is P in medical bioactive glass2O5In percentage by mole.
Furthermore, the medical bioactive glass also comprises a function regulating metal oxide, wherein the function regulating metal oxide is CuO, ZnO or Fe2O3、SnO、CeO2CoO and MnO2When mixed, in any proportion.
Furthermore, the medical bioactive glass also comprises fluoride, wherein the fluoride is CaF2、SrF2、MgF2And LaF3When mixed, in any proportion.
Further, the chloride is CaCl2、SrCl2、BaCl2、ZnCl2、LaCl3And KCl, when mixed, in any proportion; the alkali metal oxide is K2O; the alkaline earth metal oxide is one or more of MgO, CaO, BaO, and SrO, in any proportion when mixed.
Furthermore, the medical bioactive glass also comprises fluoride, wherein the fluoride is CaF2、SrF2、MgF2And LaF3When mixed, in any proportion.
Furthermore, the medical bioactive glass of the invention comprises the following raw material components in molar content:
SiO220-60mol％；
P2O53-8mol％；
0.5-56 mol% of metal chloride or crystalline hydrate thereof;
20-60 mol% of the network modifying body;
0.1-20 mol% of functional regulating metal oxide;
0.1-9 mol% of fluoride.
Furthermore, the medical bioactive glass of the invention has a phase state of amorphous bioactive glass or bioactive glass ceramic containing a crystalline phase in a bioactive glass matrix.
The preparation method of the medical bioactive glass is prepared by high-temperature melting and cold quenching (melt-quenching), and comprises the following specific steps:
1) weighing the raw materials according to the weight ratio designed by the formula, uniformly mixing, placing in a platinum crucible, carrying out melting treatment at 1250-;
2) and (3) drying the material obtained in the step (A) in an oven, and then grinding to obtain the medical bioactive glass.
In the preparation method, the cold water in the step 1) is water with the temperature of 0-30 ℃; the drying temperature of the step 2) is 60-80 ℃, and the time is 5-24 hours.
The invention also relates to the application of the medical bioactive glass in medicine, which is used as a raw material component of the following medical products: tooth protection paint, mouthwash, bone grafting materials, functional tooth pastes, dental desensitizers, root canal filling materials, composite resin filling materials, adhesives and wound dressings; the functional tooth paste comprises a whitening tooth paste and a remineralization tooth paste. The bone grafting material has good bone forming effect, and also has other adjuvant treatment effects of antibiosis, anti-inflammation, anti-tumor and the like.
Compared with the prior art, the invention has the following advantages:
1. in the bioactive glass of the present invention, SiO2A network former as a glass structure, which forms a glass network structure by the bridge oxygen; p2O5The glass structure is modified in the form of orthophosphate radicals; the metal chloride or the crystalline hydrate thereof does not influence the network connectivity of the glass, but can expand the structure of the glass and regulate the biological activity of the glass; the network modifier changes the network connectivity of the glass by destroying the bridge oxygen bond between Si and the bridge oxygen to form a non-bridge oxygen bond; fluoride also does not affect the network connectivity of the glass, but may be, for example, CaF+Or SrF+Modifying glass structure in equal forms, regulating physicochemical and biological functions of bioactive glass。
2. The NC value of bioactive glass has a certain correlation with its bioactivity (degradability and ability to produce apatite). When the NC value is more than 2.4, the bioactive glass has almost no bioactivity, and in vivo research shows that the bioactive glass has almost no osteogenesis energy; when the content is close to 2.0, the bioactive glass has good bioactivity; from 2.0 to 2.4(2.0 < NC ≦ 2.4), the bioactivity of the bioactive glass decreases with increasing NC value. When the NC value is less than 1.8, the bioactive glass is crystallized in a large amount, and the bioactivity is reduced. In the invention, because chloride is added, the network connectivity of the glass is not influenced, and meanwhile, the chloride ions can expand the glass structure, the degradability of the glass and the capability of generating apatite are improved, so when the NC value of the bioactive glass is more than 2.4, even equal to 3.18, the bioactive glass still has higher bioactivity, and simultaneously, the degradation rate of the glass is slowed down along with the increase of the NC value; when the NC of the bioactive glass is more than 1.5 and less than 2.0, the bioactive glass has excellent bioactivity, and the degradation rate of the bioactive glass is accelerated along with the increase of the chlorine content in the bioactive glass.
