CN109303933A - Ordered mesoporous material load fluorescent rare earth-POSS complex is used to enhance the preparation and product and application of bone renovating material - Google Patents
Ordered mesoporous material load fluorescent rare earth-POSS complex is used to enhance the preparation and product and application of bone renovating material Download PDFInfo
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- CN109303933A CN109303933A CN201811542780.7A CN201811542780A CN109303933A CN 109303933 A CN109303933 A CN 109303933A CN 201811542780 A CN201811542780 A CN 201811542780A CN 109303933 A CN109303933 A CN 109303933A
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- 239000000463 material Substances 0.000 title claims abstract description 67
- 239000013335 mesoporous material Substances 0.000 title claims abstract description 64
- 210000000988 bone and bone Anatomy 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 47
- 229920000728 polyester Polymers 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000002131 composite material Substances 0.000 claims abstract description 24
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 10
- 239000004626 polylactic acid Substances 0.000 claims abstract description 8
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 58
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 58
- 239000002105 nanoparticle Substances 0.000 claims description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 42
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 235000019441 ethanol Nutrition 0.000 claims description 18
- 229920001432 poly(L-lactide) Polymers 0.000 claims description 18
- 150000002910 rare earth metals Chemical class 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 15
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 claims description 14
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 14
- 230000002708 enhancing effect Effects 0.000 claims description 14
- -1 polytetrafluoroethylene Polymers 0.000 claims description 14
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 9
- 238000013019 agitation Methods 0.000 claims description 9
- 239000003446 ligand Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 229910001868 water Inorganic materials 0.000 claims description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 7
- 238000006392 deoxygenation reaction Methods 0.000 claims description 7
- 238000011065 in-situ storage Methods 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 230000007547 defect Effects 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 125000003368 amide group Chemical group 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- 206010070834 Sensitisation Diseases 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 230000008313 sensitization Effects 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 238000004020 luminiscence type Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- RBMHUYBJIYNRLY-UHFFFAOYSA-N 2-[(1-carboxy-1-hydroxyethyl)-hydroxyphosphoryl]-2-hydroxypropanoic acid Chemical compound OC(=O)C(O)(C)P(O)(=O)C(C)(O)C(O)=O RBMHUYBJIYNRLY-UHFFFAOYSA-N 0.000 claims description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052771 Terbium Inorganic materials 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229920001434 poly(D-lactide) Polymers 0.000 claims description 2
- 229910021426 porous silicon Inorganic materials 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- LLZBVBSJCNUKLL-UHFFFAOYSA-N thulium(3+);trinitrate Chemical compound [Tm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O LLZBVBSJCNUKLL-UHFFFAOYSA-N 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- KUBYTSCYMRPPAG-UHFFFAOYSA-N ytterbium(3+);trinitrate Chemical compound [Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUBYTSCYMRPPAG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- XHVNTTXKFHCRIX-UHFFFAOYSA-N CCOC(C)(O[Si](OCC)(OCC)CCCN)OCC Chemical class CCOC(C)(O[Si](OCC)(OCC)CCCN)OCC XHVNTTXKFHCRIX-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- NFQPKQCSKRLPHP-UHFFFAOYSA-N propyl cyanate Chemical compound CCCOC#N NFQPKQCSKRLPHP-UHFFFAOYSA-N 0.000 claims 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims 1
- 238000009210 therapy by ultrasound Methods 0.000 claims 1
- PKDCQJMRWCHQOH-UHFFFAOYSA-N triethoxysilicon Chemical compound CCO[Si](OCC)OCC PKDCQJMRWCHQOH-UHFFFAOYSA-N 0.000 claims 1
- 239000002086 nanomaterial Substances 0.000 abstract description 6
- 238000001727 in vivo Methods 0.000 abstract description 3
- 229920000620 organic polymer Polymers 0.000 abstract description 3
- 238000005297 material degradation process Methods 0.000 abstract description 2
- 238000000465 moulding Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 238000006731 degradation reaction Methods 0.000 description 12
- 230000015556 catabolic process Effects 0.000 description 9
- 239000011159 matrix material Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000012744 reinforcing agent Substances 0.000 description 5
- 238000002604 ultrasonography Methods 0.000 description 5
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 230000006399 behavior Effects 0.000 description 4
- 238000005266 casting Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 230000003014 reinforcing effect Effects 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 229920001897 terpolymer Polymers 0.000 description 4
- YFHICDDUDORKJB-UHFFFAOYSA-N trimethylene carbonate Chemical compound O=C1OCCCO1 YFHICDDUDORKJB-UHFFFAOYSA-N 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000006071 cream Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000338 in vitro Methods 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- OQURWGJAWSLGQG-UHFFFAOYSA-N 1-isocyanatopropane Chemical compound CCCN=C=O OQURWGJAWSLGQG-UHFFFAOYSA-N 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229920006237 degradable polymer Polymers 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000734 polysilsesquioxane polymer Polymers 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000013139 quantization Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000001356 surgical procedure Methods 0.000 description 1
- YJVUGDIORBKPLC-UHFFFAOYSA-N terbium(3+);trinitrate Chemical compound [Tb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YJVUGDIORBKPLC-UHFFFAOYSA-N 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 239000002023 wood 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
- A61L27/025—Other specific inorganic materials not covered by A61L27/04 - A61L27/12
-
- 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
-
- 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
- A61L27/58—Materials at least partially resorbable by the body
-
- 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)
- Dermatology (AREA)
- Medicinal Chemistry (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Transplantation (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of ordered mesoporous material load fluorescent rare earth-POSS complexs to be used to enhance preparation method of bone renovating material and products thereof and application.Nano material synthesizing ordered mesoporous first, then by rare earth-POSS complex by chemical bonding into mesoporous material, then to its surface be subject to it is polylactic acid modified after be added in polyester material.The degradable composite bone repairing material obtained by this method, not only there is stable fluorescence property, convenient for directly observing material degradation behavior in vivo, and the purer organic polymer of mechanical strength is highly improved, and the bone renovating material that can be applied to the higher load-bearing bony site of performance index request uses.The present invention is simple, strong operability, and the additional amount of inorganic nano material is few, and easy processing molding, gained composite material is able to satisfy the demand of clinical application.
