CN111978559B - High-strength self-solidifying composite bone implant with MOF structure and its preparation - Google Patents
High-strength self-solidifying composite bone implant with MOF structure and its preparation Download PDFInfo
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- CN111978559B CN111978559B CN202010931965.8A CN202010931965A CN111978559B CN 111978559 B CN111978559 B CN 111978559B CN 202010931965 A CN202010931965 A CN 202010931965A CN 111978559 B CN111978559 B CN 111978559B
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- bone implant
- composite bone
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- 210000000988 bone and bone Anatomy 0.000 title claims abstract description 64
- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 239000007943 implant Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 48
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- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 6
- 238000000498 ball milling Methods 0.000 claims description 50
- 150000001875 compounds Chemical class 0.000 claims description 47
- 239000000243 solution Substances 0.000 claims description 35
- 150000001491 aromatic compounds Chemical class 0.000 claims description 23
- 238000000465 moulding Methods 0.000 claims description 23
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 19
- 229910021534 tricalcium silicate Inorganic materials 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 16
- BCAARMUWIRURQS-UHFFFAOYSA-N dicalcium;oxocalcium;silicate Chemical compound [Ca+2].[Ca+2].[Ca]=O.[O-][Si]([O-])([O-])[O-] BCAARMUWIRURQS-UHFFFAOYSA-N 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- 235000019976 tricalcium silicate Nutrition 0.000 claims description 16
- JOPDZQBPOWAEHC-UHFFFAOYSA-H tristrontium;diphosphate Chemical compound [Sr+2].[Sr+2].[Sr+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JOPDZQBPOWAEHC-UHFFFAOYSA-H 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
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- 229910052918 calcium silicate Inorganic materials 0.000 claims description 10
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 claims description 10
- 235000012241 calcium silicate Nutrition 0.000 claims description 10
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- 239000001506 calcium phosphate Substances 0.000 claims description 7
- 238000005345 coagulation Methods 0.000 claims description 7
- 230000015271 coagulation Effects 0.000 claims description 7
- FNAQSUUGMSOBHW-UHFFFAOYSA-H calcium citrate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FNAQSUUGMSOBHW-UHFFFAOYSA-H 0.000 claims description 6
- 239000001354 calcium citrate Substances 0.000 claims description 6
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 claims description 6
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 6
- 235000011010 calcium phosphates Nutrition 0.000 claims description 6
- 235000019700 dicalcium phosphate Nutrition 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- 229910000386 magnesium trisilicate Inorganic materials 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 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 claims description 6
- 235000013337 tricalcium citrate Nutrition 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 5
- 239000000920 calcium hydroxide Substances 0.000 claims description 5
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- GXGAKHNRMVGRPK-UHFFFAOYSA-N dimagnesium;dioxido-bis[[oxido(oxo)silyl]oxy]silane Chemical compound [Mg+2].[Mg+2].[O-][Si](=O)O[Si]([O-])([O-])O[Si]([O-])=O GXGAKHNRMVGRPK-UHFFFAOYSA-N 0.000 claims description 5
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- 229940099273 magnesium trisilicate Drugs 0.000 claims description 5
- 235000019793 magnesium trisilicate Nutrition 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
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- 235000011132 calcium sulphate Nutrition 0.000 claims description 4
- 150000001860 citric acid derivatives Chemical class 0.000 claims description 4
- 229940093181 glucose injection Drugs 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 229910001463 metal phosphate Inorganic materials 0.000 claims description 4
- 229910052914 metal silicate Inorganic materials 0.000 claims description 4
- 239000002504 physiological saline solution Substances 0.000 claims description 4
- 239000008215 water for injection Substances 0.000 claims description 4
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- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- 239000011573 trace mineral Substances 0.000 claims description 2
- 235000013619 trace mineral Nutrition 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 claims 1
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- 150000002736 metal compounds Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 11
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 4
- 239000011574 phosphorus Substances 0.000 abstract description 4
- 150000003839 salts Chemical class 0.000 abstract description 3
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- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 11
- 238000007873 sieving Methods 0.000 description 11
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 description 6
- 229910000018 strontium carbonate Inorganic materials 0.000 description 6
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 5
- 230000024245 cell differentiation Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 4
- CABMTIJINOIHOD-UHFFFAOYSA-N 2-[4-methyl-5-oxo-4-(propan-2-yl)-4,5-dihydro-1H-imidazol-2-yl]quinoline-3-carboxylic acid Chemical compound N1C(=O)C(C(C)C)(C)N=C1C1=NC2=CC=CC=C2C=C1C(O)=O CABMTIJINOIHOD-UHFFFAOYSA-N 0.000 description 4
- WJJMNDUMQPNECX-UHFFFAOYSA-N Dipicolinic acid Natural products OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 description 4
- MPFLRYZEEAQMLQ-UHFFFAOYSA-N dinicotinic acid Chemical compound OC(=O)C1=CN=CC(C(O)=O)=C1 MPFLRYZEEAQMLQ-UHFFFAOYSA-N 0.000 description 4
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 4
- 238000007711 solidification Methods 0.000 description 4
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- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 description 3
- ONIOAEVPMYCHKX-UHFFFAOYSA-N carbonic acid;zinc Chemical compound [Zn].OC(O)=O ONIOAEVPMYCHKX-UHFFFAOYSA-N 0.000 description 3
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- 239000011667 zinc carbonate Substances 0.000 description 3
- 229910000010 zinc carbonate Inorganic materials 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
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- 229910021645 metal ion Inorganic materials 0.000 description 2
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- 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 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
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- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
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- 238000001035 drying Methods 0.000 description 1
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- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 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
- 239000007769 metal material Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/18—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/56—Porous materials, e.g. foams or sponges
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
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- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Transplantation (AREA)
- Epidemiology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Animal Behavior & Ethology (AREA)
- Dermatology (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Dispersion Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Materials For Medical Uses (AREA)
- Prostheses (AREA)
Abstract
本发明属于骨修复材料领域，具体涉及具有MOF结构的高强度自凝固复合骨植入体及其制备方法。本发明提供一种高强度自凝固复合骨植入体，所述复合骨植入体的骨架结构如式I所示。本发明根据MOF概念，设计出具有MOF骨架与多种金属盐类组成从而形成具有MOF结构的高强度自凝固复合骨植入体；所得具有MOF结构的高强度自凝固复合骨植入体初凝时间为5～60分钟；24小时其抗压强度为80～160MPa；在SBF中一周强度保持90％，失重1～5wt％；属于稳定型高强度自凝固骨修复材料；并且富含钙磷等成骨元素，具有优异的表面成骨活性，可以用于承重骨的修复、重建和替代就。 The invention belongs to the field of bone repair materials, in particular to a high-strength self-solidifying composite bone implant with MOF structure and a preparation method thereof. The present invention provides a high-strength self-solidifying composite bone implant, and the skeleton structure of the composite bone implant is shown in formula I. According to the concept of MOF, the present invention designs a high-strength self-solidifying composite bone implant with MOF structure composed of MOF skeleton and various metal salts; the obtained high-strength self-solidifying composite bone implant with MOF structure is initially coagulated The time is 5-60 minutes; the compressive strength is 80-160MPa in 24 hours; the strength is maintained at 90% for one week in SBF, and the weight loss is 1-5wt%; it is a stable high-strength self-solidifying bone repair material; and rich in calcium and phosphorus, etc. Osteogenic elements, with excellent surface osteogenic activity, can be used for the repair, reconstruction and replacement of load-bearing bones.