3. According to the NC calculation formula, the content of alkaline earth metal oxide, alkali metal oxide, silicon dioxide and phosphorus pentoxide in the medical bioactive glass is adjusted in a limited range, so that the NC value of the medical bioactive glass can be adjusted in a desired range, the physicochemical property and the biological property of the medical bioactive glass can be regulated and controlled, and the medical bioactive glass has wide application prospects, such as fluorine protective paint, mouthwash, bone grafting materials, functional tooth pastes (whitening tooth pastes and remineralization tooth pastes), desensitizers, root canal filling materials, composite resin filling materials, adhesives, wound dressing additives and the like. Similarly, when the medical bioactive glass is used as a bone grafting material, the degradation rate of the glass can be regulated and controlled by adjusting the NC value of the chlorine-containing bioactive glass, and the problem that the degradation rate of the current bone grafting material is not matched with the osteogenesis rate is solved.
4. The function-regulating metal oxides of the components of the invention, for example, those incorporating metal elements such as copper, zinc, iron, cobalt and manganese, are present in bioactive glass systemsSufficient SiO2When used for forming a glass network skeleton structure, the glass has NC regulating function, functions as a network modifier similar to alkali metal and alkaline earth metal oxides, is used for regulating the NC value of a system, has a treatment function, and additionally has antibacterial, anti-inflammatory and antitumor effects on bioactive glass.
5. The preparation method adopts a high-temperature melting and cold quenching preparation process, and the method can be used for large-scale and batch production of bioactive glass.
Drawings
These and/or other aspects and advantages of the present invention will become more apparent and more readily appreciated from the following detailed description of the embodiments of the invention, taken in conjunction with the accompanying drawings of which:
FIG. 1 is an X-ray diffraction pattern of a bioactive glass containing different network connectivity;
FIG. 2 is a graph of the concentration of calcium ions released by bioactive glasses containing different network connectivity when soaked in Tris solutions for different periods of time;
FIG. 3 is an X-ray diffraction pattern of solid powder collected after soaking bioactive glass with network connectivity of 3.35 in Tris solution for various times;
FIG. 4 is the solid powder collected after soaking bioactive glass with network connectivity of 3.27 in Tris solution for different time31P solid-state nuclear magnetic resonance wave spectrum diagram;
FIG. 5 is the solid powder collected after soaking bioactive glass with network connectivity of 1.5 in Tris solution for different time31P solid-state nuclear magnetic resonance wave spectrum diagram;
FIG. 6 is a Micro-CT image of bone tissue 4 weeks after implantation of bioactive glass as bone graft material in example 1 into skull defect of rat (BG is defect of implanted bioactive glass, C is blank control group);
FIG. 7 is a scanning electron micrograph of a bioactive glass which can be used as a mouthwash additive in example 2 after 24 hours of coculture with Streptococcus, wherein FIG. (a) shows a medium group without the bioactive glass and FIG. (b) shows a medium group with the bioactive glass;
FIG. 8 is an electron micrograph of a scanning seedling of a bioactive glass which can be used as a dental protective paint in example 3 after being soaked in artificial saliva for 24 hours.
Detailed Description
The present invention is described in further detail below by way of examples, which should not be construed as limiting the invention thereto.