Description
Technical field
The present invention relates to a kind of ordered mesoporous material load fluorescent rare earth-POSS complexs for enhancing bone renovating material
Preparation method and products thereof and application, and in particular to for one kind using rare earth mesoporous nano material as reinforcing agent and fluorescer, biology can
Degradation polyester is matrix, preparation while the composite material with fluorescent effect and self-reinforcing effect.The invention belongs to bio-medicals
Field of compound material.
Background technique
Obvious curative effects have been obtained as Bone Defect Repari and skeletal reconstruction etc. using degradable polymeric material, face
Bed application study is also being continuously increased, but phase mechanical support intensity is insufficient after degradation for single degradable polymeric material,
Degradation rate and bone healing rate mismatch etc. are always to limit the main problem of its clinical application, and biology can drop in material bodies
Solution composite material is expected to solve the above problems.
Aoxidizing silicon-based mesoporous material has some superior structural properties, such as high specific surface area, and big pore volume can
The pore size of tune and it is easy to functionalization etc., there is it in terms of the reinforcing agent as polymer and be widely applied.Such as Run
(Mater. Chem. Phys.2007,105,341) has synthesized PMMA/MCM-41 composite wood using the method for in-situ polymerization
Material, it is right to its mechanical behavior research shows that the addition of MCM-41 mesoporous material, changes the fracture mechanism and energy consumption mode of PMMA
It plays the role of activeness and quietness.In addition, being aoxidized silicon-based mesoporous for the low biocompatibility of other non-silicon materials
Material has excellent biocompatibility.So it is in bio-sensing, bio-imaging and diagnosis, biocatalysis, Bone Defect Repari and bracket
Engineering and drug delivery etc. also have broad application prospects.
Cage modle polysilsesquioxane, English name polyhedral oligomeric silsesquioxane, referred to as
POSS, general formula (RSiO3/2) n, wherein R is eight apex angle Si atom institute linking groups.POSS is the silicon alternately connected by Si-O
The inorganic kernel of oxygen skeleton composition, the group R that Si atom is connected on its eight apex angles can be reactivity or inertia base
Group.
Degradation process observation in degradation material body is mainly detected and is evaluated using Quantitative Analysis of Microstructure method at present,
Quantitative Analysis of Microstructure method is to estimate material by the shared area change of material in observation different times histotomy and tissue
Palliating degradation degree.But this method needs to make a large amount of histotomy and by image quantization, whole process is time-consuming and laborious.And
It is rare earth luminous to have the characteristics that fluorescence penetration power is strong, the internal degradation process of quantitative and intuitive detection implantation material can be used to
Without surgical procedure.Polyhedral oligomeric silsesquioxane (POSS) containing active function groups can be used as structural unit assembling
Prepare the hybrid material of different special constructions.In the research of POSS luminescent properties, POSS modified organic polymer and metal-
Organic coordination compound improves to its luminescent properties.Such as: amino POSS is synthesized with pyridine ligand with amide group
Organic inorganic hybridization ligand, then with rare earth nitrades cooperate, obtain the strong luminescent rare earth complexes of photo and thermal stability.Such as China
Application number of invention patent: 201110056754.5 are related to a kind of preparation side of luminescent rare earth complexes that amine phenyl POSS is modified
Method.
Summary of the invention
It is easy to reunite for existing fluorescent nano particle, the disadvantages of fluorescence intensity is not high, poor biocompatibility, mesh of the present invention
Be the preparation side that a kind of ordered mesoporous material load fluorescent rare earth-POSS complex is used to enhance bone renovating material is provided
Method.
Another object of the present invention is: providing a kind of ordered mesoporous material load fluorescent rare earth-of above method preparation
POSS complex is for enhancing bone renovating material product.
Another object of the present invention is to: a kind of application of the said goods is provided.