Description
Technical Field
The invention belongs to the field of bone repair materials, and particularly relates to a high-strength self-solidifying composite bone implant with an MOF structure and a preparation method thereof.
Background
Bones are the support system of the human body, and bear the core system of the weight, movement and activities of the human body. Main bone body injuries of load-bearing bones caused by various factors need to be repaired and replaced in time to maintain the normal supporting function of the load-bearing bones. At present, more than 8000 ten thousand patients with various severe arthritis in China exist, about 75 ten thousand patients with limb disabilities exist, and about 300 ten thousand patients with newly increased bone injury are simultaneously added every year. With the accelerated aging process in China, the number of patients suffering from orthopedic diseases in China will increase rapidly, thereby driving the accelerated expansion of the market of orthopedic medical instruments.
The biology and mechanics is one of the determining factors for the function of bone repair materials and repaired tissues. The traditional ceramic materials and metal materials are far different from bone tissue in mechanical strength, hardness, rigidity and elastic modulus, so that stress shielding is often caused, and the problems of loosening of repair materials, abrasion and necrosis of bone tissues, separation and the like often occur.
The metal-organic framework Materials (MOFs) are coordination polymers which develop rapidly in the last decade, have three-dimensional pore structures, generally take metal ions as connecting points, and organic ligands support and form space 3D extension, are another important novel porous material besides zeolite and carbon nanotubes, and are widely applied to catalysis, energy storage and separation. Currently, MOFs have become an important research direction for many chemical branches of inorganic chemistry, organic chemistry, and the like. Scientists such as kitagawa, Yaghi, etc. are well known in this regard.
Metal-organic frameworks (Metal-organic frameworks) refer to crystalline porous materials with periodic network structures formed by self-assembly of transition Metal ions and organic ligands. The method has the advantages of high porosity, low density, large specific surface area, regular pore channels, adjustable pore diameter, diversity and tailorability of topological structures and the like. Mainly comprises two important components, namely nodes (connectors) and connecting bridges (linkers); that is, the MOFs are framework structures composed of organic ligands (connecting bridges) with different numbers of connections and metal ion junctions.
There have been no reports in the prior art relating to high strength self-setting composite bone implants having MOF structures.
Disclosure of Invention
Aiming at the defects, the invention provides the high-strength self-solidification composite bone implant with the MOF structure and the preparation method thereof, the strength of the obtained bone implant exceeds a great amount of heat-release and inert organic glass bone cement PMMA implant materials in the polymerization process, can reach 150MPa, is rich in osteogenic elements such as calcium, phosphorus and the like, has excellent surface osteogenic activity, can be used for repairing, reconstructing and replacing bearing bones, belongs to stable high-strength self-solidification bone repair materials, and has wide application prospect in repairing, reconstructing and replacing various bearing bones.
The technical scheme of the invention is as follows:
the invention aims to solve the first technical problem of providing a high-strength self-solidifying composite bone implant, wherein the skeleton structure of the composite bone implant is shown as a formula I:
wherein said AR ═ is
At least one of; and M is a metal element.
Further, the high strength self-solidifying composite bone implant has a metal-organic framework, or MOF, structure.
Further, M is an alkali metal or transition metal element with a valence state of two or more, preferably an osteogenic metal element and a human body trace element, such as calcium, zinc, magnesium, iron, strontium, yttrium, copper, manganese, and the like; the metal is the point of attachment to the MOF structural framework.
Further, the high-strength self-solidifying composite bone implant is prepared by reacting a carboxyl-containing aromatic compound and a metal-containing compound (MX) under the action of a solidifying liquid, wherein the mass ratio of the carboxyl-containing aromatic compound to the metal-containing compound is as follows: 10-60: 90-40, wherein the solid-to-liquid ratio is 1: 0.3-1.2 g/ml; the aromatic compound containing carboxyl is a bi-or tri-carboxyl aromatic compound.
Further, the high-strength self-setting composite bone implant is prepared by the following method: firstly, uniformly mixing a carboxyl-containing aromatic compound and a metal-containing compound in a ball milling mode to obtain a compound; then adding the solidification liquid into the compound, and uniformly stirring; finally, the high-strength self-solidifying composite bone implant with the MOF structure is obtained through processing and forming.
Further, the ball milling speed is 100-200 r/min (preferably 120-150 r/min), and the ball milling time is 2-12 hours (preferably 4-8 hours).
Further, the carboxyl group-containing aromatic compound is selected from at least one of the following compounds: terephthalic acid, isophthalic acid, trimesic acid, 4' -biphenyldicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, 1, 4-naphthalenedicarboxylic acid, 2, 6-pyridinedicarboxylic acid, 3, 5-pyridinedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid or 2, 5-furandicarboxylic acid.