Example 1:
the medical bioactive glass is bioactive glass ceramic with bioactive glass matrix containing small amount of crystal phase and is prepared with SiO2、P2O5、CaF2、K2O、CaO，MnO2、CaCl2Prepared by high-temperature melting and cold quenching (melt-quenching), wherein P is2O5The content of (B) is 5.0 mol%; CaF2The content of (1) is 3.0mol percent, CaCl2The content of (B) is 14.0 mol%; MnO2The content of (B) is 5.0 mol%; in addition, the content of the composition components of the bioactive glass satisfies the following conditions: NC is 2.5;
the medical bioactive glass is prepared by high-temperature melting and cold quenching (melt-quenching), and comprises the following specific steps:
1) weighing the raw materials according to the weight ratio of the formula design, uniformly mixing, placing in a platinum crucible, carrying out melting treatment at 1580 ℃ for 1h, and placing the obtained uniform mixture in cold water for quenching;
2) the material obtained in the step is placed in an oven for drying at 60 ℃ for 24 hours, and then medical bioactive glass with the particle size of 100-1000um is obtained by grinding.
The medical bioactive glass prepared by the method is used as bioactive glass of bone grafting materials.
Example 2:
the medical bioactive glass is amorphous phase bioactive glass and is made of SiO2、P2O5、CaO、CaCl2CuO is prepared by a melt-quenching (melt-quench) process at high temperature, wherein P is2O5The content of (1) is 3.0mol percent, CaCl2Is 56.0 mol%, the content of CuO is 1 mol%, and the composition of the bioactive glassThe content of the components meets the following requirements: NC is 1.6;
the medical bioactive glass is prepared by high-temperature melting and cold quenching (melt-quenching), and comprises the following specific steps:
1) weighing the raw materials according to the weight ratio of the formula design, uniformly mixing, placing in a platinum crucible, carrying out melting treatment for 1h at 1250 ℃, and placing the obtained uniform mixture in cold water for quenching;
2) and (3) placing the material obtained in the step (A) in an oven at 80 ℃ for 5 hours, and then grinding to obtain the medical bioactive glass with the particle size of less than 38 um.
The medical bioactive glass prepared by the method can be used as bioactive glass with an antibacterial mouth wash additive.
Example 3:
the bioactive glass ceramic containing small amount of crystal phase in bioactive glass matrix is prepared from SiO2、P2O5、SrO、ZnO、CaO、SrCl2、SrF2Prepared by a melt-quenching method (melt-quenching), wherein P is2O5Is 4.0 mol%, SrF2Is 1.0 mol%, SrCl2Is 0.5 mol%, and the content of ZnO is 0.1 mol%, and in addition, the content of the components of the bioactive glass satisfies the following conditions: NC is 1.8;
the medical bioactive glass is prepared by high-temperature melting and cold quenching (melt-quenching), and comprises the following specific steps:
1) weighing the raw materials according to the weight ratio of the formula design, uniformly mixing, placing in a platinum crucible, carrying out melting treatment at 1450 ℃ for 1h, and placing the obtained uniform mixture in cold water for quenching;
2) and (3) drying the material obtained in the step in an oven at 70 ℃ for 10 hours, and then grinding to obtain the medical bioactive glass with the particle size of less than 38 um. The bioactive glass for medical use as an additive for a dental protective paint prepared as described above.
Example 4:
the medical bioactive glass is a bioactive glass baseThe bioactive glass ceramic containing small amount of crystal phase is SiO2、P2O5、SnO、MgO、CaO、LaF2、CaCl2、LaCl3Prepared by a melt-quenching method (melt-quenching), wherein P is2O5Is 1.0 mol%, LaF3Is 1.0 mol% of CaCl2、LaCl3Is 3.0 mol%, and in addition, the content of the components of the bioactive glass satisfies the following conditions: NC is 2.7;
the medical bioactive glass is prepared by high-temperature melting and cold quenching (melt-quenching), and comprises the following specific steps:
1) weighing the raw materials according to the weight ratio of the formula design, uniformly mixing, placing in a platinum crucible, carrying out melting treatment at 1580 ℃ for 1h, and placing the obtained uniform mixture in cold water for quenching;
2) and (3) drying the material obtained in the step in an oven at 65 ℃ for 20 hours, and then grinding to obtain the medical bioactive glass with the particle size of less than 38 um.