The object of the invention is realized by following proposal: a kind of ordered mesoporous material load fluorescent rare earth-POSS complex use
It is that biography energy ligand sensitization is dilute with amino POSS using ordered meso-porous silicon oxide as carrier in the preparation method of enhancing bone renovating material
The preparation method of the nano material of native ionoluminescence, includes the following steps:
1), the preparation of fabricated in situ ordered mesoporous material load amino POSS
Silane coupling agent modifies amido POSS.A certain amount of amino POSS is added in 100 mL three-necked bottles, is then poured into 20
ML n,N-Dimethylformamide stirs under nitrogen protection to its dissolution as reaction dissolvent, triethoxy is then slowly added dropwise
Silicon substrate propyl isocyanate (TEPIC), the molar ratio of amino POSS and TEPIC are 1:1 ~ 1:5；Reaction system is set to maintain nitrogen atmosphere
In enclosing, 80 C are stirred at reflux 6 ~ 48 h, and reaction terminates natural cooling, and Rotary Evaporators remove solvent, obtain clear yellow viscous oily liquid
Body is denoted as POSS-Si；
P123 surfactant is add to deionized water, stirring is allowed to dissolve under 35 C, and certain density salt is then added
The mixed solution of ethyl orthosilicate (TEOS) and POSS-Si is slowly added dropwise in acid in whipping process, makes the P123/TEOS/
POSS-Si/HCl/H2Molar ratio between O reactant is 0.0172/0.96/0.04/6/208.33, is added dropwise, and is continued
It is put into the stainless steel cauldron that polytetrafluoroethylene (PTFE) is bushing after stirring 24 h under the conditions of 35 C, 12 ~ 48 h of crystallization under 100 C,
Deionized water repeatedly washed product to neutrality；After being dried under 65 C, is extracted 2 days, be dried to obtain with ethyl alcohol in Soxhlet extractor
The POSS of ordered mesoporous material load, is denoted as (SBA-15)-POSS；
2), the preparation of ordered mesoporous material supported rare earth-POSS complex
By a certain amount of hybrid mesoporous material (SBA-15)-POSS, rare earth nitrate solution and Lin Feiluolin (phen) ligand
It is added in ethanol solution, makes Re3+The molar ratio of/(SBA-15)-POSS/phen is 1/3/1, stirs lower back flow reaction 6 ~ 48
H is filtered, is washed repeatedly with ethyl alcohol and obtain solid sample powder, be dried in vacuo under 65 C, product is denoted as (SBA-15)-POSS-Re
(phen) nano particle；
3), the preparation of the modified ordered mesoporous material in polylactic acid surface
Dried (SBA-15)-POSS-Re (phen) nano particle is weighed, a certain amount of lactide (LLA) and catalyst add
Enter into the toluene solvant of water removal deoxygenation, the mass ratio between LLA and (SBA-15)-POSS-Re (phen) nano particle is 1/
1~10/1；It reacts 12 ~ 48 hours, is cooled to room temperature under 120 °C under nitrogen protection and magnetic agitation, product centrifuge separation,
With a large amount of chloroform (CHCl3) the non-grafted PLLA in the surface (SBA-15)-POSS-Re (phen) of solvent washing removing；Most
The precipitated product isolated afterwards is dried under vacuum to constant weight under 50 °C, obtains the nano particle of PLLA modification, and product is denoted as
PLLA-(SBA-15)-POSS-Re(phen)；
4), the preparation of the order mesoporous composite degradable bone renovating material of polyester/fluorescence
Polyester copolymer is dissolved in CH with the concentration of 5 ~ 20 w/v% first2Cl2In solvent, secondly, by after modified
PLLA- (SBA-15)-POSS-Re (phen) dry particle is added in polyester copolymer solution, passes through magnetic agitation and ultrasound
Processing is transferred in quartzy box natural volatile dry after being mixed uniformly, be finally dried under vacuum under room temperature constant weight to get
To the order mesoporous composite degradable bone renovating material of polyester/fluorescence, wherein PLLA- (SBA-15)-POSS-Re (phen) particle
Additive amount are as follows: 1-20 wt%.
The method of the present invention to have simultaneously reinforcing agent and the nano particle of fluorescer effect carry out it is polymer-modified after addition
Into the polyester matrix for needing to be promoted mechanical property, degradable polymer is not only set to meet the requirement of bone renovating material, and can
Directly to observe the degradation of bone renovating material in vivo.
The present invention solves the challenges such as degradation material later period mechanical support is insufficient, and degradation behavior can not be observed in vitro, with
Degradable poly lactyl random copolymer is matrix, using the rare earth mesoporous material after polylactic acid modified as reinforcing agent and fluorescence
Agent prepares while having self-reinforcing effect and can observe the bone renovating material of degradation process in vitro.
The rare earth nitrate solution are as follows: terbium nitrate, europium nitrate, ytterbium nitrate, thulium nitrate have the rare earth of fluorescent characteristic
One of nitrate.
The structure index of the ordered mesoporous material are as follows: aperture is 2-10 nm, and pore volume is 0.5 ~ 1.5 cm3/ g,
BET specific surface area is 500 ~ 1500 m2/g。
The silane coupling agent is aminopropyl trimethoxysilane, aminopropyl triethoxysilane, bis- (2- ethoxys)-
One of 3- aminopropyl triethoxysilane, N- β (aminoethyl)-γ-aminopropyltrimethoxysilane.
The catalyst is one of stannous octoate, zinc oxide, zinc, zinc chloride.
The polyester base is mainly that polylactide and its copolymer is Poly L-lactic acid (PLLA), poly- L-lactic acid
(PDLA), poly- D, L- lactide (PDLLA), poly lactic-co-glycolic acid (PLGA), polylactic acid-caprolactone (PLA-PCL), poly- cream
One of acid-trimethylene carbonate-glycolide (PLTG).
The present invention provides a kind of ordered mesoporous material load fluorescent rare earth-POSS complex for enhancing bone renovating material,
It is prepared according to any of the above-described the method.