Further, the metal-containing compound (MX) is selected from at least two of the following: metal oxides, metal carbonates, metal sulfates, metal phosphates, metal silicates, metal citrates or alkali metals.
Still further, the metal-containing compound is selected from at least two of the following: MgO, CaO, SrO, ZnO, ZrO, MgCO3、CaCO3 SrCO3 ZnCO3 SrCO3、ZrCO3Tricalcium silicate (Ca3SiO5, C3S), dicalcium silicate (2CaO · SiO2, C2S), calcium hydroxide, calcium citrate, calcium phosphate, calcium hydrogen phosphate, calcium sulfate, strontium phosphate or magnesium trisilicate.
Further, the coagulation liquid is at least one of water for injection, physiological saline or glucose injection.
The second technical problem to be solved by the present invention is to provide a method for preparing the above high-strength self-setting composite bone implant, the method comprising: prepared by reacting a carboxyl-containing aromatic compound with a metal-containing compound (MX) under the action of a coagulating liquid, wherein the mass ratio of the carboxyl-containing aromatic compound to the metal-containing compound is as follows: 10-60: 90-40, wherein the solid-to-liquid ratio is 1: 0.3-1.2 g/ml; the aromatic compound containing carboxyl is a bi-or tri-carboxyl aromatic compound.
Further, the preparation method of the high-strength self-solidifying composite bone implant comprises the following steps: firstly, uniformly mixing a carboxyl-containing aromatic compound and a metal-containing compound in a ball milling mode to obtain a compound; then adding the solidification liquid into the compound, and uniformly stirring; finally, the high-strength self-solidifying composite bone implant with the MOF structure is obtained through processing and forming.
Further, in the method, the ball milling speed is 100-200 rpm (preferably 120-150 rpm), and the ball milling time is 2-12 hours (preferably 4-8 hours).
Further, in the above method, the carboxyl group-containing aromatic compound is at least one selected from the group consisting of: terephthalic acid, isophthalic acid, trimesic acid, 4' -biphenyldicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, 1, 4-naphthalenedicarboxylic acid, 2, 6-pyridinedicarboxylic acid, 3, 5-pyridinedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid or 2, 5-furandicarboxylic acid.
Further, in the above method, the metal-containing compound (MX) is selected from at least two of the following: metal oxides, metal carbonates, metal sulfates, metal phosphates, metal silicates, metal citrates or alkali metals.
Still further, in the above method, the metal-containing compound is selected from at least two of: MgO, CaO, SrO, ZnO, ZrO, MgCO3、CaCO3 SrCO3 ZnCO3 SrCO3、ZrCO3Tricalcium silicate (Ca)3SiO5，C3S), dicalcium silicate (2 CaO. SiO)2，C2S), calcium hydroxide, calcium citrate, calcium phosphate, calcium hydrogen phosphate, calcium sulfate, strontium phosphate or magnesium trisilicate.
In the above method, the coagulation solution is at least one of water for injection, physiological saline, and a glucose injection solution.
Further, in the above method, the method of forming includes: injection molding, abrasive molding or 3D printing molding to form the desired shape.
Further, in the method, in the processes of stirring, uniformly mixing and processing and forming, the temperature is not more than 40 ℃ (no burn or damage is caused to biological tissues), and the pH is 6.0-8.0, so that the bone tissue repair and reconstruction are facilitated.
The invention has the beneficial effects that:
according to the MOF concept, the invention designs a high-strength self-solidifying composite bone implant which is composed of an MOF framework and a plurality of metal salts so as to form an MOF structure; the initial setting time of the obtained high-strength self-setting composite bone implant with the MOF structure is 5-60 minutes; the compressive strength is 80-160 MPa after 24 hours; keeping the strength for one week in the SBF for 90 percent, and losing weight for 1-5 percent; belongs to a stable high-strength self-solidifying bone repairing material; the bone-forming powder is rich in bone-forming elements such as calcium, phosphorus and the like, has excellent surface bone-forming activity, and can be used for repairing, reconstructing and replacing load-bearing bones; in addition, the invention has fast forming time.
Detailed Description
The invention provides a high-strength self-solidifying composite bone implant, the skeleton structure of which is shown as formula I:
further, the high-strength self-solidifying composite bone implant is prepared by reacting a carboxyl-containing aromatic compound and a metal-containing compound (MX) under the action of a solidifying liquid, wherein the mass ratio of the carboxyl-containing aromatic compound to the metal-containing compound is as follows: 10-60: 90-40, the solid-to-liquid ratio is 1: 0.3-1.2 g/ml (namely the ratio of the solid (the aromatic compound containing carboxyl group + MX) to the coagulating liquid is 1: 0.3-1.2 (g/ml)); the aromatic compound containing carboxyl is a bi-or tri-carboxyl aromatic compound.
The invention designs a high-strength self-solidifying composite bone implant which is composed of an MOF framework and a plurality of metal salts according to an MOF concept so as to form a MOF structure. The strength of the material exceeds that of a large amount of exothermic and inert organic glass bone cement PMMA implant material in the polymerization process, can reach 150MPa, is rich in osteogenic elements such as calcium, phosphorus and the like, has excellent surface osteogenic activity, and can be used for repairing, reconstructing and replacing bearing bones.
In the present invention, the bi-or tri-carboxy aromatic compound is at least one of the following compounds:
terephthalic acid (TPA)
Isophthalic acid
Trimesic acid
4,4' -Biphenyldicarboxylic acid
2, 6-naphthalenedicarboxylic acidFormic acid
1, 4-naphthalenedicarboxylic acid
The reaction mixture of 2, 6-pyridinedicarboxylic acid,
3, 5-Pyridinedicarboxylic acid
1, 4-cyclohexanedicarboxylic acid,
Or 2, 5-furandicarboxylic acid
And the like.
In the present invention, the metal-containing compound MX is selected from at least two of the following: oxides (MgO, CaO, SrO, ZnO, ZrO, etc.), carbonates (MgCO)3、CaCO3 SrCO3 ZnCO3 SrCO3、ZrCO3Etc.), tricalcium silicate (Ca)3SiO5，C3S), dicalcium silicate (2 CaO. SiO)2，C2S), calcium hydroxide [ Ca (OH) ]2]Calcium citrate (C)12H10Ca3O14) Calcium phosphate (Ca)3(PO4)2) Calcium hydrogen phosphate (CaHO)4P), calcium sulfate (CaSO)4.0.5H2O), strontium phosphate (Sr)3(PO4)2) Or magnesium trisilicate Mg2O8Si3And the like.
