CN118105538B - Modified fiber reinforced PEEK bone scaffold material and preparation method thereof - Google Patents
Modified fiber reinforced PEEK bone scaffold material and preparation method thereof Download PDFInfo
- Publication number
- CN118105538B CN118105538B CN202410257828.9A CN202410257828A CN118105538B CN 118105538 B CN118105538 B CN 118105538B CN 202410257828 A CN202410257828 A CN 202410257828A CN 118105538 B CN118105538 B CN 118105538B
- Authority
- CN
- China
- Prior art keywords
- modified
- carbon fiber
- peek
- scaffold material
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000004696 Poly ether ether ketone Substances 0.000 title claims abstract description 86
- 229920002530 polyetherether ketone Polymers 0.000 title claims abstract description 86
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 210000000988 bone and bone Anatomy 0.000 title claims abstract description 60
- 239000000463 material Substances 0.000 title claims abstract description 47
- 239000000835 fiber Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 79
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 43
- 239000004917 carbon fiber Substances 0.000 claims abstract description 43
- 238000007731 hot pressing Methods 0.000 claims abstract description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 19
- KDHWOCLBMVSZPG-UHFFFAOYSA-N 3-imidazol-1-ylpropan-1-amine Chemical compound NCCCN1C=CN=C1 KDHWOCLBMVSZPG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 54
- 239000000243 solution Substances 0.000 claims description 36
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 238000004321 preservation Methods 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 241000872931 Myoporum sandwicense Species 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 10
- -1 4-butyl Chemical group 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 229960001760 dimethyl sulfoxide Drugs 0.000 claims description 8
- 238000007037 hydroformylation reaction Methods 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- 150000001299 aldehydes Chemical class 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 238000002390 rotary evaporation Methods 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 claims description 2
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 12
- PFKFTWBEEFSNDU-UHFFFAOYSA-N carbonyldiimidazole Chemical compound C1=CN=CN1C(=O)N1C=CN=C1 PFKFTWBEEFSNDU-UHFFFAOYSA-N 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 11
- 239000002131 composite material Substances 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 5
- 208000035143 Bacterial infection Diseases 0.000 abstract description 4
- 208000022362 bacterial infectious disease Diseases 0.000 abstract description 4
- 230000002980 postoperative effect Effects 0.000 abstract description 3
- 230000004071 biological effect Effects 0.000 abstract description 2
- 239000012567 medical material Substances 0.000 abstract description 2
- 238000010883 osseointegration Methods 0.000 abstract description 2
- 238000004132 cross linking Methods 0.000 abstract 1
- 238000005191 phase separation Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 13
- 238000001514 detection method Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 9
- 239000007943 implant Substances 0.000 description 8
- 210000004027 cell Anatomy 0.000 description 7
- 231100000135 cytotoxicity Toxicity 0.000 description 7
- 230000003013 cytotoxicity Effects 0.000 description 7
- LOKCTEFSRHRXRJ-UHFFFAOYSA-I dipotassium trisodium dihydrogen phosphate hydrogen phosphate dichloride Chemical compound P(=O)(O)(O)[O-].[K+].P(=O)(O)([O-])[O-].[Na+].[Na+].[Cl-].[K+].[Cl-].[Na+] LOKCTEFSRHRXRJ-UHFFFAOYSA-I 0.000 description 7
- 239000002953 phosphate buffered saline Substances 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000012779 reinforcing material Substances 0.000 description 5
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 4
- 229920004695 VICTREX™ PEEK Polymers 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000021164 cell adhesion Effects 0.000 description 4
- 239000012091 fetal bovine serum Substances 0.000 description 4
- 125000002883 imidazolyl group Chemical group 0.000 description 4
- 238000002513 implantation Methods 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- UCSJYZPVAKXKNQ-HZYVHMACSA-N streptomycin Chemical compound CN[C@H]1[C@H](O)[C@@H](O)[C@H](CO)O[C@H]1O[C@@H]1[C@](C=O)(O)[C@H](C)O[C@H]1O[C@@H]1[C@@H](NC(N)=N)[C@H](O)[C@@H](NC(N)=N)[C@H](O)[C@H]1O UCSJYZPVAKXKNQ-HZYVHMACSA-N 0.000 description 4
- 150000008053 sultones Chemical group 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- 239000006144 Dulbecco’s modified Eagle's medium Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 241000191967 Staphylococcus aureus Species 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 230000001054 cortical effect Effects 0.000 description 3
- 201000010099 disease Diseases 0.000 description 3
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 3
- 238000000338 in vitro Methods 0.000 description 3
- 238000001727 in vivo Methods 0.000 description 3
- 238000011534 incubation Methods 0.000 description 3
- 210000000963 osteoblast Anatomy 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 230000035755 proliferation Effects 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- 238000001356 surgical procedure Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 2
- 206010028980 Neoplasm Diseases 0.000 description 2
- 229930182555 Penicillin Natural products 0.000 description 2
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 description 2
- 108010087230 Sincalide Proteins 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 241000191963 Staphylococcus epidermidis Species 0.000 description 2
- 241000194019 Streptococcus mutans Species 0.000 description 2
- 229910052586 apatite Inorganic materials 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 210000001124 body fluid Anatomy 0.000 description 2
- 239000010839 body fluid Substances 0.000 description 2
- ANUZKYYBDVLEEI-UHFFFAOYSA-N butane;hexane;lithium Chemical compound [Li]CCCC.CCCCCC ANUZKYYBDVLEEI-UHFFFAOYSA-N 0.000 description 2
- 238000010609 cell counting kit-8 assay Methods 0.000 description 2
- 230000012292 cell migration Effects 0.000 description 2
- 230000004663 cell proliferation Effects 0.000 description 2
- 238000012258 culturing Methods 0.000 description 2
- 231100000263 cytotoxicity test Toxicity 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000001976 improved effect Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229940049954 penicillin Drugs 0.000 description 2
- 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 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- IZTQOLKUZKXIRV-YRVFCXMDSA-N sincalide Chemical compound C([C@@H](C(=O)N[C@@H](CCSC)C(=O)NCC(=O)N[C@@H](CC=1C2=CC=CC=C2NC=1)C(=O)N[C@@H](CCSC)C(=O)N[C@@H](CC(O)=O)C(=O)N[C@@H](CC=1C=CC=CC=1)C(N)=O)NC(=O)[C@@H](N)CC(O)=O)C1=CC=C(OS(O)(=O)=O)C=C1 IZTQOLKUZKXIRV-YRVFCXMDSA-N 0.000 description 2
- 229960005322 streptomycin Drugs 0.000 description 2
- 230000004083 survival effect Effects 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 208000006386 Bone Resorption Diseases 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 1
- 239000007836 KH2PO4 Substances 0.000 description 1
- 239000006142 Luria-Bertani Agar Substances 0.000 description 1
- 208000002193 Pain Diseases 0.000 description 1