The present invention provides a kind of ordered mesoporous material load fluorescent rare earth-POSS complex and exists for enhancing bone renovating material
Application in Bone Defect Repari
The present invention is using the polyhedral oligomeric silsesquioxane with ordered structure unit as the cooperation of sensitization rare earth luminescence
Then object is loaded in ordered mesoporous material, be conducive to improve rare earth element luminous efficiency and stability, while improving dilute
The biocompatibility of earth elements.The poly- cream of one layer of oligomer is further coated on mesoporous material matrix using chemical grafting method
Acid, to improve the compatibility of nano particle.Novel nano particle prepared by the present invention can be used as reinforcing agent, compatilizer and glimmering
Photo etching is added in polyester matrix by the method for solution blending, not only increases the mechanical property of polymer, while can play
It monitors the degradation behavior of repair materials in vivo in real time, has expanded degradable polyester matrix in the application in bone renovating material field.
The degradable composite bone repairing material obtained by this method not only has stable fluorescence property, convenient for internal
Material degradation behavior is directly observed, and the purer organic polymer of mechanical strength is highly improved, and can be applied to performance index and wants
The bone renovating material of higher load-bearing bony site is asked to use.The present invention is simple, strong operability, inorganic nano material
Additional amount it is few, easy processing molding, gained composite material is able to satisfy the demand of clinical application.
Detailed description of the invention
Fig. 1 is the order mesoporous nano particle of fluorescent rare earth ((SBA-15)-POSS-Tb (phen)) prepared by embodiment 1
SEM figure；
Fig. 2 is the TEM of the order mesoporous nano particle of fluorescent rare earth ((SBA-15)-POSS-Tb (phen)) prepared by embodiment 1
Figure；
Fig. 3 is excitation (a) and transmitting (b) fluorescence of (SBA-15)-POSS-Tb (phen) nano particle prepared by embodiment 1
Spectrogram；
Fig. 4 is PLLA- (SBA-15)-POSS-Tb (phen) nano particle of 5% content of polyester prepared by embodiment 1 and addition
Composite material stress-strain diagram；
Fig. 5 is the SEM of the order mesoporous nano particle of fluorescent rare earth ((SBA-15)-POSS-Eu (phen)) prepared by embodiment 2
Figure；
Fig. 6 is the TEM of the order mesoporous nano particle of fluorescent rare earth ((SBA-15)-POSS-Eu (phen)) prepared by embodiment 2
Figure；
Fig. 7 is excitation (a) and transmitting (b) fluorescence of (SBA-15)-POSS-Eu (phen) nano particle prepared by embodiment 2
Spectrogram.
Specific embodiment
Below by way of specific embodiment, the technical scheme of the present invention will be further described.Embodiment below is to this
The further explanation of invention, and do not limit the scope of the invention.
Embodiment 1
A kind of ordered mesoporous material load fluorescent rare earth-POSS complex is used to enhance the preparation method of bone renovating material, to have
Sequence mesopore silicon oxide is carrier, is the preparation method for passing the nano material of energy ligand sensitization rare earth luminescence with amino POSS,
As follows:
1), the preparation of the POSS of fabricated in situ ordered mesoporous material load
Silane coupling agent modifies amido POSS: 1 mmol, 0.875 g amino POSS being added in 100 mL three-necked bottles, then
20 mL DMF are injected, stirs to it be completely dissolved under nitrogen protection, then, are slowly added dropwise 2 mmol, 0.500 g's
TEPIC is stirred at reflux 12 h in 80 C in nitrogen atmosphere, and Rotary Evaporators remove solvent, and reaction terminates natural cooling, removes solvent,
Clear yellow viscous oily liquid is obtained, POSS-Si is obtained；
1.0 g P123 surfactants are added in 7.5 g deionized waters, 30 g 2 are added under 35 C after stirring and dissolving
Then the mixed solution of ethyl orthosilicate (TEOS) and POSS-Si is slowly added dropwise in whipping process, drips for mmol hydrochloric acid
Finish, continues to be put into the stainless steel cauldron that polytetrafluoroethylene (PTFE) is bushing after stirring 24 h under the conditions of 35 C, under the conditions of 100 C
48 h of crystallization, deionized water repeatedly washed product to neutrality.After being dried under 65 C, extracted 2 days in Soxhlet extractor with ethyl alcohol,
Being dried to obtain white solid powder is hybrid mesoporous material, is denoted as (SBA-15)-POSS；
2), the preparation of ordered mesoporous material supported rare earth-POSS complex
Hybrid mesoporous material SBA-15-POSS, rare earth terbium nitrate and Lin Feiluolin (phen) ligand are added to ethanol solution
In, with molar ratio Tb3+: in the ethanol solution that SBA-15-POSS:phen=1:3:1 is added to, lower 12 h of back flow reaction is stirred,
It filters, is washed repeatedly with ethyl alcohol and obtain solid sample powder, be dried in vacuo under 65 C, obtain (SBA-15)-POSS-Tb (phen)
Nano particle.