The medical bioactive glass prepared by the method is used as a composite resin filling material.
Example 5:
the medical bioactive glass is bioactive glass ceramic with bioactive glass matrix containing small amount of crystal phase and is prepared with SiO2、P2O5、K2O、Fe2O3、MgO、CaO、KCl、ZnCl2、BaCl2Prepared by high-temperature melting and cold quenching (melt-quenching), wherein P is2O5Is 8.0 mol%, Fe2O3The content of (B) is 3.0 mol%; KCl, ZnCl2And BaCl2Is 12.0 mol%, and the ratio between them is 1:1:1, and in addition, the content of the composition components of the bioactive glass satisfies: NC is 3.35;
the medical bioactive glass is prepared by high-temperature melting and cold quenching (melt-quenching), and comprises the following specific steps:
1) weighing the raw materials according to the weight ratio of the formula design, uniformly mixing, placing in a platinum crucible, carrying out melting treatment for 1h at 1620 ℃, and placing the obtained uniform mixture in cold water for quenching;
2) the material obtained in the step is placed in an oven for drying at 70 ℃ for 12 hours, and then medical bioactive glass with the particle size of 100-1000um is obtained by grinding.
The medical bioactive glass prepared by the method can be used as a bone grafting material with anti-tumor potential.
Example 6:
the medical bioactive glass is amorphous phase bioactive glass and is made of SiO2、P2O5、CaO，SrCl2CeO, CuO and CoO are prepared by a melt-quenching method (melt-quench), wherein P is2O5Is 5.0 mol%, SrCl2Is 25.0 mol%, the total content of CeO, CuO and CoO is 20 mo%, and the ratio of the CeO, the CuO and the CoO is 1:1:2, and in addition, the content of the components of the bioactive glass satisfies the following conditions: NC is 2.1;
the medical bioactive glass is prepared by high-temperature melting and cold quenching (melt-quenching), and comprises the following specific steps:
1) weighing the raw materials according to the weight ratio of the formula design, uniformly mixing, placing in a platinum crucible, carrying out melting treatment at 1380 ℃ for 1h, and placing the obtained uniform mixture in cold water for quenching;
2) and (3) drying the material obtained in the step in an oven at 75 ℃ for 12 hours, and then grinding to obtain the medical bioactive glass with the particle size of less than 38 um.
The bioactive glass of the medical wound auxiliary material additive prepared by the method is used for treating wounds.
Example 7:
the medical bioactive glass is amorphous phase bioactive glass and is made of SiO2、P2O5、CaO，MgF2、CaCl2SrO is prepared by a melt-quenching (melt-quenching) method at high temperature, wherein P is2O5Content of (2) is 4.5 mol%, MgF20.5 mol% of CaCl2In an amount of 30.0 mol%, and further, the microorganismThe content of the composition components of the active glass meets the following requirements: NC is 1.5;
the medical bioactive glass is prepared by high-temperature melting and cold quenching (melt-quenching), and comprises the following specific steps:
1) weighing the raw materials according to the weight ratio of the formula design, uniformly mixing, placing in a platinum crucible, carrying out melting treatment for 1h at 1410 ℃, and placing the obtained uniform mixture in cold water for quenching;
2) and (3) drying the material obtained in the step in an oven at 80 ℃ for 10 hours, and then grinding to obtain the medical bioactive glass with the particle size of less than 38 um.
The bioactive glass prepared by the method is used as a desensitizer additive.
Experimental example:
FIG. 1 is an X-ray diffraction pattern of a bioactive glass containing different network connectivity.
All glass glasses as shown in fig. 1 contain an amorphous glass phase, wherein hydroxyapatite is contained in the glass with NC less than 2.57; the bioactive glass with NC value more than 3.18 contains a small amount of SiO except for a glass phase2A crystalline phase.