- 208000037099 Prosthesis Failure Diseases 0.000 description 1
- 206010066902 Surgical failure Diseases 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 102000004142 Trypsin Human genes 0.000 description 1
- 108090000631 Trypsin Proteins 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 230000003698 anagen phase Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008468 bone growth Effects 0.000 description 1
- 230000024279 bone resorption Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 238000004113 cell culture Methods 0.000 description 1
- 239000006143 cell culture medium Substances 0.000 description 1
- 238000003570 cell viability assay Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000002784 cytotoxicity assay Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007850 degeneration Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 210000002744 extracellular matrix Anatomy 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011151 fibre-reinforced plastic Substances 0.000 description 1
- 210000002950 fibroblast Anatomy 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000003902 lesion Effects 0.000 description 1
- 230000033001 locomotion Effects 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 230000000399 orthopedic effect Effects 0.000 description 1
- 230000011164 ossification Effects 0.000 description 1
- 201000008482 osteoarthritis Diseases 0.000 description 1
- 230000009818 osteogenic differentiation Effects 0.000 description 1
- 230000036407 pain Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 210000002966 serum Anatomy 0.000 description 1
- 239000012679 serum free medium Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 210000001626 skin fibroblast Anatomy 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 230000008733 trauma Effects 0.000 description 1
- 239000012588 trypsin Substances 0.000 description 1
Classifications
-
- 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
- A61L27/02—Inorganic materials
- A61L27/08—Carbon ; Graphite
-
- 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
- A61L27/54—Biologically active materials, e.g. therapeutic substances
-
- 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
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
- A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
-
- 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
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Medicinal Chemistry (AREA)
- Public Health (AREA)
- General Health & Medical Sciences (AREA)
- Transplantation (AREA)
- Epidemiology (AREA)
- Veterinary Medicine (AREA)
- Animal Behavior & Ethology (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Dermatology (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Biomedical Technology (AREA)
- Molecular Biology (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials For Medical Uses (AREA)
Abstract
The application discloses a modified fiber reinforced PEEK bone scaffold material and a preparation method thereof, and relates to the technical field of medical materials. The preparation method of the bone scaffold material comprises the following steps: s1: treating PEEK with concentrated sulfuric acid to obtain sulfonated polyether-ether-ketone; s2: the sulfonated polyether-ether-ketone is grafted with 1- (3-aminopropyl) imidazole after being activated by N, N' -carbonyl diimidazole, so as to obtain a component I; s3: crosslinking the modified carbon fiber with the first component to obtain modified PEEK; s4: and (3) carrying out hot pressing on the modified PEEK to obtain the modified fiber reinforced PEEK bone scaffold material. The modified PEEK prepared by the method is obtained by stable chemical bonding between PEEK and modified carbon fiber, and the problem of phase separation between the carbon fiber and PEEK is effectively solved; the application improves the biological activity of the carbon fiber/PEEK composite material, improves the antibacterial activity of the composite material, and effectively reduces the problems of osseointegration and postoperative bacterial infection.
Description
Technical Field
The invention relates to the technical field of medical materials, in particular to a modified fiber reinforced PEEK bone scaffold material and a preparation method thereof.
Background
Diseases such as tumors, osteoarthritis, trauma and degeneration often lead to irreversible damage to bone tissue. Surgery is often the most effective treatment when bone tissue lesions are severe or when large bone defects or normal bone tissue anatomy are destroyed by surgery. The application of the orthopedic internal fixation is helpful for reconstructing normal bone tissue structure, recovering normal movement function, relieving symptoms and pains of patients and promoting postoperative recovery of patients. At present, metal implantation materials represented by titanium and novel high-performance engineering plastics represented by polyether-ether-ketone are widely applied to the field of orthopaedics. However, the elastic modulus (116.3+ -1.2 GPa) of the titanium alloy is far higher than the elastic modulus (4-30 GPa) of human bone, so that a stress shielding effect is caused, namely, a metal material with higher modulus bears more load, and bone tissue with lower modulus only bears lower load, so that biological influences such as bone mass loss, delayed healing and the like are caused, and the occurrence rate of late stage complications such as bone resorption, adjacent segmental diseases, prosthesis loosening and the like of the implant after implantation of the endophyte is greatly increased, and even surgical failure is finally caused. In addition, radiation cannot penetrate through metal materials in radiation examination, artifacts can be generated around the metal implant, so that evaluation of a clinician on the disease condition of a patient can be influenced, and effective radiation dose received by a tumor part and surrounding tissues can be influenced in the radiation treatment process.
In contrast, polyether-ether-ketone has excellent chemical stability, X-ray transmittance and elastic modulus similar to that of human cortical bone, and can reduce stress shielding effect. However, the elastic modulus of polyether-ether-ketone (3-4 GPa) is similar to that of human cortical bone (4-30 GPa), but the modulus is still insufficient. At present, the mechanical strength of the composite is mainly enhanced by adding reinforcing materials to the polyetheretherketone. The common reinforcing materials comprise glass fiber, titanium, carbon nano tube, carbon fiber and the like, wherein the carbon fiber has good mechanical property and biocompatibility, and is widely applied to the field of bone implants to extract the mechanical property of Gao Jumi ether ketone, but the chemical inertness of the surface of the carbon fiber and the hydrophobicity of polyether ether ketone lead to poor interface combination of the carbon fiber and the polyether ether ketone and low interlayer shear strength, thus affecting the overall mechanical property of the composite material. Moreover, polyetheretherketone, like other polymers, has the characteristic of low surface energy, which, due to the relatively hydrophobic surface, limits cell adhesion, forming a biologically inert surface, which results in polyetheretherketone not being able to promote the attachment, proliferation, etc. of osteoblasts after implantation in vivo.