3), the preparation of the modified ordered mesoporous material in polylactic acid surface
By in the reaction flask of 1 g (SBA-15)-POSS-Tb (phen) nano particle to water removal deoxygenation, nitrogen protection and magnetic force are stirred
It mixes down, 0.0016 mL Sn (Oct) of silane coupling agent is added2The toluene solvant of 40 mL water removal deoxygenation is dissolved in 5 g lactides
In, 24 h are reacted under 120 °C.Centrifuge separation, with a large amount of chloroform (CHCl3) washing remove it is non-grafted in (SBA-15)-
The PLLA on the surface POSS-Tb (phen).Finally, the precipitated product isolated is dried in vacuo under 50 °C, PLLA modification is obtained
Nano particle PLLA- (SBA-15)-POSS-Tb (phen)；
4), the preparation of the order mesoporous composite degradable bone renovating material of polyester/fluorescence
Enhanced type composite material film with fluorescent functional is prepared by ultrasonic disperse and solution casting method: being handed over first by third
Poly- (lactic acid-glycolide-trimethylene carbonate) that ester/glycolide/trimethylene carbonate molar ratio is 90/5/5
(PLGT) terpolymer is dissolved in dichloromethane solvent, and concentration is 10 w/v%；Secondly, being 5 wt%'s by mass fraction
PLLA- (SBA-15)-POSS-Tb (phen) nano particle is added in above-mentioned copolymer solution, passes through magnetic agitation and ultrasound
Wave processing is transferred in quartzy box after being uniformly dispersed volatilizees naturally, to be dried under vacuum to constant weight under room temperature, obtains order mesoporous material
The reinforcing degradable bone renovating material of material load fluorescent rare earth-POSS complex and polyester copolymer, i.e. polyester/fluorescence are orderly
Composite mesoporous degradable bone renovating material.
Fig. 1 is that the SEM of (SBA-15)-POSS-Tb (phen) nano particle schemes.As seen from the figure, the nanoparticle size is big
About 600 nm are in vermiform, the ropy that composition average-size is 2 μm.
Fig. 2 is that the TEM of (SBA-15)-POSS-Tb (phen) nano particle schemes.As seen from the figure, which has
Six side's symmetrical structures of sequence mesoporous material.
Fig. 3 is excitation (a) and transmitting (b) fluorogram of (SBA-15)-POSS-Tb (phen) nano particle.It can by figure
See, the materials show green light characteristic emission peak of rare earth terbium ion.
Fig. 4 is pure polyester polymers and PLLA- (SBA-15)-POSS-Tb (phen) nano particle for adding 5% content
The stress-strain diagram of composite material.As seen from the figure, after adding a certain amount of novel inorganic nano particle, composite material
The purer polyester copolymer of mechanical property obviously increase.
Embodiment 2
A kind of ordered mesoporous material load fluorescent rare earth-POSS complex is used to enhance the preparation method of bone renovating material, step
It is approximate with embodiment 1, in the steps below:
1), the preparation of the POSS of fabricated in situ ordered mesoporous material load
Silane coupling agent modifies amido POSS: 1 mmol, 0.875 g amino POSS being added in 100 mL three-necked bottles, then
20 mLDMF are injected, are stirred under nitrogen protection to its dissolution, stirred under nitrogen atmosphere is slowly added dropwise 2 after being completely dissolved to it
The TEPIC of 0.500 g of mmol is stirred at reflux 12 h in 80 C in nitrogen atmosphere, reaction terminates natural cooling, Rotary Evaporators
Except solvent, clear yellow viscous oily liquid is obtained, POSS-Si is denoted as and obtains POSS-Si；
1.0 g P123 surfactants are added in 7.5 g deionized waters, 30 g 2 are added under 35 C after stirring and dissolving
Then the mixed solution of ethyl orthosilicate (TEOS) and POSS-Si is slowly added dropwise in whipping process, drips for mmol hydrochloric acid
Finish, continues to be put into the stainless steel cauldron that polytetrafluoroethylene (PTFE) is bushing after stirring 24 h under the conditions of 35 C, under the conditions of 100 C
48 h of crystallization, washed product to neutrality；After being dried under 65 C, is extracted 2 days in Soxhlet extractor with ethyl alcohol, be dried to obtain white
Solid powder is hybrid mesoporous material, is denoted as (SBA-15)-POSS；
2), the preparation of ordered mesoporous material supported rare earth-POSS complex
Hybrid mesoporous material (SBA-15)-POSS, rare earth europium nitrate solution and Lin Feiluolin (phen) ligand are added to second
In alcoholic solution, with molar ratio Eu3+: SBA-15-POSS:phen=1:3:1 is added in the ethanol solution of rare earth nitric acid, stirring
Lower 12 h of back flow reaction is filtered, is washed repeatedly with ethyl alcohol and obtain solid sample powder, be dried in vacuo under 65 C, obtain (SBA-
15)-POSS-Eu (phen) nano particle；
3), the preparation of the modified ordered mesoporous material in polylactic acid surface
By 1 g (SBA-15)-POSS-Eu (phen) nano particle, 0.0016 mL Sn (Oct)2It is dissolved in 5 g lactides
40 mL are removed water in the toluene solvant of deoxygenation, react 24 h under 120 °C under nitrogen protection and magnetic agitation；It is cooled to room
Temperature, centrifuge separation are washed with a large amount of chloroforms and remove the non-grafted PLLA in the surface (SBA-15)-POSS-Eu (phen).Most
Afterwards, the precipitated product isolated is dried under vacuum to constant weight under 50 °C, obtains the nano particle PLLA- (SBA- of PLLA modification
15)-POSS-Eu(phen)。
4), the preparation of the order mesoporous composite degradable bone renovating material of polyester/fluorescence
Enhanced type composite material film with fluorescent functional is prepared by ultrasonic disperse and solution casting method: being handed over first by third
Poly- (lactic acid-glycolide-trimethylene carbonate) that ester/glycolide/trimethylene carbonate molar ratio is 90/5/5
(PLGT) terpolymer is dissolved in dichloromethane solvent, and concentration is 10 w/v%；Secondly, being 5 wt%'s by mass fraction
PLLA- (SBA-15)-POSS-Eu (phen) nano particle is added in above-mentioned copolymer solution, passes through magnetic agitation and ultrasound
Wave processing is transferred in quartzy box after being uniformly dispersed volatilizees naturally, to be dried under vacuum to constant weight under room temperature, obtains order mesoporous material
The reinforcing degradable bone renovating material of material load fluorescent rare earth-POSS complex and polyester copolymer, i.e. polyester/fluorescence are orderly
Composite mesoporous degradable bone renovating material.