The reaction of forming the MOF framework structure by the high-strength self-solidifying composite bone implant with the MOF structure is a rapid reaction in the presence of a solidifying liquid, and the general formula is as follows:
specifically, the reaction process is as follows:
the following examples are given to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.
Example 1
16.6g of terephthalic acid, 24.4g of 4,4' -biphenyldicarboxylic acid, 22.8g of tricalcium silicate dried at 120 ℃ and 25.6g of strontium phosphate are mixed and ball-milled, the ball-milling speed is 150r/m, and the mixture is sieved in a 120-mesh sieve after ball-milling for 6 hours; 88g of the complex were obtained.
Weighing 10g of the obtained compound, adding 8ml of water, uniformly stirring, and then placing the slurry body into a polytetrafluoroethylene mold with the diameter of 6mm and the diameter of 12mm for molding; taking out the sample after 10 minutes, and measuring the compressive strength after 2 hours and 24 hours; and testing the degradation speed and the bone cell growth rate. And (3) testing results: 2-hour compressive strength: 20MPa, 24-hour compressive strength: 90 MPa; compressive strength at 72 hours: 120 MPa.
According to the following steps of 1:30 (mass ratio) is put into a shaking table with SBF at 37 ℃, and the shaking speed is 60 times/min, so as to carry out degradation experiments. 0.58% of degradation in the first day, 2.05% of degradation in the first week, 3.52% of degradation in the second week, 3.75% of degradation in the third week and 5.12% of degradation in the fourth week; degradation is 5.15% in the fifth week; degradation is 5.12% in the eighth week; degradation is carried out for 5.02% in the twelfth week; degradation is 5.08% in the sixteenth week; degradation was 5.02% in the twentieth week. The first week pH was 8.05, the second week pH 7.85, the third week pH 7.66, the fourth week pH 7.51, the fifth week pH 7.50, the eighth week pH 7.50.
Soaking for 72 hours at 37 ℃ according to the standard of 0.2g/ml, filtering to obtain extracting solutions, culturing osteoblasts of mice by using the extracting solutions with the original concentration and diluted by 5 times respectively, and observing and analyzing cell morphology and cell growth and differentiation rate for 24 hours, 48 hours and 72 hours; the results of the original concentration and 5-fold dilution of the extract are respectively: 92% and 102%.
Example 2
Mixing 21.1g of trimesic acid, 22.8g of tricalcium silicate dried at 120 ℃ and 25.6g of strontium phosphate, carrying out ball milling at the ball milling speed of 150r/m, and sieving in a 120-mesh sieve after ball milling for 6 hours; 68g of the complex were obtained.
Weighing 10g of the obtained compound, adding 8ml of water, uniformly stirring, and then placing the slurry body into a polytetrafluoroethylene mold with the diameter of 6mm and the diameter of 12mm for molding; taking out the sample after 10 minutes, and measuring the compressive strength after 2 hours and 24 hours; and testing the degradation speed and the bone cell growth rate.
And (3) testing results: 2-hour compressive strength: 28MPa, 24-hour compressive strength: 102 MPa; compressive strength at 72 hours: 135 MPa.
The degradation experiment was carried out by placing the mixture in a shaker at 37 ℃ SBF according to a mass ratio of 1:30 and shaking the mixture at a speed of 60 times/min: 1.15% of degradation in the first day, 2.21% of degradation in the first week, 3.13% of degradation in the second week, 3.85% of degradation in the third week and 4.96% of degradation in the fourth week; degradation is 5.03% in the fifth week; degradation is carried out for 5.01% in the eighth week; degradation is 5.08% in the twelfth week; degradation is 5.03% in the sixteenth week; degradation was 5.05% in the twentieth week. The first week pH was 7.52, the second week pH,7.35, the third week pH was 7.45, the fourth week pH was 7.45, the fifth week pH was 7.45, and the eighth week pH was 7.43.
Soaking for 72 hours at 37 ℃ according to the standard of 0.2g/ml, filtering to obtain extracting solutions, culturing osteoblasts of mice by using the extracting solutions with the original concentration and diluted by 5 times respectively, and observing and analyzing cell morphology and cell growth and differentiation rate for 24 hours, 48 hours and 72 hours; the results of the original concentration and 5-fold dilution of the extract are respectively: 98% and 109%.
Example 3
Mixing 21.1g of trimesic acid, 21.6g of 2, 6-naphthalene dicarboxylic acid, 45.6g of tricalcium silicate dried at 120 ℃ and 20.6g of calcium sulfate hemihydrate, carrying out ball milling at the ball milling speed of 150r/m, and sieving in a 120-mesh sieve after ball milling for 6 hours; 105g of the complex were obtained.
Weighing 10g of the obtained compound, adding 8ml of water, uniformly stirring, and then placing the slurry body into a polytetrafluoroethylene mold with the diameter of 6mm and the diameter of 12mm for molding; taking out the sample after 10 minutes, and measuring the compressive strength after 2 hours and 24 hours; and testing the degradation speed and the bone cell growth rate.
And (3) testing results: 2-hour compressive strength: 22MPa, 24-hour compressive strength: 110 MPa; compressive strength at 72 hours: 150 MPa.
The degradation experiment was carried out by placing the mixture in a shaker at 37 ℃ SBF according to a mass ratio of 1:30 and shaking the mixture at a speed of 60 times/min. 1.61% of degradation in the first day, 2.35% of degradation in the first week, 3.75% of degradation in the second week, 4.32% of degradation in the third week and 5.49% of degradation in the fourth week; degradation is 5.56% in the fifth week; degradation is 5.62% in the eighth week; degradation is 5.35% in the twelfth week; degradation at sixteenth week is 5.18%; degradation was 5.36% in the twentieth week. The first week pH was 7.75, the second week pH was 7.38, the third week pH was 7.43, the fourth week pH was 7.45, the fifth week pH was 7.43, and the eighth week pH was 7.45.