FIG. 2 is a schematic diagram showing the concentration of calcium ions released by bioactive glass containing different network connectivity when soaked in Tris solution for different time periods.
As shown in figure 2, the chlorine-containing bioactive glass with NC being more than or equal to 1.5 and less than or equal to 3.35 can be degraded after being soaked in the Tris solution for 1 hour, which indicates that the chlorine-containing bioactive glass has high bioactivity as well even if the NC value is more than 2.4; meanwhile, the release amount of calcium ions of the glass with the NC value larger than 2.57 is smaller than that of the glass with the NC value smaller than or equal to 2.57, which indicates that the degradation rate of the glass can be adjusted by regulating and controlling the NC value of the chlorine-containing bioactive glass on the premise of ensuring that the glass has bioactivity.
FIG. 3 is an X-ray diffraction pattern of solid powder collected after soaking bioactive glass with network connectivity of 3.35 in Tris solution for various times.
As shown in fig. 3, after the bioactive glass with NC value of 1.5 is soaked in Tris solution for one hour, the strength of the amorphous glass signal (25-32 ° (2 θ)) in the XRD pattern is reduced, and the signal (20-25 ° (2 θ)) of the silica gel layer is enhanced, indicating that rapid degradation occurs in the glass, and the silica gel layer is generated; with the prolonging of the soaking time, the signal intensity of the amorphous glass is gradually weakened, the signal peak intensity matched with the hydroxyapatite is gradually enhanced, and no obvious change is caused after 9 hours; these suggest that the glass-ceramic has a high bioactivity, degradation of the glass is visible after 1 hour of soaking, significant apatite formation is visible after 6 hours, and almost all phosphate released from the glass is consumed for hydroxyapatite formation at 9 hours.
FIG. 4 is the solid powder collected after soaking bioactive glass with network connectivity of 3.27 in Tris solution for different time31P solid state nmr boph.
As shown in FIG. 4, the bioactive glass having an NC value of 3.27 before and after soaking in Tris solution31The P solid-state nuclear magnetic resonance wave spectrum is a single peak. Non-soaked bioactive glass (0h)31The chemical shift of P is around 2.5ppm, suggesting that in the original glass, P is in the form of orthophosphate radical and is formed by CaCl+Balancing valence electrons. After soaking in Tris solution, of bioactive glass31The chemical shift of P is shifted to 3.0ppm and from 3h to 24h,31the half-peak width of the P signal peak gradually decreased, these suggest that after soaking, P is in the form of orthophosphate and is mainly composed of Ca2+The equilibrium electrons quickly generate hydroxyapatite, and the generated hydroxyapatite amount is gradually increased from 3h to 24 h. Therefore, the bioactivity of the chlorine-containing bioactive glass can break through the limit that the bioactive glass has almost no bioactivity when the NC value is more than 2.4, and still has good bioactivity when the NC value is 3.27.
FIG. 5 is the solid powder collected after soaking bioactive glass with network connectivity of 1.5 in Tris solution for different time31P solid state nmr boph.
As shown in FIG. 4, the bioactive glass having an NC value of 1.5 before and after soaking in Tris solution31The P solid-state nuclear magnetic resonance wave spectrum is a single peak. Non-soaked bioactive glass (0h)31The chemical shift of P is around 2.6ppm, suggesting that in the original glass, P is in the form of orthophosphate radical and is formed by CaCl+Balancing valence electrons. After soaking in Tris solution, of bioactive glass31The chemical shift of P is shifted to 3.0ppm and from 3h to 9h,31the half-peak width of the P signal peak gradually decreases from 9h to 24h,31the half-width of the P signal peak is almost unchanged. These suggest that the bioactive glass with NC value of 1.5 can rapidly generate hydroxyapatite after being soaked in Tris for 3 hours, the generated hydroxyapatite amount is gradually increased from 3 hours to 9 hours, and the generated hydroxyapatite amount is almost unchanged after 9 hours. Therefore, the bioactive glass with the NC value of 1.5 has good bioactivity.