Fig. 5 is that the SEM of (SBA-15)-POSS-Eu (phen) nano particle schemes.As seen from the figure, the nanoparticle size is big
About 600 nm are in vermiform, the ropy that composition average-size is 2 μm.
Fig. 6 is that the TEM of (SBA-15)-POSS-Eu (phen) nano particle schemes.As seen from the figure, which has
The hexagonal phase structure of sequence mesoporous material.
Fig. 7 is excitation (a) and transmitting (b) fluorogram of (SBA-15)-POSS-Eu (phen) nano particle.It can by figure
See, the materials show green light characteristic emission peak of rare-earth europium ion.
Embodiment 3
A kind of ordered mesoporous material load fluorescent rare earth-POSS complex is used to enhance the preparation method of bone renovating material, step
It is approximate with embodiment 1, in the steps below:
1), the preparation of the POSS of fabricated in situ ordered mesoporous material load
1 mmol, 0.875 g amino POSS are dissolved in 20 mL DMF, after stirred under nitrogen atmosphere is completely dissolved to it
It being slowly added dropwise the TEPIC of 2 mmol, 0.500 g, is stirred at reflux 12 h in 80 C in nitrogen atmosphere, Rotary Evaporators remove solvent,
Obtain POSS-Si；
1.0 g P123 surfactants are added in 7.5 g deionized waters, 30 g 2 are added under 35 C after stirring and dissolving
Then the mixed solution of ethyl orthosilicate (TEOS) and POSS-Si is slowly added dropwise in mmol hydrochloric acid in whipping process.It drips
To finish, 24 h are stirred in continuation under the conditions of 35 C, 48 h of crystallization under the conditions of 100 C, washed product to neutrality, after being dried under 65 C,
It is extracted 2 days in Soxhlet extractor with ethyl alcohol, being dried to obtain white solid powder is hybrid mesoporous material, is denoted as (SBA-15)-
POSS。
2), the preparation of ordered mesoporous material supported rare earth-POSS complex
By a certain amount of hybrid mesoporous material SBA-15-POSS with molar ratio Yb3+: SBA-15-POSS:phen=1:3:1 adds
Enter into the ethanol solution of rare earth ytterbium nitrate, stirs lower 12 h of back flow reaction, filter, washed repeatedly with ethyl alcohol and obtain solid sample
Powder is dried in vacuo under 65 C, obtains (SBA-15)-POSS-Yb (phen) nano particle.
3), the preparation of the modified ordered mesoporous material in polylactic acid surface
By 1 g (SBA-15)-POSS-Yb (phen) nano particle, 0.0016 mL Sn (Oct)2It is dissolved in 5 g lactides
40 mL are removed water in the toluene solvant of deoxygenation, and 24 h are reacted under 120 °C.Centrifuge separation washs removing not with a large amount of chloroforms
Graft on the PLLA on the surface (SBA-15)-POSS-Yb (phen).Finally, the precipitated product isolated is dry in 50 °C of lower vacuum
It is dry, obtain nano particle PLLA- (SBA-15)-POSS-Yb (phen) of PLLA modification.
4), the preparation of the order mesoporous composite degradable bone renovating material of polyester/fluorescence
Enhanced type composite material film with fluorescent functional is prepared by ultrasonic disperse and solution casting method: being handed over first by third
Poly- (lactic acid-glycolide-trimethylene carbonate) that ester/glycolide/trimethylene carbonate molar ratio is 90/5/5
(PLGT) terpolymer is dissolved in dichloromethane solvent, and concentration is 10 w/v%.Secondly, being 5 wt%'s by mass fraction
PLLA- (SBA-15)-POSS-Yb (phen) nano particle is added in above-mentioned copolymer solution, passes through magnetic agitation and ultrasound
Wave processing is transferred in quartzy box after being uniformly dispersed volatilizees naturally, arrives to be dried under vacuum to constant weight under room temperature order mesoporous
The reinforcing degradable bone renovating material of material load fluorescent rare earth-POSS complex and polyester copolymer.