Soaking at 37 deg.C for 72 hr according to 0.2g/ml standard, filtering to obtain extractive solution, culturing mouse osteoblast with the extractive solution at original concentration and diluted 5 times, and observing and analyzing cell morphology for 24 hr, 48 hr and 72 hr. The results of the original concentration and 5-fold dilution of the extract are respectively: 95 percent and 99 percent.
Example 4
Mixing and ball-milling 16.7g of 3, 5-pyridinedicarboxylic acid, 22.8g of tricalcium silicate dried and filtered at 120 ℃, 23.4g of monocalcium phosphate and 12.6g of strontium phosphate, wherein the ball-milling speed is 150r/m, and sieving in a 120-mesh sieve after ball-milling for 6 hours; 75g of the complex were obtained.
Weighing 10g of the obtained compound, adding 8ml of water, uniformly stirring, and then placing the slurry body into a polytetrafluoroethylene mold with the diameter of 6mm and the diameter of 12mm for molding; taking out the sample after 10 minutes, and measuring the compressive strength after 2 hours and 24 hours; and testing the degradation speed and the bone cell growth rate.
And (3) testing results: 2-hour compressive strength: 30MPa, 24-hour compressive strength: 88 MPa; compressive strength at 72 hours: 132 MPa.
The degradation experiment was carried out by placing the mixture in a shaker at 37 ℃ SBF according to a mass ratio of 1:30 and shaking the mixture at a speed of 60 times/min. 0.58% of degradation in the first day, 2.05% of degradation in the first week, 3.52% of degradation in the second week, 3.75% of degradation in the third week and 7.05% of degradation in the fourth week; degradation is 7.02% in the fifth week; degradation is 7.00% in the eighth week; degradation is 7.01% in the twelfth week; degradation is 6.98% in the sixteenth week; degradation 7.02% by twentieth week. The first week pH was 7.52, the second week pH,7.29, the third week pH was 7.46, the fourth week pH was 7.45, the fifth week pH was 7.39, and the eighth week pH was 7.41.
Soaking at 37 deg.C for 72 hr according to 0.2g/ml standard, filtering to obtain extractive solution, culturing mouse osteoblast with the extractive solution at original concentration and diluted 5 times, and observing and analyzing cell morphology for 24 hr, 48 hr and 72 hr. The results of the original concentration and 5-fold dilution of the extract are respectively: 95% and 101%.
Example 5
Taking 16.6g of 2, 5-furandicarboxylic acid, 24.4g of 4,4' -biphenyldicarboxylic acid, 17.2g of dicalcium silicate dried at 120 ℃, 10.0g of magnesium carbonate and 25.6g of strontium phosphate, mixing and carrying out ball milling, wherein the ball milling speed is 150r/m, and sieving in a 120-mesh sieve after ball milling for 6 hours; 90g of the complex were obtained.
Weighing 10g of the obtained compound, adding 8ml of water, uniformly stirring, and then placing the slurry body into a polytetrafluoroethylene mold with the diameter of 6mm and the diameter of 12mm for molding. Taking out the sample after 10 minutes, and measuring the compressive strength after 2 hours and 24 hours; and testing the degradation speed and the bone cell growth rate.
And (3) testing results: 2-hour compressive strength: 15MPa, 24-hour compressive strength: 800 MPa; compressive strength at 72 hours: 110 MPa.
The degradation experiment was carried out by placing the mixture in a shaker at 37 ℃ SBF according to a mass ratio of 1:30 and shaking the mixture at a speed of 60 times/min. 1.52% of degradation in the first day, 2.33% of degradation in the first week, 3.58% of degradation in the second week, 4.66% of degradation in the third week and 5.38% of degradation in the fourth week; degradation is 6.25% in the fifth week; 7.182% degradation in the eighth week; degradation is 7.15% in the twelfth week; degradation is 7.09% in the sixteenth week; degradation was 7.11% in the twentieth week. pH 7.95 for week one, pH 7.55 for week two, pH 7.52 for week three, pH 7.45 for week four, pH 7.46 for week five and pH 7.50 for week eight.
Soaking at 37 deg.C for 72 hr according to 0.2g/ml standard, filtering to obtain extractive solution, culturing mouse osteoblast with the extractive solution at original concentration and diluted 5 times, and observing and analyzing cell morphology for 24 hr, 48 hr and 72 hr. The results of the original concentration and 5-fold dilution of the extract are respectively: 98% and 106%.
Example 6
Taking 15.6g of 2, 5-furandicarboxylic acid, 16.6g of terephthalic acid, 22.8g of tricalcium silicate dried at 120 ℃, 17.2g of dicalcium silicate dried at 120 ℃, 15.0g of calcium sulfate and 25.6g of magnesium phosphate, mixing and carrying out ball milling, wherein the ball milling speed is 150r/m, and sieving in a 120-mesh sieve after ball milling for 6 hours to obtain 110g of the compound.
Weighing 10g of the obtained compound, adding 8ml of water, uniformly stirring, and then placing the slurry body into a polytetrafluoroethylene mold with the diameter of 6mm and the diameter of 12mm for molding; taking out the sample after 10 minutes, and measuring the compressive strength after 2 hours and 24 hours; and testing the degradation speed and the bone cell growth rate.
And (3) testing results: 2-hour compressive strength: 32MPa, 24-hour compressive strength: 95 MPa; compressive strength at 72 hours: the degradation experiment was carried out by placing 128MPa in a shaker of SBF at 37 ℃ in a mass ratio of 1:30 and shaking at a speed of 60 times/min. 1.88 percent of degradation in the first day, 2.75 percent of degradation in the first week, 3.64 percent of degradation in the second week, 4.35 percent of degradation in the third week and 5.05 percent of degradation in the fourth week; degradation is 5.55% in the fifth week; degradation is 6.26% in the eighth week; degradation is 6.65% in the twelfth week; degradation is 6.50% in the sixteenth week; degradation was 6.. 02% in the twentieth week. The first week pH was 7.78, the second week pH,7.65, the third week pH was 7.53, the fourth week pH was 7.45, the fifth week pH was 7.43, and the eighth week pH was 7.43.