FIG. 6 is a Micro-CT image of bone tissue 4 weeks after implantation of bioactive glass as a bone graft material in example 1 into a skull defect of a rat (BG is a defect into which bioactive glass is implanted, C is a blank control group).
FIG. 6: (a) Micro-CT positive images of bone tissues 4 weeks after implanting the bioactive glass BG as the bone grafting material in rats in the skull defect of the rat in example 1, and (b) is a sectional view; as shown in fig. 6, the BG-implanted bone defect region had a large amount of new bone formation, and the newly formed bone tissue penetrated almost the entire defect region, while only a small amount of new bone formation was observed in the control group. Therefore, the bioactive glass has good osteogenesis effect, can be used as a bone grafting material, and is used for clinical bone defect repair.
FIG. 7 is a scanning electron micrograph of a bioactive glass which can be used as a mouthwash additive in example 2 after 24 hours of cocultivation with Streptococcus, wherein FIG. (a) shows a medium group containing no bioactive glass, and FIG. (b) shows a medium group containing bioactive glass.
As shown in FIG. 7, the culture medium containing bioactive glass can significantly destroy the structure and activity of Streptococcus, and thus inhibit or kill bacteria, compared with the culture medium group without bioactive glass. Therefore, the bioactive glass provided by the invention has good antibacterial effect and can be used as an additive of mouthwash or root canal sealant.
FIG. 8 is a scanning electron micrograph of a bioactive glass which can be used as a dental protective paint in example 3 after being soaked in artificial saliva for 24 hours.
As shown in figure 8, the bioactive glass designed by the invention can be rapidly degraded in saliva to release fluoride ions, and generates fluorapatite needle crystals which have good acid resistance, and the released fluoride ions also have the effects of inhibiting demineralization and promoting remineralization.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the inventive concept of the present invention, which falls into the protection scope of the present invention.
Claims (10)
1. A medical bioactive glass is characterized in that: comprises the following raw material components:
SiO2、P2O5metal chloride or crystalline hydrate thereof, network modifier;
the network modifier comprises an alkali metal oxide or/and an alkaline earth metal oxide;
the network connectivity NC of the medical bioactive glass is 1.5-3.35;
the calculation formula of NC is:
in the formula:
is SiO in medical bioactive glass2The molar percentage of (A); mMOIs the mol percentage content of the alkaline earth metal oxide in the medical bioactive glass;
is the mol percentage content of alkali metal oxide in the medical bioactive glass;
is P in medical bioactive glass2O5In percentage by mole.
2. The medical bioactive glass of claim 1, wherein:
also comprises a function adjusting metal oxide which is CuO, ZnO and Fe2O3、SnO、CeO2CoO and MnO2When mixed, in any proportion.
3. The medical bioactive glass of claim 1, wherein:
also comprises fluoride which is CaF2、SrF2、MgF2And LaF3When mixed, in any proportion.
4. The medical bioactive glass of claim 1, wherein:
the chloride is CaCl2、SrCl2、BaCl2、ZnCl2、LaCl3And KCl, when mixed, in any proportion;
the alkali metal oxide is K2O; the alkaline earth metal oxide is one or more of MgO, CaO, BaO, and SrO, in any proportion when mixed.
5. The medical bioactive glass of claim 2, wherein:
also comprises fluoride which is CaF2、SrF2、MgF2And LaF3When mixed, in any proportion.
6. The medical bioactive glass of claim 5, wherein: the molar contents of the raw material components are as follows:
SiO220-60mol％；
P2O53-8mol％；
0.5-56 mol% of metal chloride or crystalline hydrate thereof;
20-60 mol% of the network modifying body;
0.1-20 mol% of functional regulating metal oxide;
0.1-9 mol% of fluoride.
7. The medical bioactive glass of claim 6, wherein: the medical bioactive glass has amorphous bioactive glass or bioactive glass ceramic with bioactive glass matrix containing crystalline phase.