Embodiment 4
A kind of ordered mesoporous material load fluorescent rare earth-POSS complex is used to enhance the preparation method of bone renovating material, step
It is approximate with embodiment 1, in the steps below:
1), the preparation of the POSS of fabricated in situ ordered mesoporous material load
1 mmol, 0.875 g amino POSS are dissolved in 20 mL DMF, after stirred under nitrogen atmosphere is completely dissolved to it
It being slowly added dropwise the TEPIC of 2 mmol, 0.500 g, is stirred at reflux 12 h in 80 C in nitrogen atmosphere, Rotary Evaporators remove solvent,
Obtain POSS-Si；
1.0 g P123 surfactants are added in 7.5 g deionized waters, 30 g 2 are added under 35 C after stirring and dissolving
Then the mixed solution of ethyl orthosilicate (TEOS) and POSS-Si is slowly added dropwise in mmol hydrochloric acid in whipping process.It drips
Finish, 24 h are stirred in continuation under the conditions of 35 C, 48 h of crystallization under the conditions of 100 C, washed product to neutrality.After being dried under 65 C,
It is extracted 2 days in Soxhlet extractor with ethyl alcohol, is dried to obtain the hybrid mesoporous material of white solid powder, is denoted as (SBA-15)-
POSS。
2), the preparation of ordered mesoporous material supported rare earth-POSS complex
By a certain amount of hybrid mesoporous material SBA-15-POSS with molar ratio Tm3+3 ︰ 1 of ︰ SBA-15-POSS ︰ phen=1 ︰ adds
Enter into the ethanol solution of rare earth thulium nitrate, stirs lower 12 h of back flow reaction, filter, washed repeatedly with ethyl alcohol and obtain solid sample
Powder is dried in vacuo under 65 C, obtains (SBA-15)-POSS-Tm (phen) nano particle.
3), the preparation of the modified ordered mesoporous material in polylactic acid surface
By 1 g (SBA-15)-POSS-Tm (phen) nano particle, 0.0016 mL Sn (Oct)2It is dissolved in 5 g lactides
40 mL are removed water in the toluene solvant of deoxygenation, and 24 h are reacted under 120 °C.Centrifuge separation washs removing not with a large amount of chloroforms
Graft on the PLLA on the surface (SBA-15)-POSS-Tm (phen).Finally, the precipitated product isolated is dry in 50 °C of lower vacuum
It is dry, obtain nano particle PLLA- (SBA-15)-POSS-Tm (phen) of PLLA modification.
4), the preparation of the order mesoporous composite degradable bone renovating material of polyester/fluorescence
Enhanced type composite material film with fluorescent functional is prepared by ultrasonic disperse and solution casting method.Third is handed over first
Poly- (lactic acid-glycolide-trimethylene carbonate) that ester/glycolide/trimethylene carbonate molar ratio is 90/5/5
(PLGT) terpolymer is dissolved in dichloromethane solvent, and concentration is 10 w/v%.Secondly, being 5 wt%'s by mass fraction
PLLA- (SBA-15)-POSS-Tm (phen) nano particle is added in above-mentioned copolymer solution, passes through magnetic agitation and ultrasound
Wave processing is transferred in quartzy box after being uniformly dispersed volatilizees naturally, arrives to be dried under vacuum to constant weight under room temperature order mesoporous
The reinforcing degradable bone renovating material of material load fluorescent rare earth-POSS complex and polyester copolymer.
Claims (9)
1. a kind of ordered mesoporous material load fluorescent rare earth-POSS complex is used to enhance the preparation method of bone renovating material,
It is characterized in that, is the nanometer material for passing energy ligand sensitization rare earth luminescence with amino POSS using ordered meso-porous silicon oxide as carrier
The preparation method of material includes the following:
1), the preparation of the POSS of fabricated in situ ordered mesoporous material load
Silane coupling agent modifies amido POSS: amino POSS being added in 100 mL three-necked bottles, 20 mL N, N- are then poured into
Dimethylformamide (DMF) reaction dissolvent stirs under nitrogen protection to its dissolution, it is different that triethoxy silicon substrate is then slowly added dropwise
Propyl cyanate (TEPIC) makes molar ratio 1:1 ~ 1:5 of amino POSS and TEPIC；Reaction system is set to maintain nitrogen atmosphere
In, 80 C are stirred at reflux 6 ~ 48 h, and reaction terminates natural cooling, removes solvent, obtains clear yellow viscous oily liquid, be denoted as POSS-
Si；
P123 surfactant is add to deionized water, stirring is allowed to dissolve under 35 C, hydrochloric acid is then added, stirred
The mixed solution of ethyl orthosilicate (TEOS) and POSS-Si is slowly added dropwise in journey, makes P123/TEOS/POSS-Si/HCl/H2O is anti-
Answering the molar ratio between object is 0.0172/0.96/0.04/6/208.33, is added dropwise, and 24 h are stirred in continuation under the conditions of 35 C
It is put into the stainless steel cauldron that polytetrafluoroethylene (PTFE) is bushing afterwards, 12 ~ 48 h of crystallization under 100 C, deionized water washs production repeatedly
Object is to neutrality；After being dried under 65 C, is extracted 2 days in Soxhlet extractor with ethyl alcohol, be dried to obtain hybrid mesoporous material, be denoted as
(SBA-15)-POSS；
2), the preparation of ordered mesoporous material supported rare earth-POSS complex
Hybrid mesoporous material (SBA-15)-POSS, rare earth nitrate solution and Lin Feiluolin (phen) ligand are added to second
In alcoholic solution, making rare earth nitrades/(SBA-15)-POSS/phen molar ratio is 1/3/1, stirs lower back flow reaction 6 ~ 48
H is filtered, is washed repeatedly with ethyl alcohol and obtain solid sample powder, be dried in vacuo under 65 C, product is denoted as (SBA-15)-POSS-Re
(phen) nano particle；
3), the preparation of the modified ordered mesoporous material in polylactic acid surface
Dried (SBA-15)-POSS-Re (phen) nano particle is weighed, a certain amount of lactide (LLA) and catalyst add
Enter to water removal deoxygenation toluene solvant in, LLA and it is amino modified after (SBA-15)-POSS-Re (phen) nano particle between
Mass ratio be 1/1 ~ 10/1；It reacts 12 ~ 48 hours, is cooled to room temperature under 120 °C under nitrogen protection and magnetic agitation,
Product centrifuge separation, with a large amount of chloroform (CHCl3) solvent washing remove it is non-grafted in (SBA-15)-POSS-Re (phen)
The PLLA on surface；The precipitated product being finally separating out is dried under vacuum to constant weight under 50 °C, obtains the nanometer of PLLA modification
Grain, product are denoted as PLLA- (SBA-15)-POSS-Re (phen)；
4), the preparation of the order mesoporous composite degradable bone renovating material of polyester/fluorescence
Polyester copolymer is dissolved in CH with the concentration of 5 ~ 20 w/v% first2Cl2In solvent, secondly, by the PLLA- after modified
(SBA-15)-POSS-Re (phen) dry particle is added in polyester copolymer solution, will by magnetic agitation and ultrasonic treatment
It is transferred in quartzy box natural volatile dry after mixing, be finally dried under vacuum under room temperature constant weight to get to polyester/
The order mesoporous composite degradable bone renovating material of fluorescence, the wherein additive amount of PLLA- (SBA-15)-POSS-Re (phen) particle
Are as follows: 1-20 wt%.