Soaking at 37 deg.C for 72 hr according to 0.2g/ml standard, filtering to obtain extractive solution, culturing mouse osteoblast with the extractive solution at original concentration and diluted 5 times, and observing and analyzing cell morphology for 24 hr, 48 hr and 72 hr. The results of the original concentration and 5-fold dilution of the extract are respectively: 91% and 100%.
Example 7
Mixing 16.6g of terephthalic acid, 24.4g of 4,4' -biphenyldicarboxylic acid, 22.8g of tricalcium silicate dried at 120 ℃, 4.1 g of magnesium oxide and 25.6g of strontium phosphate, and carrying out ball milling at the ball milling speed of 150r/m for 6 hours, and sieving in a 120-mesh sieve; 68g of the complex were obtained.
Weighing 10g of the obtained compound, adding 8ml of water, uniformly stirring, and then placing the slurry body into a polytetrafluoroethylene mold with the diameter of 6mm and the diameter of 12mm for molding. Taking out the sample after 10 minutes, and measuring the compressive strength after 2 hours and 24 hours; and testing the degradation speed and the bone cell growth rate.
And (3) testing results: 2-hour compressive strength: 15MPa, 24-hour compressive strength: 85 MPa; compressive strength at 72 hours: 125MPa is put into a shaking table of SBF at 37 ℃ according to the mass ratio of 1:30, and the shaking speed is 60 times/min. Degradation experiments were performed. 0.88 percent of degradation in the first day, 1.97 percent of degradation in the first week, 2.55 percent of degradation in the second week, 3.13 percent of degradation in the third week and 4.06 percent of degradation in the fourth week; 4.91% in the fifth week; degradation is carried out for 5.05% in the eighth week; degradation is carried out for 5.02% in the twelfth week; degradation is 5.02% in the sixteenth week; degradation was 4.99% in the twentieth week. The first week pH was 8.36, the second week pH was 7.66, the third week pH was 7.52, the fourth week pH was 7.45, the fifth week pH was 7.46, and the eighth week pH was 7.50.
Soaking at 37 deg.C for 72 hr according to 0.2g/ml standard, filtering to obtain extractive solution, culturing mouse osteoblast with the extractive solution at original concentration and diluted 5 times, and observing and analyzing cell morphology for 24 hr, 48 hr and 72 hr. The results of the original concentration and 5-fold dilution of the extract are respectively: 92% and 102%.
Example 8
Mixing 42.1g of trimesic acid, 22.8g of tricalcium silicate dried and filtered at 120 ℃, 17.2g of dicalcium silicate dried and filtered, 15.6g of calcium phosphate and 25.6g of strontium phosphate, and carrying out ball milling at the ball milling speed of 150r/m for 6 hours, and then sieving in a 120-mesh sieve; 120g of the complex were obtained.
Weighing 10g of the obtained compound, adding 6ml of water, uniformly stirring, and then placing the slurry body into a polytetrafluoroethylene mold with the diameter of 6mm and the diameter of 12mm for molding. Taking out the sample after 10 minutes, and measuring the compressive strength after 2 hours and 24 hours; and testing the degradation speed and the bone cell growth rate.
And (3) testing results: 2-hour compressive strength: 28MPa, 24-hour compressive strength: 90 MPa; compressive strength at 72 hours: 150MPa is put into a shaking table of SBF at 37 ℃ according to the mass ratio of 1:30, and the shaking speed is 60 times/min. Degradation experiments were performed.
1.58% of degradation in the first day, 2.12% of degradation in the first week, 3.36% of degradation in the second week, 3.85% of degradation in the third week and 4.99% of degradation in the fourth week; degradation is 5.01% in the fifth week; degradation is 5.5% in the eighth week; degradation is carried out for 5.02% in the twelfth week; degradation is 5.06% in the sixteenth week; degradation was 5.03% in the twentieth week. The first week pH was 7.75, the second week pH was 7.49, the third week pH was 7.50, the fourth week pH was 7.46, the fifth week pH was 7.46, and the eighth week pH was 7.50.
Soaking at 37 deg.C for 72 hr according to 0.2g/ml standard, filtering to obtain extractive solution, culturing mouse osteoblast with the extractive solution at original concentration and diluted 5 times, and observing and analyzing cell morphology for 24 hr, 48 hr and 72 hr. The results of the original concentration and 5-fold dilution of the extract are respectively: 95 percent and 108 percent.
Example 9
Weighing 16.7g of 2, 6-pyridinedicarboxylic acid, 16.6g of terephthalic acid, 22.8g of tricalcium silicate dried at 120 ℃, 18.3g of hydroxyapatite and 25.6g of strontium phosphate, mixing, ball-milling at the ball-milling speed of 150r/m, and sieving in a 120-mesh sieve after ball-milling for 6 hours. 98g of the complex were obtained.
Weighing 10g of the obtained compound, adding 8ml of water, uniformly stirring, and then placing the slurry body into a polytetrafluoroethylene mold with the diameter of 6mm and the diameter of 12mm for molding. Taking out the sample after 10 minutes, and measuring the compressive strength after 2 hours and 24 hours; and testing the degradation speed and the bone cell growth rate.
And (3) testing results: 2-hour compressive strength: 12MPa, 24-hour compressive strength: 75 MPa; compressive strength at 72 hours: placing the mixture into a shaking table with SBF at 37 ℃ under the pressure of 110MPa according to the mass ratio of 1:30, and shaking at the speed of 60 times/min; degradation experiments were performed. 1.05% of degradation in the first day, 1.87% of degradation in the first week, 2.52% of degradation in the second week, 2.75% of degradation in the third week and 5.12% of degradation in the fourth week; degradation is 5.15% in the fifth week; degradation is 5.12% in the eighth week; degradation is carried out for 5.02% in the twelfth week; 3.08% in the sixteenth week; degradation was 3.32% in the twentieth week. The first week pH was 7.55, the second week pH was 7.17, the third week pH was 7.45, the fourth week pH was 7.50, the fifth week pH was 7.47, and the eighth week pH was 7.45.