Disclosure of Invention
The invention aims to provide a modified fiber reinforced PEEK bone scaffold material and a preparation method thereof, which solve the following technical problems:
The existing polyether-ether-ketone modification is realized by adding a reinforcing material, and the chemical inertness of the surface of the reinforcing material and the hydrophobicity of the polyether-ether-ketone lead to poor interface combination of the reinforcing material and the polyether-ether-ketone and low interlayer shear strength, so that the overall mechanical property of the composite material is affected.
The aim of the invention can be achieved by the following technical scheme:
a preparation method of a modified fiber reinforced PEEK bone scaffold material comprises the following steps:
S1: adding PEEK and concentrated sulfuric acid into a reaction bottle A, controlling the temperature to be 50-70 ℃, carrying out heat preservation reaction for 6-9h under the stirring condition, adding ice water for washing, and drying to obtain sulfonated polyether-ether-ketone;
S2: adding sulfonated polyether-ether-ketone, N' -carbonyl diimidazole and methyl sulfoxide into a reaction kettle A, uniformly dispersing, controlling the temperature to be 50-60 ℃, adding 1- (3-aminopropyl) imidazole, carrying out heat preservation and stirring for 3-6h, washing and drying to obtain a component I;
s3: adding modified carbon fiber and toluene into a reaction kettle B, adding a first component, controlling the temperature to be 70-80 ℃, preserving the heat for 6-12 hours, and performing rotary evaporation to obtain modified PEEK;
s4: and (3) hot-pressing the modified PEEK to obtain the modified fiber reinforced PEEK bone scaffold material.
As a further aspect of the invention: in S1, the concentrated sulfuric acid is 85-98wt% sulfuric acid water solution, and the addition ratio of PEEK to the concentrated sulfuric acid is 1g:8-12mL.
As a further aspect of the invention: the addition ratio of the sulfonated polyether ether ketone, the N, N' -carbonyl diimidazole, the methyl sulfoxide and the 1- (3-aminopropyl) imidazole in the S2 is 10g:2-5g:100-200mL:1-1.5g.
As a further aspect of the invention: the addition ratio of the component I to the modified carbon fiber to the methyl sulfoxide in the S3 is 10g:1-10g:100-500mL.
As a further aspect of the invention: the specific contents of the hot pressing in the S4 are as follows: hot pressing under 140-260MPa at 150-350deg.C for 10-60min.
As a further aspect of the invention: the preparation method of the modified carbon fiber comprises the following steps:
A1: adding carbon fiber and hydrochloric acid solution into a reaction kettle C, controlling the temperature to be 90-100 ℃, carrying out heat preservation reaction for 3-6h, washing with water, and drying to obtain hydroxylated carbon fiber;
a2: adding the hydroxylated carbon fiber and NaIO 4 solution into a reaction kettle D, controlling the temperature to be 40-60 ℃, carrying out heat preservation reaction for 10-60min, washing with water, and drying to obtain the hydroformylation carbon fiber;
a3: under nitrogen atmosphere, tetrahydrofuran and 1, 4-butyl sultone are added into a reaction bottle, the temperature is controlled to be-70 to-60 ℃, n-butyl lithium solution is added under the stirring condition, the mixture is uniformly dispersed, aldehyde carbon fiber is added, the temperature is naturally raised to normal temperature under the stirring condition, and the mixture is washed and dried to obtain the modified carbon fiber.
As a further aspect of the invention: in A1, the hydrochloric acid solution is 3-6mol/L hydrochloric acid aqueous solution, and the solid-liquid ratio of the carbon fiber to the hydrochloric acid solution is 10g:50-200mL.
As a further aspect of the invention: in A2, naIO 4 solution is 0.1-0.3mol/L NaIO 4 water solution, and the solid-liquid ratio of the hydroxylated carbon fiber and NaIO 4 solution is 10g:50-200mL.
As a further aspect of the invention: in A3, the n-butyllithium solution is 2-3mol/L n-butyllithium n-hexane solution, and the adding ratio of tetrahydrofuran, 1, 4-butylsultone, n-butyllithium solution and aldehyde carbon fiber is 100-200mL:3.4-6.8g:20-50mL:10g.
A modified fiber reinforced PEEK bone scaffold material is prepared by any one of the preparation methods.
The invention has the beneficial effects that:
(1) Firstly, sulfonating PEEK powder by utilizing concentrated sulfuric acid, and grafting sulfonic acid groups on PEEK molecular chains to obtain sulfonated PEEK; and then, activating a sulfonic acid group on sulfonated PEEK by using N, N' -carbonyl diimidazole, and then, reacting with 1- (3-aminopropyl) imidazole, so that the imidazole group is grafted on a PEEK molecular chain to obtain a component I. The application uses hydrochloric acid solution to heat treat carbon fiber to obtain carbon fiber with surface rich in hydroxylation, and uses NaIO 4 to carry out hydroformylation on the carbon fiber; and finally, reacting the 1, 4-butanesulfonic acid lactone with aldehyde groups on the surface of the carbon fiber, and grafting the sultone groups on the surface of the carbon fiber to obtain the modified carbon fiber. The application utilizes the reaction of polyether-ether-ketone grafted with imidazole groups on molecular chains and carbon fiber grafted with sultone groups on the surface to obtain modified PEEK. The modified PEEK prepared by the method is obtained by firmly chemically bonding PEEK and modified carbon fibers, so that the interface interaction force of PEEK and carbon fibers is improved, the problem of separation of carbon fibers and PEEK is effectively solved, and the carbon fibers and PEEK are tightly connected.