2. ordered mesoporous material load fluorescent rare earth-POSS complex is for enhancing bone renovating material according to claim 1
Preparation method, it is characterised in that it is described except solvent uses Rotary Evaporators.
3. ordered mesoporous material load fluorescent rare earth-POSS complex is for enhancing bone renovating material according to claim 1
Preparation method, it is characterised in that the rare earth nitrades be the rare earth nitrades with fluorescent characteristic, include at least: nitric acid
One of terbium, europium nitrate, ytterbium nitrate, thulium nitrate.
4. ordered mesoporous material load fluorescent rare earth-POSS complex is for enhancing bone renovating material according to claim 1
Preparation method, it is characterised in that the structure index of the ordered mesoporous material are as follows: aperture be 2-10 nm, pore volume 0.5
~1.5 cm3/ g, BET specific surface area are 500 ~ 1500 m2/g。
5. ordered mesoporous material load fluorescent rare earth-POSS complex is for enhancing bone renovating material according to claim 1
Preparation method, it is characterised in that the silane coupling agent be aminopropyl trimethoxysilane, aminopropyl triethoxysilane,
One of bis- (2- ethoxy) -3- aminopropyl triethoxysilanes, N- β (aminoethyl)-γ-aminopropyltrimethoxysilane.
6. ordered mesoporous material load fluorescent rare earth-POSS complex is for enhancing bone renovating material according to claim 1
Preparation method, it is characterised in that the catalyst be one of stannous octoate, zinc oxide, zinc, zinc chloride.
7. ordered mesoporous material load fluorescent rare earth-POSS complex is for enhancing bone renovating material according to claim 1
Preparation method, it is characterised in that the polyester base is polylactide and its copolymer, include at least Poly L-lactic acid (PLLA),
Poly- L-lactic acid (PDLA), poly- D, L- lactide (PDLLA), poly lactic-co-glycolic acid (PLGA), polylactic acid-caprolactone (PLA-
PCL), one of polylactic acid-trimethylene carbonate-glycolide (PLTG).
8. a kind of ordered mesoporous material load fluorescent rare earth-POSS complex is for enhancing bone renovating material, it is characterised in that root
It is prepared according to any the method for claim 1-7.
9. a kind of load fluorescent rare earth-POSS complex of ordered mesoporous material according to claim 8 is for enhancing Bone Defect Repari
Application of the material in Bone Defect Repari.
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| CN110448726A (en) * | 2019-08-19 | 2019-11-15 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of preparation method of polyester/nano combined bone renovating material of fluorescent rare earth MOF |
| CN112082980A (en) * | 2020-10-12 | 2020-12-15 | 青海大学 | Preparation method of carbon dot-based ion imprinting fluorescence sensor |
| CN112940342A (en) * | 2021-02-24 | 2021-06-11 | 四川大学 | Method for preparing open-cell ZIF-8/polymer composite foam material by utilizing solid-phase shearing and grinding technology |
| CN114366851A (en) * | 2021-12-31 | 2022-04-19 | 江苏阳生生物股份有限公司 | Bone repair material for massive defects of mandible |
| CN115197693A (en) * | 2021-04-09 | 2022-10-18 | 中国科学院理化技术研究所 | NIR-II region luminous core-shell structure nano particle and preparation method and application thereof |
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| CN114366851B (en) * | 2021-12-31 | 2022-09-02 | 江苏阳生生物股份有限公司 | Bone repair material for massive defects of mandible |
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Effective date of registration: 20231225 Address after: Building C, No. 888 Huanhu West Second Road, Pudong New Area, Shanghai, April 2012 Patentee after: Guona Star (Shanghai) Nanotechnology Development Co.,Ltd. Address before: 201109 Shanghai city Minhang District Jianchuan Road No. 468 Patentee before: SHANGHAI NATIONAL ENGINEERING RESEARCH CENTER FOR NANOTECHNOLOGY Co.,Ltd. |