Soaking at 37 deg.C for 72 hr according to 0.2g/ml standard, filtering to obtain extractive solution, culturing mouse osteoblast with the extractive solution at original concentration and diluted 5 times, and observing and analyzing cell morphology for 24 hr, 48 hr and 72 hr. The results of the original concentration and 5-fold dilution of the extract are respectively: 90% and 100%.
Example 10
Weighing 17.2g of 1, 4-cyclohexanedicarboxylic acid, 24.4g of 4,4' -biphenyldicarboxylic acid, 22.8g of tricalcium silicate dried at 120 ℃, 17.2g of dicalcium silicate dried at 120 ℃,10 g of calcium sulfate and 25.6g of strontium phosphate, mixing, carrying out ball milling at the ball milling speed of 150r/m, and sieving in a 120-mesh sieve after ball milling for 6 hours. 115g of the complex were obtained.
Weighing 10g of the obtained compound, adding 8ml of water, uniformly stirring, and then placing the slurry body into a polytetrafluoroethylene mold with the diameter of 6mm and the diameter of 12mm for molding. Taking out the sample after 10 minutes, and measuring the compressive strength after 2 hours and 24 hours; and testing the degradation speed and the bone cell growth rate.
And (3) testing results: 2-hour compressive strength: 15MPa, 24-hour compressive strength: 81 MPa; compressive strength at 72 hours: 108MPa is put into a shaking table of SBF at 37 ℃ according to the mass ratio of 1:30, and the shaking speed is 60 times/min. Degradation experiments were performed.
1.08% of degradation in the first day, 2.56% of degradation in the first week, 3.88% of degradation in the second week, 4.69% of degradation in the third week and 5.68% of degradation in the fourth week; degradation is 6.36% in the fifth week; degradation is 7.12% in the eighth week; degradation is 7.15% in the twelfth week; degradation is 7.12% in the sixteenth week; degradation was 7.10% in the twentieth week. The first week pH was 7.65, the second week pH was 7.22, the third week pH was 7.35, the fourth week pH was 7.41, the fifth week pH was 7.41, and the eighth week pH was 7.40.
Soaking at 37 deg.C for 72 hr according to 0.2g/ml standard, filtering to obtain extractive solution, culturing mouse osteoblast with the extractive solution of original concentration and diluted 5 times, and observing and analyzing cell morphology for 24 hr, 48 hr and 72 hr. The results of the original concentration and 5-fold dilution of the extract are respectively: 93 percent and 107 percent.
Comparative example 1
23g of 120 ℃ dried tricalcium silicate and 26g of strontium phosphate are weighed, mixed and ball-milled at a ball-milling rate of 150r/m, and sieved in a 120-mesh sieve after ball-milling for 6 hours. 49g of the complex were obtained.
Weighing 10g of the obtained compound, adding 8ml of water, uniformly stirring, and then placing the slurry body into a polytetrafluoroethylene mold with the diameter of 6mm and the diameter of 12mm for molding. Taking out the sample after 10 minutes, and measuring the compressive strength after 2 hours and 24 hours; and testing the degradation speed and the bone cell growth rate.
And (3) testing results: 2-hour compressive strength: 5MPa, 24-hour compressive strength: 20 MPa; compressive strength at 72 hours: 35 MPa.
The degradation experiment was carried out by placing the mixture in a shaker at 37 ℃ SBF according to a mass ratio of 1:30 and shaking the mixture at a speed of 60 times/min. 1.22% of degradation in the first day, 2.58% of degradation in the first week, 3.35% of degradation in the second week, 4.36% of degradation in the third week and 4.59% of degradation in the fourth week; 4.96% in the fifth week; 4.93% degradation in the eighth week; degradation is 5.15% in the twelfth week; 4.99% degradation in the sixteenth week; degradation was 5.05% in the twentieth week. The first week pH was 10.88, the second week pH 9.62, the third week pH 9.65, the fourth week pH 9.12, the fifth week pH 8.75, the eighth week pH 8.70.
Soaking at 37 deg.C for 72 hr according to 0.2g/ml standard, filtering to obtain extractive solution, culturing mouse osteoblast with the extractive solution of original concentration and diluted 5 times, and observing and analyzing cell morphology for 24 hr, 48 hr and 72 hr. The results of the original concentration and 5-fold dilution of the extract are respectively: 55% and 82%.
Comparative example 2
Respectively weighing 20g of tricalcium silicate (CaSS1) and 20g of calcium sulfate hemihydrate (CaSS2), mixing, ball-milling at the ball-milling speed of 150r/m, and filtering in a 120-mesh sieve after ball-milling for 6 hours. 39.75g of the complex were obtained.
Weighing 10g of the obtained compound, adding 5ml of water, uniformly stirring, and then placing the slurry body into a polytetrafluoroethylene mold with the diameter of 6mm and the diameter of 12mm for molding. Taking out the sample after 10 minutes, and measuring the compressive strength after 2 hours and 24 hours; and testing the degradation speed and the bone cell growth rate.
And (3) testing results: 2-hour compressive strength: 3.9MPa, 24-hour compressive strength: 35 MPa; compressive strength at 72 hours: 39 MPa.
Put into a shaking table with SBF at 37 ℃ according to the mass ratio of 1:30, and shake at the speed of 60 times/min. 5.35% of degradation in the first day, 25.16% of degradation in the first week, 28.51% of degradation in the second week, 32.33% of degradation in the third week and 41.11% of degradation in the fourth week; 45.09% degradation in the fifth week; 46.63% degradation in the eighth week; 46.95% degradation in the twelfth week; degradation at 46.33% in the sixteenth week; 46.15% degradation in the twentieth week; 46.23% degradation in the twenty-sixth week.
Soaking for 72 hr at 37 deg.C according to 0.2g/ml standard, filtering to obtain extractive solution, culturing mouse osteoblast with the extractive solution at original concentration and diluted 5 times, and observing and analyzing cell morphology and cell growth and differentiation rate for 24 hr, 48 hr and 72 hr. The results for the original concentration and 5-fold dilution were: 50 percent and 85 percent.