(2) According to the application, PEEK is treated by concentrated sulfuric acid, so that a three-dimensional nano-network structure appears on the surface of PEEK, bone tissue grows into a gap, the porous structure can increase the binding force between an implant and bone, the porous structure is similar to the microenvironment provided by extracellular matrixes, cell attachment and proliferation are facilitated, the porosity and pore diameter are favorable for cell migration, the mechanical interlocking between polyether-ether-ketone and bone is enhanced, and bone growth and body fluid transfer are promoted; also improves the biological activity of PEEK, has the capability of inducing the functions of pre-osteoblast, including initial cell adhesion, proliferation and osteogenic differentiation in vitro, and remarkably enhances the integration of bone and the bonding strength of human bone and implant in vivo and the capability of apatite formation.
(3) The modified PEEK prepared by the method is obtained by stable chemical bonding between PEEK and modified carbon fiber, and not only antibacterial groups but also sulfonic acid groups are generated in the preparation process; wherein, the antibacterial group obtained by ring opening of the imidazole group and the sultone group has high-efficiency antibacterial performance and higher biocompatibility, and does not generate drug resistance.
The sulfuric acid group obtained by ring opening of the imidazolyl and the sultone group can be decomposed into SO 3- and H +, the sulfuric acid group is negatively charged and can attract positively charged calcium ions, and phosphate particles with positive charges and negative charges are obtained on the surface, SO that a metastable phase hydration precursor cluster composed of calcium hydrophosphate is formed and finally converted into stable bone-like apatite, the in-vivo bioactivity of the material is improved, and the bone formation conversion is promoted; in addition, the negatively charged surface is more attractive for cell adhesion proteins, prevents the adhesion of nonspecific proteins, has disinfection performance, can prevent infection, and improves the success rate of implantation surgery.
The preparation method of the application improves the bioactivity of the carbon fiber/PEEK composite material, effectively solves the problem of poor antibacterial activity caused by the bioinert property of the PEEK surface, improves the antibacterial activity of the composite material, effectively reduces the bacterial infection condition as an implant material, effectively inhibits the increment film formation of staphylococcus aureus and staphylococcus epidermidis, and effectively reduces the problems of osseointegration and postoperative bacterial infection.
Detailed Description
The following description will clearly and fully describe the technical solutions of the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The preparation method of the modified carbon fiber in the embodiment 1 comprises the following steps:
A1: adding 50g of carbon fiber (model 3KT300 carbon fiber produced by Toli industry Co., ltd.) and 500mL of 3mol/L hydrochloric acid aqueous solution into a reaction kettle C, controlling the temperature to 90 ℃, carrying out heat preservation reaction for 6 hours, washing with water, and drying to obtain hydroxylated carbon fiber;
A2: adding 50g of hydroxylated carbon fiber and 500mL of 0.3mol/L NaIO 4 aqueous solution into a reaction kettle D, controlling the temperature to be 60 ℃, carrying out heat preservation reaction for 30min, washing with water, and drying to obtain the hydroformylation carbon fiber;
A3: under nitrogen atmosphere, 500mL of tetrahydrofuran and 17g of 1, 4-butyl sultone are added into a reaction bottle, the temperature is controlled to be-70 ℃, 100mL of 2mol/L n-butyllithium n-hexane solution is added under stirring, the mixture is uniformly dispersed, 50g of hydroformylation carbon fiber is added, the mixture is naturally heated to normal temperature under stirring, and the mixture is washed and dried to obtain the modified carbon fiber.
The preparation method of the modified carbon fiber in the embodiment 2 comprises the following steps:
A1: adding 50g of carbon fiber (model 3KT300 carbon fiber produced by Toli industry Co., ltd.) and 500mL of 3mol/L hydrochloric acid aqueous solution into a reaction kettle C, controlling the temperature to 90 ℃, carrying out heat preservation reaction for 6 hours, washing with water, and drying to obtain hydroxylated carbon fiber;
A2: adding 50g of hydroxylated carbon fiber and 500mL of 0.3mol/L NaIO 4 aqueous solution into a reaction kettle D, controlling the temperature to be 60 ℃, carrying out heat preservation reaction for 30min, washing with water, and drying to obtain the hydroformylation carbon fiber;
A3: 700mL of tetrahydrofuran and 25g of 1, 4-butyl sultone are added into a reaction bottle under the nitrogen atmosphere, the temperature is controlled to be-65 ℃, 150mL of 2mol/L n-butyl lithium n-hexane solution is added under the stirring condition, the dispersion is uniform, 50g of aldehyde carbon fiber is added, the temperature is naturally raised to normal temperature under the stirring condition, and the modified carbon fiber is obtained after washing and drying.
Example 3 the method of preparing the modified carbon fiber comprises the steps of:
A1: adding 50g of carbon fiber (model 3KT300 carbon fiber produced by Toli industry Co., ltd.) and 500mL of 3mol/L hydrochloric acid aqueous solution into a reaction kettle C, controlling the temperature to 90 ℃, carrying out heat preservation reaction for 6 hours, washing with water, and drying to obtain hydroxylated carbon fiber;
A2: adding 50g of hydroxylated carbon fiber and 500mL of 0.3mol/L NaIO 4 aqueous solution into a reaction kettle D, controlling the temperature to be 60 ℃, carrying out heat preservation reaction for 30min, washing with water, and drying to obtain the hydroformylation carbon fiber;
A3: under nitrogen atmosphere, 1000mL of tetrahydrofuran and 34g of 1, 4-butyl sultone are added into a reaction bottle, the temperature is controlled to be minus 60 ℃, 250mL of 3mol/L n-butyl lithium n-hexane solution is added under stirring, the mixture is uniformly dispersed, 50g of aldehyde carbon fiber is added, the mixture is naturally heated to normal temperature under stirring, and the mixture is washed and dried to obtain the modified carbon fiber.