8. The process for preparing a bioactive glass for medical use according to any of claims 1 to 7, wherein: the method comprises the following steps:
1) weighing the raw materials according to the weight ratio designed by the formula, uniformly mixing, placing in a platinum crucible, carrying out melting treatment at 1250-;
2) and (3) drying the material obtained in the step (A) in an oven, and then grinding to obtain the medical bioactive glass.
9. The method for preparing the medical bioactive glass according to claim 6, wherein the method comprises the following steps: the cold water in the step 1) is water with the temperature of 0-30 ℃;
the drying temperature of the step 2) is 60-80 ℃, and the time is 5-24 hours.
10. The medical bioactive glass of any of claims 1-7, for use in medicine, wherein: used as raw material components of the following medical products: tooth protection paint, mouthwash, bone grafting materials, functional tooth pastes, dental desensitizers, root canal filling materials, composite resin filling materials, adhesives and wound dressings; the functional tooth paste comprises a whitening tooth paste and a remineralization tooth paste.
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| WO2023051559A1 (en) * | 2021-09-28 | 2023-04-06 | 中南大学 | Medical bioactive glass, preparation method therefor, and application thereof |
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| CN1480419A (en) * | 2002-07-15 | 2004-03-10 | 宾得株式会社 | CaO-SiO2-base bioactive glass and sintered calcium orthophosphate glass using such raw material |
| FR2860786A1 (en) * | 2003-10-14 | 2005-04-15 | Pentax Corp | BIOACTIVE GLASS BASED ON CAO-MGO-SIO AND CALCIUM PHOSPHATE GLASS USING THE SAME |
| WO2008015117A2 (en) * | 2006-08-01 | 2008-02-07 | Unilever Plc | Biomaterials, their preparation and use |
| CN101500622A (en) * | 2006-06-16 | 2009-08-05 | 帝国创新有限公司 | Bioactive glass |
| US20160051457A1 (en) * | 2013-03-28 | 2016-02-25 | Queen Mary And Westfield College University Of London | Chlorine-containing silicate glasses and glass ceramics |
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| DE69820863T2 (en) * | 1997-04-03 | 2004-12-09 | Corning Inc. | CLEAR APATIT GLASS CERAMICS |
| PT105617A (en) * | 2011-04-05 | 2012-10-08 | Univ Aveiro | COMPOSITION OF BIOACTIVE GLASS, ITS USE AND RESPECTIVE METHOD OF OBTAINING |
| CN113666632A (en) * | 2021-09-28 | 2021-11-19 | 中南大学 | Medical bioactive glass and preparation method and application thereof |
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- 2021-09-28 CN CN202111144492.8A patent/CN113666632A/en active Pending
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| CN1480419A (en) * | 2002-07-15 | 2004-03-10 | 宾得株式会社 | CaO-SiO2-base bioactive glass and sintered calcium orthophosphate glass using such raw material |
| FR2860786A1 (en) * | 2003-10-14 | 2005-04-15 | Pentax Corp | BIOACTIVE GLASS BASED ON CAO-MGO-SIO AND CALCIUM PHOSPHATE GLASS USING THE SAME |
| CN101500622A (en) * | 2006-06-16 | 2009-08-05 | 帝国创新有限公司 | Bioactive glass |
| CN104876439A (en) * | 2006-06-16 | 2015-09-02 | 帝国创新有限公司 | Bioactive glass |
| WO2008015117A2 (en) * | 2006-08-01 | 2008-02-07 | Unilever Plc | Biomaterials, their preparation and use |
| US20160051457A1 (en) * | 2013-03-28 | 2016-02-25 | Queen Mary And Westfield College University Of London | Chlorine-containing silicate glasses and glass ceramics |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2023051559A1 (en) * | 2021-09-28 | 2023-04-06 | 中南大学 | Medical bioactive glass, preparation method therefor, and application thereof |
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| WO2023051559A1 (en) | 2023-04-06 |
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