The compound bisphosphonate is absent, has better compressive strength, poorer biological performance, unsatisfactory cell differentiation and proliferation, fast degradation in the early stage, and stable and difficult degradation in the fifth week, and is not beneficial to the continuous regeneration and reconstruction of bone tissues.
Comparative example 3
20g of calcium citrate, 15g of calcium hydrogen phosphate (CaSS2) and 15g of calcium sulfate hemihydrate are mixed and ball-milled at a ball milling rate of 150r/m, and are filtered in a 120-mesh sieve after ball milling for 6 hours. 49.00g of the complex was obtained.
Weighing 10g of the obtained compound, adding 6ml of water, uniformly stirring, and then placing the slurry body into a polytetrafluoroethylene mold with the diameter of 6mm and the diameter of 12mm for molding. Taking out the sample after 10 minutes, and measuring the compressive strength after 2 hours and 24 hours; and testing the degradation speed and the bone cell growth rate.
And (3) testing results: 2-hour compressive strength: 1.8MPa, 24-hour compressive strength: 14.5 MPa.
Put into a shaking table with SBF at 37 ℃ according to the mass ratio of 1:30, and shake at the speed of 60 times/min. Degradation experiments were performed. SBF is put into the cured product within 5 hours, so that a good shape can be protected, and the product is gradually degraded from the surface; after 24 hours of drying, the pellets will crack and become small when exposed to SBF for half an hour. 7.55% of degradation in the first day, 15.22% of degradation in the first week, 23.97% of degradation in the second week, 31.69% of degradation in the third week and 35.65% of degradation in the fourth week; degradation is carried out by 40.15% in the fifth week; degradation is 45.55% in the eighth week; 51.51% degradation in the twelfth week; 56.02% degradation in the sixteenth week; 60.18% degradation in the twentieth week; degradation was 63.33% in the twenty-sixth week.
Soaking for 72 hours at 37 ℃ according to the standard of 0.2g/ml, filtering to obtain extracting solutions, culturing osteoblasts of mice by using the extracting solutions with the original concentration and diluted by 5 times respectively, and observing and analyzing cell morphology and cell growth and differentiation rate for 24 hours, 48 hours and 72 hours; the results of the original concentration and the 5-fold dilution cell proliferation rate are respectively as follows: 80% and 95%.
Comparative example 4
Weighing 22g of 120 ℃ dried tricalcium silicate, 18g of hydroxyapatite and 25g of strontium phosphate, mixing, ball-milling at a ball-milling speed of 150r/m, and sieving in a 120-mesh sieve after ball-milling for 6 hours; 52g of the complex were obtained.
Weighing 10g of the obtained compound, adding 8ml of water, uniformly stirring, and then placing the slurry body into a polytetrafluoroethylene mold with the diameter of 6mm and the diameter of 12mm for molding. Taking out the sample after 10 minutes, and measuring the compressive strength after 2 hours and 24 hours; and testing the degradation speed and the bone cell growth rate.
And (3) testing results: 2-hour compressive strength: 3.5MPa, 24-hour compressive strength: 21 MPa; compressive strength at 72 hours: placing the mixture into a shaking table with SBF at 37 ℃ under the pressure of 32MPa according to the mass ratio of 1:30, and shaking at the speed of 60 times/min; degradation experiments were performed. 1.01 percent of degradation in the first day, 1.85 percent of degradation in the first week, 2.67 percent of degradation in the second week, 2.75 percent of degradation in the third week and 3.18 percent of degradation in the fourth week; 3.39% in the fifth week; 3.50% degradation in the eighth week; 3.65% degradation in the twelfth week; 3.60% degradation in the sixteenth week; degradation was 3.59% in the twentieth week. pH 11.35 for week one, pH 10.57 for week two, pH 9.96 for week three, pH 9.50 for week four, pH 9.31 for week five and pH 8.92 for week eight.
Soaking at 37 deg.C for 72 hr according to 0.2g/ml standard, filtering to obtain extractive solution, culturing mouse osteoblast with the extractive solution at original concentration and diluted 5 times, and observing and analyzing cell morphology for 24 hr, 48 hr and 72 hr. The results of the original concentration and 5-fold dilution of the extract are respectively: 45 percent and 80 percent.
Comparative example 5
Mixing 23g of tricalcium silicate dried at 120 ℃,10 g of dicalcium silicate dried at 120 ℃,10 g of calcium sulfate and 25g of strontium phosphate, carrying out ball milling at the ball milling speed of 150r/m, and sieving in a 120-mesh sieve after ball milling for 6 hours; 65g of the complex were obtained.
Weighing 10g of the obtained compound, adding 8ml of water, uniformly stirring, and then placing the slurry body into a polytetrafluoroethylene mold with the diameter of 6mm and the diameter of 12mm for molding. Taking out the sample after 10 minutes, and measuring the compressive strength after 2 hours and 24 hours; and testing the degradation speed and the bone cell growth rate.
And (3) testing results: 2-hour compressive strength: 3MPa, 24-hour compressive strength: 23 MPa; compressive strength at 72 hours: 38MPa is put into a shaking table of SBF at 37 ℃ according to the mass ratio of 1:30, and the shaking speed is 60 times/min. Degradation experiments were performed. 3.02% of degradation in the first day, 4.56% of degradation in the first week, 4.98% of degradation in the second week, 5.31% of degradation in the third week and 5.88% of degradation in the fourth week; degradation is 6.36% in the fifth week; degradation is 7.15% in the eighth week; degradation is 7.18% in the twelfth week; degradation at 7.16% in the sixteenth week; degradation was 7.15% in the twentieth week. The first week pH was 11.22, the second week pH,10.85, the third week pH was 10.36, the fourth week pH was 9.72, the fifth week pH was 9.55, and the eighth week pH was 9.50.
Soaking at 37 deg.C for 72 hr according to 0.2g/ml standard, filtering to obtain extractive solution, culturing mouse osteoblast with the extractive solution of original concentration and diluted 5 times, and observing and analyzing cell morphology for 24 hr, 48 hr and 72 hr. The results of the original concentration and 5-fold dilution of the extract are respectively: 45 percent and 81 percent.
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