Example 4a method for preparing a modified fiber reinforced PEEK bone scaffold material comprising the steps of:
S1: 100g PEEK (PEEK 450PF powder manufactured by Victrex Co., UK) and 800mL 85wt% sulfuric acid aqueous solution are added into a reaction bottle A, the temperature is controlled to be 50 ℃, the reaction is carried out for 6 hours under the condition of stirring, ice water is added for washing, and the sulfonated polyether-ether-ketone is obtained after drying;
s2: adding 100g of sulfonated polyether-ether-ketone, 20g of N, N' -carbonyl diimidazole and 1000mL of methyl sulfoxide into a reaction kettle A, uniformly dispersing, controlling the temperature to be 50 ℃, adding 10g of 1- (3-aminopropyl) imidazole, carrying out heat preservation and stirring for 3h, washing and drying to obtain a component I;
S3: adding 25g of the modified carbon fiber prepared in the embodiment 1 and 500mL of toluene into a reaction kettle B, adding 50g of component I, controlling the temperature to be 70 ℃, preserving the heat for 6 hours, and performing rotary evaporation to obtain modified PEEK;
s4: and (3) hot-pressing the modified PEEK for 20min under the hot-pressing pressure of 140MPa and the hot-pressing temperature of 150 ℃ to obtain the modified fiber reinforced PEEK bone scaffold material.
Example 5a method for preparing a modified fiber reinforced PEEK bone scaffold material comprising the steps of:
S1: 100g PEEK (PEEK 450PF powder manufactured by Victrex Co., UK) and 1000mL of 90wt% sulfuric acid aqueous solution are added into a reaction bottle A, the temperature is controlled to be 60 ℃, the reaction is carried out for 6 hours under the condition of stirring, ice water is added for washing, and the sulfonated polyether-ether-ketone is obtained after drying;
S2: adding 100g of sulfonated polyether-ether-ketone, 35g of N, N' -carbonyl diimidazole and 1500mL of methyl sulfoxide into a reaction kettle A, uniformly dispersing, controlling the temperature to be 55 ℃, adding 12g of 1- (3-aminopropyl) imidazole, carrying out heat preservation and stirring for 3h, washing and drying to obtain a component I;
S3: adding 25g of the modified carbon fiber prepared in the embodiment 2 and 2000mL of toluene into a reaction kettle B, adding 50g of component I, controlling the temperature to be 75 ℃, preserving the heat for 9 hours, and performing rotary evaporation to obtain modified PEEK;
s4: and (3) hot-pressing the modified PEEK for 20min under the hot-pressing pressure of 140MPa and the hot-pressing temperature of 150 ℃ to obtain the modified fiber reinforced PEEK bone scaffold material.
Example 6 a method for preparing a modified fiber reinforced PEEK bone scaffold material comprising the steps of:
s1: adding 100g PEEK (PEEK 450PF powder manufactured by Victrex Co., UK) and 800-1200mL of 85-98wt% sulfuric acid aqueous solution into a reaction bottle A, controlling the temperature to be 50-70 ℃, performing heat preservation reaction for 6-9h under stirring, adding ice water for washing, and drying to obtain sulfonated polyether-ether-ketone;
S2: adding 100g of sulfonated polyether-ether-ketone, 50g of N, N' -carbonyl diimidazole and 2000mL of methyl sulfoxide into a reaction kettle A, uniformly dispersing, controlling the temperature to be 60 ℃, adding 15g of 1- (3-aminopropyl) imidazole, carrying out heat preservation and stirring for 6h, washing and drying to obtain a component I;
S3: adding 25g of the modified carbon fiber prepared in the embodiment 3 and 2500mL of toluene into a reaction kettle B, adding 50g of component I, controlling the temperature to be 80 ℃, preserving the heat for 12 hours, and performing rotary evaporation to obtain modified PEEK;
s4: and (3) hot-pressing the modified PEEK for 20min under the hot-pressing pressure of 140MPa and the hot-pressing temperature of 150 ℃ to obtain the modified fiber reinforced PEEK bone scaffold material.
The preparation method of the modified carbon fiber of comparative example 1 comprises the following steps:
A1: adding 50g of carbon fiber (model 3KT300 carbon fiber produced by Toli industry Co., ltd.) and 500mL of 3mol/L hydrochloric acid aqueous solution into a reaction kettle C, controlling the temperature to 90 ℃, carrying out heat preservation reaction for 6 hours, washing with water, and drying to obtain hydroxylated carbon fiber;
A2: 50g of hydroxylated carbon fiber and 500mL of 0.3mol/L NaIO 4 aqueous solution are added into a reaction kettle D, the temperature is controlled at 60 ℃, the reaction is carried out for 30min under the heat preservation, and the modified carbon fiber is obtained after washing and drying.
Comparative example 2 in comparison with example 4, comparative example 2 was merely equivalent substitution of the modified carbon fiber prepared in example 1 added in example 4 with carbon fiber (model 3KT300 carbon fiber manufactured by eastern industrial company of japan), and the remaining components were completely identical to the preparation method in example 4.
Comparative example 3 in comparison with example 4, comparative example 3 was merely replaced with the modified carbon fiber prepared in example 1 added in example 4 in an equivalent amount to the modified carbon fiber prepared in comparative example 1, and the remaining components were completely identical to the preparation method in example 4.
Comparative example 4a method for preparing a modified fiber reinforced PEEK bone scaffold material comprising the steps of:
S1: 100g PEEK (PEEK 450PF powder manufactured by Victrex Co., UK) and 800mL 85wt% sulfuric acid aqueous solution are added into a reaction bottle A, the temperature is controlled to be 50 ℃, the reaction is carried out for 6 hours under the condition of stirring, ice water is added for washing, and the sulfonated polyether-ether-ketone is obtained after drying;
S2: adding 25g of the modified carbon fiber prepared in the embodiment 1 and 500mL of toluene into a reaction kettle B, adding 50g of sulfonated polyether-ether-ketone, controlling the temperature to be 70 ℃, preserving the heat for 6 hours, and performing rotary evaporation to obtain modified PEEK;
S3: and (3) hot-pressing the modified PEEK for 20min under the hot-pressing pressure of 140MPa and the hot-pressing temperature of 150 ℃ to obtain the modified fiber reinforced PEEK bone scaffold material.
Performance detection
(1) Contact angle: a drop of 2uL deionized water was free-falling from the needle (od=1 mm, id=0.82 mm) onto the composite surface using a SL2008 water contactor test. The included angle between the solid-liquid interfaces is measured as the water contact angle until the liquid drop is stabilized on the surface of the bone scaffold material, and the detection result is shown in table 1;
(2) Water absorption and swelling ratio:
Phosphate buffer is prepared: 1000mLPBS contains 8.0g NaCl, 0.2g KCl and 3.63g Na 2HPO4·12H2O、0.24g KH2PO4, and is stirred until the materials are fully dissolved, the pH is adjusted to 7.4 by 10mL/L NaOH, and the materials are packaged, autoclaved and stored at 4 ℃;
Detecting content: the volume V Dry and weight W Dry of the sample when dried were recorded and the bone scaffolding material was soaked in 50mL centrifuge tubes filled with Phosphate Buffered Saline (PBS) for 16 days. The bone scaffold material was taken out of PBS, rapidly dried, and the volume V Wet state and weight W Wet state at this time were measured, the water absorption η, the swelling ratio δ were calculated as follows, and the detection results are shown in table 1:
Water absorption η= [ (W Wet state -W Dry ）/W Dry ] ×100%
Swelling ratio δ= [ (V Wet state -V Dry ）/V Dry ] ×100%
Table 1: statistical table of performance test data for examples 4-6 and comparative examples 2-4
As can be seen from table 1, the contact angles of the bone scaffold materials prepared in examples 4 to 6 of the present application are close to 70 °, and 70 ° is the angle most suitable for cell adhesion, which can accelerate cell migration; in addition, the water absorption and swelling rate of the bone scaffold material prepared by the application are 0% after being soaked in PBS for 16 days, and the quality and the volume are unchanged, namely, the shape and the structure of the bone scaffold material prepared by the application are not changed in a body fluid environment, so that the stability of the structure and the function of an implant is ensured, and the support and reconstruction of surrounding bone tissues are ensured.
(3) Mechanical properties
① Tensile strength: according to GB/T1040.2-2006, determination of tensile Property of Plastic, an electronic universal testing machine (Instron-1121,Instron Corp,USA) is adopted, the test is carried out under the conditions of the test temperature of 23 ℃ and the test speed of 2mm/s, and the detection results are shown in Table 2;
② Compressive strength: according to GB/T1041-2008 'determination of Plastic compression Property', an electronic universal testing machine (Instron-1121,Instron Corp,USA) is adopted for detection under the conditions of an experiment temperature of 23 ℃ and an experiment speed of 5mm/s, and the detection results are shown in Table 2;
③ Flexural strength: according to GB/T9341-2008 'determination of Plastic bending Property', an electronic universal testing machine (Instron-1121,Instron Corp,USA) is adopted for detection under the conditions of an experiment temperature of 23 ℃ and an experiment speed of 2mm/s, and the detection results are shown in Table 2;
④ Shear strength: according to GB/T3355-2005 method for testing longitudinal and transverse shearing of fiber-reinforced plastics, an electronic universal tester (Instron-1121,Instron Corp,USA) is used
Table 2: mechanical property detection data statistics table for examples 4-6 and comparative examples 2-4
As can be seen from Table 2, the tensile strength and the elastic modulus of the bone scaffold material prepared by the present application are more similar to those of human cortical bone.
(4) Antibacterial properties: the antibacterial ability was evaluated by E.coli (E.coli; CICC 10003), staphylococcus aureus (S.aureus; CICC 0001) and Streptococcus mutans (S.mutans; CICC 10438). The bone scaffolds prepared in examples 4 to 6 and comparative examples 2 to 4 were sterilized overnight at 121℃in an autoclave. A 20uL bacterial suspension at a concentration of 10 5 CFU/mL was dropped on a sample of a 24-well plate, followed by culturing the well plate at 37 ℃ for 24 hours, then taking out the plate to dilute the bacteria on the sample in the 24-well plate with PBS solution, diluting the dissociated bacterial solution 10, 100 and 1000 times sequentially with PBS, adding 100uL of the diluted suspension to a standard LB agar plate for incubation at 37 ℃ for 24 hours, and calculating the antibacterial ratio R by the following formula:
R/%=[（B-C）/B]×100%
Wherein, R-antibacterial rate,%; average colony number of the B-blank control group sample and CFU (circulating fluid Unit); c-average colony number of the antibacterial sample and CFU; the detection results are shown in Table 3;
table 3: tables for statistics of antibacterial property test data of examples 4 to 6 and comparative examples 2 to 4
As shown in Table 3, the bone scaffold materials prepared in examples 4-6 of the present application have good antibacterial properties, and as implant materials, can effectively inhibit the proliferation of Staphylococcus aureus and Staphylococcus epidermidis to form a film, and reduce bacterial infection.
(5) In vitro cytotoxicity assays
Leaching solution: immersing the bone scaffold materials prepared in examples 4-6 and comparative examples 2-4 in a DMEM+F12 serum-free medium, wherein the ratio of the surface area to the leaching medium is 0.6cm 2/mL, the total area is 17.6cm 2, placing in a incubator for 96 hours, and taking the supernatant for preservation at 4 ℃;
Cell culture: selecting a mouse fibroblast strain NIH3T3, human osteoblasts HFOB and primary cultured human skin fibroblast HSF, and culturing in a serum cell culture medium (DMEM) containing 89% of DMEM+F12, 10% of Fetal Bovine Serum (FBS), 1% of penicillin and streptomycin at 37 ℃ under a CO 2 concentration of 5% and a 95% humidity condition;
Measurement of the degree of cell proliferation: cells in the flask were grown to the read-out period, digested with digests (1% EDTA 2mL+1% trypsin 10mL+0.01mol/L PBS 88mL, pH 7.2), seeded on 96-well plates, cell counted with 1X 10 3 added per well, after 4-6h cell attachment, the experimental group was changed to leach broth (89% leach, 10% Fetal Bovine Serum (FBS), 1% penicillin and streptomycin), 0.1mL of broth added per well, and 7 plates of 96-well plates were seeded. The measurement was performed every 24 hours. Adding 10uLCCK-8 solution (10% of the culture solution in each well) into each well, placing into a CO 2 incubator for incubation for 2 hours, and reading the optical density OD value (wavelength 450 nm) in a ELx800 microplate reader;
Cytotoxicity experiments were performed using the CCK-8 method (CCK-8;Dojindo Molecular Technology, japan): cells in logarithmic growth phase, which were passaged three times or more, were planted in two 96-well plates at a concentration of 105/mL, and were divided into nine groups, a first plate group of 6 groups of 10 wells each, a second plate group of 3 groups of 10 wells each. Adding 100uL of culture solution into each well, measuring once every 24 hours, adding 10uLCCK-8 solutions (accounting for 10% of the culture solution in each well), placing into a CO 2 incubator for incubation for 2 hours, and reading Optical Density (OD) value (wavelength 450 nm) in a ELx enzyme label instrument; cytotoxicity was reflected by Relative Growth Rate (RGR), cytotoxicity criteria for RGR assay are shown in Table 4, and detection results are shown in Table 5;
table 4: cytotoxicity criteria for RGR assay
Table 5: cell viability assay data statistics for examples 4-6, comparative examples 2-4
As can be seen from Table 5, the bone scaffold material prepared by the application has good biocompatibility, and in vitro cytotoxicity test, the relative cell survival rate of the bone scaffold material prepared by the application in examples 4-6 is 93-98% within 7 days of culture, the corresponding cytotoxicity level is 1, and the cell survival rate and cytotoxicity level of the bone scaffold material prepared by the application are equivalent to those of pure titanium (89-98% RGR) and PEEK (85-96% RGR), which indicates that the bone scaffold material prepared by the application has no obvious cytotoxicity.
The foregoing describes one embodiment of the present invention in detail, but the description is only a preferred embodiment of the present invention and should not be construed as limiting the scope of the invention. All equivalent changes and modifications within the scope of the present invention are intended to be covered by the present invention.
Claims (9)
1. The preparation method of the modified fiber reinforced PEEK bone scaffold material is characterized by comprising the following steps:
S1: adding PEEK and concentrated sulfuric acid into a reaction bottle A, controlling the temperature to be 50-70 ℃, carrying out heat preservation reaction for 6-9h under the stirring condition, adding ice water for washing, and drying to obtain sulfonated polyether-ether-ketone;
S2: adding sulfonated polyether-ether-ketone, N' -carbonyl diimidazole and methyl sulfoxide into a reaction kettle A, uniformly dispersing, controlling the temperature to be 50-60 ℃, adding 1- (3-aminopropyl) imidazole, carrying out heat preservation and stirring for 3-6h, washing and drying to obtain a component I;
s3: adding modified carbon fiber and toluene into a reaction kettle B, adding a first component, controlling the temperature to be 70-80 ℃, preserving the heat for 6-12 hours, and performing rotary evaporation to obtain modified PEEK;
s4: hot-pressing the modified PEEK to obtain a modified fiber reinforced PEEK bone scaffold material;
the preparation method of the modified carbon fiber comprises the following steps:
A1: adding carbon fiber and hydrochloric acid solution into a reaction kettle C, controlling the temperature to be 90-100 ℃, carrying out heat preservation reaction for 3-6h, washing with water, and drying to obtain hydroxylated carbon fiber;
a2: adding the hydroxylated carbon fiber and NaIO 4 solution into a reaction kettle D, controlling the temperature to be 40-60 ℃, carrying out heat preservation reaction for 10-60min, washing with water, and drying to obtain the hydroformylation carbon fiber;
a3: under nitrogen atmosphere, tetrahydrofuran and 1, 4-butyl sultone are added into a reaction bottle, the temperature is controlled to be-70 to-60 ℃, n-butyl lithium solution is added under the stirring condition, the mixture is uniformly dispersed, aldehyde carbon fiber is added, the temperature is naturally raised to normal temperature under the stirring condition, and the mixture is washed and dried to obtain the modified carbon fiber.
2. The preparation method of the modified fiber reinforced PEEK bone scaffold material according to claim 1, wherein the concentrated sulfuric acid in S1 is 85-98wt% sulfuric acid water solution, and the addition ratio of PEEK to concentrated sulfuric acid is 1g:8-12mL.
3. The preparation method of the modified fiber reinforced PEEK bone scaffold material according to claim 2, wherein the addition ratio of sulfonated polyether ether ketone, N' -carbonyl diimidazole, methyl sulfoxide and 1- (3-aminopropyl) imidazole in S2 is 10g:2-5g:100-200mL:1-1.5g.
4. The preparation method of the modified fiber reinforced PEEK bone scaffold material according to claim 1, wherein the addition ratio of the component I, the modified carbon fiber and the toluene in the S3 is 10g:1-10g:100-500mL.
5. The preparation method of the modified fiber reinforced PEEK bone scaffold material according to claim 1, wherein the specific contents of the hot pressing in S4 are as follows: hot pressing under 140-260MPa at 150-350deg.C for 10-60min.
6. The preparation method of the modified fiber reinforced PEEK bone scaffold material according to claim 1, wherein the hydrochloric acid solution in A1 is 3-6mol/L hydrochloric acid aqueous solution, and the solid-to-liquid ratio of carbon fibers and hydrochloric acid solution is 10g:50-200mL.
7. The preparation method of the modified fiber reinforced PEEK bone scaffold material according to claim 1, wherein the NaIO 4 solution in A2 is 0.1-0.3mol/L NaIO 4 aqueous solution, and the solid-liquid ratio of the hydroxylated carbon fiber to the NaIO 4 solution is 10g:50-200mL.
8. The preparation method of the modified fiber reinforced PEEK bone scaffold material according to claim 1, wherein the n-butyllithium solution in A3 is 2-3mol/L n-butyllithium n-hexane solution, and the addition ratio of tetrahydrofuran, 1, 4-butanesulfonic acid lactone, n-butyllithium solution and aldehyde carbon fiber is 100-200mL:3.4-6.8g:20-50mL:10g.
9. A modified fibre reinforced PEEK bone scaffold material, characterized in that it is made by the preparation method according to any one of claims 1-8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410257828.9A CN118105538B (en) | 2024-03-07 | 2024-03-07 | Modified fiber reinforced PEEK bone scaffold material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410257828.9A CN118105538B (en) | 2024-03-07 | 2024-03-07 | Modified fiber reinforced PEEK bone scaffold material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN118105538A CN118105538A (en) | 2024-05-31 |
| CN118105538B true CN118105538B (en) | 2024-07-26 |
Family
ID=91211916
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410257828.9A Active CN118105538B (en) | 2024-03-07 | 2024-03-07 | Modified fiber reinforced PEEK bone scaffold material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118105538B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN119015496B (en) * | 2024-08-14 | 2025-09-16 | 苏州真懿医疗有限公司 | Preparation method of polyetheretherketone auditory ossicular prosthesis and polyetheretherketone auditory ossicular prosthesis |
| CN118895033A (en) * | 2024-09-27 | 2024-11-05 | 浙江科赛新材料科技有限公司 | A PEEK composite material and its preparation method and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110627955A (en) * | 2019-09-23 | 2019-12-31 | 华东理工大学 | Zwitterionization-based polyvinylimidazole terpolymer and preparation method and application |
| CN112778564A (en) * | 2021-01-06 | 2021-05-11 | 吉林大学 | Carbon fiber reinforced polyether-ether-ketone composite material, and biological activity improvement method and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR112012016027B1 (en) * | 2009-12-11 | 2019-01-15 | Difusion Technologies, Inc. | production method of polyetheretherketone antimicrobial implants |
| CN114316355B (en) * | 2022-01-06 | 2022-10-04 | 中山大学 | Long-acting renewable antibacterial polyether-ether-ketone and preparation method and application thereof |
| CN116333216B (en) * | 2023-03-07 | 2025-04-08 | 中南大学 | Imidazolyl zwitterionic polymer, PVDF membrane modified by imidazolyl zwitterionic polymer and modification method of imidazolyl zwitterionic polymer |
| CN117626665A (en) * | 2023-12-07 | 2024-03-01 | 东华大学 | A bioactive carbon fiber material and its preparation method, composite material and application |
-
2024
- 2024-03-07 CN CN202410257828.9A patent/CN118105538B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110627955A (en) * | 2019-09-23 | 2019-12-31 | 华东理工大学 | Zwitterionization-based polyvinylimidazole terpolymer and preparation method and application |
| CN112778564A (en) * | 2021-01-06 | 2021-05-11 | 吉林大学 | Carbon fiber reinforced polyether-ether-ketone composite material, and biological activity improvement method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN118105538A (en) | 2024-05-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN118105538B (en) | Modified fiber reinforced PEEK bone scaffold material and preparation method thereof | |
| de Souza et al. | Phosphorylation of chitosan to improve osteoinduction of chitosan/xanthan-based scaffolds for periosteal tissue engineering | |
| US9272045B2 (en) | Method of tissue repair using a composite material | |
| Suneetha et al. | Bone-like apatite formation in biocompatible phosphate-crosslinked bacterial cellulose-based hydrogels for bone tissue engineering applications | |
| US20090074837A1 (en) | Bioresorbable Calcium-Deficient Hydroxyapatite Hydrogel Composite | |
| Yilmaz et al. | From a plant secretion to the promising bone grafts: Cryogels of silicon-integrated quince seed mucilage by microwave-assisted sol–gel reaction | |
| CN115475283B (en) | Tissue engineering bone constructed based on hydrogel material and preparation method and application thereof | |
| de Olyveira et al. | Surface physical chemistry properties in coated bacterial cellulose membranes with calcium phosphate | |
| CN111961227B (en) | A kind of graphene quantum dot/hydrogel composite material, its preparation method and application | |
| CN114452441A (en) | Skull repairing polyether-ether-ketone material and preparation method thereof | |
| CN110507842B (en) | Bacterial cellulose/hyaluronic acid/epsilon-polylysine functional dressing and preparation method thereof | |
| Sowmya et al. | Biocompatible β-chitin hydrogel/nanobioactive glass ceramic nanocomposite scaffolds for periodontal bone regeneration | |
| Zhou et al. | Surface configuration of microarc oxidized Ti with regionally loaded chitosan hydrogel containing ciprofloxacin for improving biological performance | |
| Han et al. | An antibacterial membrane based on Janus bacterial cellulose with nano-sized copper oxide through polydopamine conjugation for infectious wound healing | |
| CN112876724B (en) | Polyether-ether-ketone composite material containing osteogenesis-promoting medicine and preparation method and application thereof | |
| Akturk et al. | Optimization and characterization of poly (ℇ-caprolactone) nanofiber mats doped with bioactive glass and copper metal nanoparticles | |
| CN114796582A (en) | Preparation method of bacteriostatic gel containing graphene oxide | |
| CN108219360B (en) | Medical polyether-ether-ketone composite material and preparation method thereof | |
| PL240725B1 (en) | Biomaterial based on natural polysaccharide - β-1,3-glucan (curdlan) and ceramics for applications in bone tissue engineering and method of its preparation | |
| CN117482294A (en) | Bionic rejection-resistant porous titanium alloy implant and preparation method and application thereof | |
| Qin et al. | Green synthetic sodium alginate-glycerol-MXene nanocomposite membrane with excellent flexibility and mineralization ability for guided bone regeneration | |
| CN120242147B (en) | Articular cartilage repair material and preparation method thereof | |
| CN112057667A (en) | Degradable and absorbable biological hemostatic material | |
| Bayraktar | Biopolymer Bacterial Cellulose Produced by Bacteria and its Use in Health | |
| Sowmyaa et al. | Biocompatible β-chitin hydrogel/nanobioactive glass ceramic nanocomposite scaffolds for periodontal bone regeneration |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |