CN110448726A - A kind of preparation method of polyester/nano combined bone renovating material of fluorescent rare earth MOF - Google Patents
A kind of preparation method of polyester/nano combined bone renovating material of fluorescent rare earth MOF Download PDFInfo
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Abstract
The present invention relates to a kind of polyester/fluorescent rare earth MOF nano combined bone renovating material preparation methods, using terephthalic acid (TPA) and lactic acid as organic ligand, using luminescence rare earth ion as metal unit, construct a kind of preparation method of luminescence generated by light MOF nano material.The degradable composite bone repairing material obtained by this method, internal luminescent properties are excellent, penetration into tissue is strong, degradation behavior in material bodies is directly observed convenient for external, the purer terpolymer 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 rare earth MOF additional amount 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 polyester/fluorescent rare earth MOF nano combined bone renovating material preparation methods, and in particular to one
Kind using biodegradable polyesters as matrix, rare earth MOF nano material is reinforcing agent and tracer, preparation have simultaneously self-reinforcing with
The bone-repairing composite material of fluorescent effect.The invention belongs to bio-medical composition fields.
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 degradable polymeric material, material bodies
It is always to limit the main problem of its clinical application that interior degradation process, which can not carry out implementing tracking etc., and biodegradable composite wood
Material is expected to solve the above problems.
Such as mechanical performance, degradation efficiency of entire material can be changed by changing component allotment for copolymer
Etc. performances and cause more to pay close attention to.Wherein, polylactic acid-trimethylene carbonate-glycolide (PLLA-TMC-GA) ternary polymerization
Object is recent it has been reported that in this terpolymer as the potentiality that bio-medical material is applied, and polylactic acid (PLLA) component mentions
For mechanical strength guarantee, a small amount of polyglycolide (PGA) can accelerate the degradation rate of copolymer, meanwhile, the poly- Sanya of elastomer
The introducing of methyl carbonic (PTMC) component can improve the toughness of copolymer, and since its catabolite is neutrality, Ke Yitong
When reduce inflammation risk.Therefore, in degradable synthesized polymer material in bone renovating bracket material field, compared to pure poly- cream
The toughness of acid is poor, the problems such as poly-caprolactone degradation time is slow, PLLA-TMC-GA(PLGA) terpolymer can be by flexible
Molecular Design obtain having the characteristics that meet bone repairing support different mechanical properties and degradation rate etc. and require.But people
The Young's modulus of cortex bone is between 15-20 GPa in body, and compression strength is between 100-200 MPa, the Young mould of cancellous bone
For amount between 0.1-2 GPa, compression strength, should be with human body autologous bone as ideal bone renovating material between 2-20 MPa
Mechanical strength match.Therefore, PLTG terpolymer be applied to bone tissue engineer there is still a need in terms of add
To improve.
In recent years, the synthesis of nano rare earth metal organic frame (MOF) material and its in biomedicine, especially in tumour
Application study in terms of diagnosing and treating causes scientists and widely pays close attention to.MOF is famous with its porosity, wide at present
It is general to be applied to multiple fields, such as nonlinear optics, gas absorption, catalysis and chemical sensitisation.In order to expand the application model of MOF
It encloses, more and more novel MOF composite materials are developed.Have between metal ion and macromolecule polar group extremely strong
Interaction, the interaction provide chance for high molecular performance improvement, become the high molecular hot spot of blending and modifying.And it is dilute
Coordination can occur with hydroxyl, carboxyl, amino etc. for earthmetal cations, this property is that rare earth ion polydactyl acid class is high
Molecule provides theoretical basis.With carboxyl coordination can occur for the rare earth ion that MOF material itself contains, and its organic is matched
Body and poly-lactic acid material have certain compatibility again, and therefore, rare earth MOF/ lactic acid composite material is promoted in its mechanical property
Aspect has potential application.Again since rare earth MOF has unique optical property, it is for example glimmering to can be used for bio-imaging
Light imaging, and the rare earth luminous body for having the characteristics that fluorescence penetration power is strong, being used to quantitatively with intuitive detection implantation material
Interior degradation process is without performing the operation.
Therefore, the present invention attempts to solve degradation material later period mechanical support deficiency, and degradation behavior can not be observed in vitro
It challenges, using degradable poly (lactic acid-glycolide-trimethylene carbonate) random copolymer as matrix, is with rare earth-lactic acid MOF
Fluorescer prepares while having self-reinforcing effect and can observe the bone renovating material of implantation material degradation process in vitro.
Summary of the invention
For it is existing it is degradable it is material implanted can not carry out real-time monitoring in vitro, it is a kind of poly- the invention reside in providing
Ester/fluorescent rare earth MOF nano combined bone renovating material preparation method, it is a kind of using terephthalic acid (TPA) and lactic acid as organic ligand,
Using luminescence rare earth ion as metal unit, a kind of preparation method of luminescence generated by light MOF nano material is constructed.This method is to utilize
The porosity and fluorescence feature of rare earth MOF, is added to as reinforcing agent and fluorescer and needs to be promoted mechanical property
In polyester matrix, degradable polymer is not only set to meet the requirement of bone renovating material, and can directly observe implantation in vitro
The degradation process of internal bone renovating material.
The present invention adopts the following technical scheme: a kind of polyester/fluorescent rare earth MOF nano combined bone renovating material preparation side
Method, using luminescence rare earth ion as metal unit, constructs a kind of luminescence generated by light MOF using terephthalic acid (TPA) and lactic acid as organic ligand
The preparation method of nano material, mainly comprises the steps that
1) preparation of Rare Earth Europium organic frame (Eu-MOF) nano particle
By terephthalic acid (TPA) (H2IPA it) is dissolved in the mixed solution of dimethylformamide (DMF) and water with europium salt, it is described
H2The molar ratio of IPA and europium salt is 1/10 ~ 1/1, and micro polyvinylpyrrolidone (PVP, K30) is added as surface-active
Agent, 100 DEG C of oil baths stir 5 ~ 30 min, after filtering, are dried in vacuo at room temperature, obtain Eu-MOF nano-particle product；
2) surface of Eu-MOF nano particle is modified
Dried Eu-MOF nano particle and lactic acid (HL) are added in ethanol solution, the Eu-MOF nano particle
Molar ratio with HL is 1/1 ~ 2/1, stirs lower 6 ~ 48 h of back flow reaction, filters, washed repeatedly with ethyl alcohol and obtain solid sample powder
End is dried in vacuo at 65 DEG C, and product is denoted as Eu-HL-MOF；
3) degradable polyester/rare earth MOF composite material preparation
Terpolymer polyester is dissolved in CH first2Cl2In solvent, polyester copolymer solution is obtained；Secondly, being by additive amount
Eu-MOF nano particle after the surface of 1-20 wt% is modified is added in polyester copolymer solution, by magnetic agitation and is surpassed
Sonication is transferred to natural volatile dry in quartzy box after being mixed uniformly, constant weight is finally dried under vacuum under room temperature, i.e.,
Obtain degradable polyester/rare earth MOF composite material.
Wherein, europium salt is europium nitrate, is also possible to: terbium nitrate, ytterbium nitrate, thulium nitrate etc. have the rare earth nitre of fluorescent characteristic
One of hydrochlorate.
In the present invention, the volume ratio of the mixed solution of the DMF and water is 1/4.
The concentration of heretofore described terpolymer polyester is 5 ~ 20 w/v%.
Further, the terpolymer polyester is poly- (lactic acid-glycolide-trimethylene carbonate) ternary polymerization
Object.
In the present invention, in poly- (lactic acid-glycolide-trimethylene carbonate) terpolymer, three kinds of monomers
Molar ratio lactide/glycolides/trimethylene carbonate is 98/1/1 ~ 80/10/10.
The present invention has the advantages that
The present invention is good by the excellent penetrability of luminescent properties using the terephthalic acid (TPA) of biography energy excellent effect as the organic ligand of MOF
Metal ligand of the rare earth ion as MOF, lactic modified, which is further added, makes its Ligands as rare earth element, not only
Increasing biography can act on, and improve rare earth element luminous efficiency and stability, and improve the biocompatibility of MOF nano particle.
The method that novel light-emitting MOF nano particle prepared by the present invention passes through solution blending as reinforcing agent, fluorescer and compatilizer
It is added in poly- (lactic acid-glycolide-trimethylene carbonate) random copolymer matrix, not only acts as real time monitoring implantation material
The effect of degradation behavior in vivo, while the mechanical property of polymer can be increased, degradable polyester is expanded in bone renovating material
The application in field.
The degradable composite bone repairing material obtained by this method, internal luminescent properties are excellent, and penetration into tissue is strong, just
Degradation behavior in material bodies is directly observed in external, the purer terpolymer of mechanical strength is highly improved, applicable property
The bone renovating material of the energy higher load-bearing bony site of index request uses.The present invention is simple, strong operability, rare earth
MOF additional amount is few, and easy processing molding, gained composite material is able to satisfy the demand of clinical application.
Detailed description of the invention
Fig. 1 is the transmission electron microscope figure of Eu-MOF nano particle prepared by embodiment 1；
Fig. 2 is the transmission electron microscope figure of the Eu-HL-MOF nano particle after modified prepared by embodiment 1；
Fig. 3 is the XRD diagram of MOF nano particle prepared by embodiment 1；
The excitation and transmitting fluorescence spectra that Fig. 4 is Eu-HL-MOF prepared by embodiment 1；
Fig. 5 is answering for the Eu-HL-MOF nano particle of 5% content of pure terpolymer (PLTG) prepared by embodiment 1 and addition
The stress-strain diagram of condensation material (PLTG/5%MOF)；
Fig. 6 is the transmission electron microscope figure of the Tb-HL-MOF nano particle after modified prepared by embodiment 2；
The excitation and transmitting fluorescence spectra that Fig. 7 is Tb-HL-MOF prepared by embodiment 2；
Fig. 8 is answering for the Eu-HL-MOF nano particle of 2% content of pure terpolymer (PLTG) prepared by embodiment 3 and addition
The stress-strain diagram of condensation material (PLTG/2%MOF)；
Fig. 9 is pure terpolymer (PLTG) prepared by embodiment 4 and the Eu-HL-MOF nano particle for adding 10% content
The stress-strain diagram of composite material (PLTG/10%MOF).
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 preparation method of polyester/nano combined bone renovating material of fluorescent rare earth MOF, which is characterized in that with terephthalic acid (TPA)
A kind of preparation side of luminescence generated by light MOF nano material is constructed using luminescence rare earth ion as metal unit with lactic acid for organic ligand
Method, according to the following steps:
1) preparation of Rare Earth Europium organic frame (Eu-MOF) nano particle
By 0.17g H2IPA and 0.45 g Eu (NO3)3·6H2O is dissolved in the mixed of 6 mL dimethylformamides (DMF) and 24 mL water
Close in solution, the polyvinylpyrrolidone-K30(PVP, K30 of 0.6 g be added) it is used as surfactant, reactant is in 100 DEG C of temperature
Under degree, 10 min of oil bath agitating and heating is dried in vacuo at room temperature after filtering, obtains Eu-MOF nano-particle product.Fig. 1 is Eu-
The transmission electron microscope figure of MOF nano particle, as seen from the figure, Eu-MOF nano particle are uniform spherome, and average grain diameter is
40 nm。
2) surface of Eu-MOF nano particle is modified
1g dried Eu-MOF nano particle and 0.09 g lactic acid (HL) are added in ethanol solution, reaction is stirred at reflux
12 h are filtered, are washed repeatedly with ethyl alcohol and obtain solid sample powder, be dried in vacuo at 65 DEG C, product is denoted as Eu-HL-MOF.Fig. 2
The transmission electron microscope figure of Eu-HL-MOF nano particle after for modification obtains Eu-HL- as seen from the figure after lactic acid is coordinated
MOF nano particle still keeps the pattern of uniform spherome, and average grain diameter is 50 nm.
The XRD diagram of Eu-HL-MOF nano particle of the Fig. 3 for Eu-MOF nano particle and after being modified.As seen from the figure, two kinds
More sharp diffraction maximum is presented in the XRD diagram of MOF, it was demonstrated that its crystallinity is relatively high, the diffraction maximum of Eu-HL-MOF nano particle
Intensity is slightly lower compared with Eu-MOF nano particle, illustrates that the introducing of lactic acid causes the crystallinity decline of MOF nano particle.
The excitation and transmitting fluorescence spectra that Fig. 4 is Eu-HL-MOF.As seen from the figure, materials show rare-earth europium ion
Feux rouges characteristic emission peak illustrates that the nano material has feux rouges imaging function.
3) degradable polyester/rare earth MOF composite material preparation
Poly- (lactic acid-glycolide-trimethylene carbonate) terpolymer (90/5/5) of 10 g is dissolved in 100 mL
CH2Cl2In solvent, 0.5 g rare earth MOF nano particle of the surface after modified is added in polyester copolymer solution, is passed through
Magnetic agitation and ultrasonic treatment are transferred to natural volatile dry in quartzy box after being mixed uniformly, finally vacuum is dry under room temperature
It is dry to constant weight to get arrive degradable polyester/rare earth MOF composite material.
Fig. 5 is pure terpolymer (PLTG) and adds the composite material of the Eu-HL-MOF nano particle of 5% content
(PLTG/5%MOF) stress-strain diagram, it is as seen from the figure, compound after the novel inorganic nano particle for adding 5% content
The purer PLTG copolymer of the mechanical property of material obviously increases, tensile strength, and Young's modulus is respectively with elongation at break
38.9 MPa, 1.62 MPa and 275.1%, purer PLTG have been respectively increased 41.5%, 34.2% and 37.6%.
Embodiment 2
A kind of polyester/nano combined bone renovating material of fluorescent rare earth MOF, prepares according to the following steps:
Firstly, by 0.17g H2IPA and 0.44 g Tb (NO3)3·6H2O is dissolved in 6 mL dimethylformamides (DMF) and 24 mL
In the mixed solution of water, the polyvinylpyrrolidone-K30(PVP, K30 of 0.6 g is added) it is used as surfactant.Reactant exists
At a temperature of 100 DEG C, 10 min of oil bath agitating and heating is dried in vacuo at room temperature after filtering, obtains product Eu-MOF nano particle.
Secondly, 1g dried Tb-MOF nano particle and 0.09 g lactic acid (HL) are added in ethanol solution, stir
12 h of back flow reaction is mixed, is filtered, is washed repeatedly with ethyl alcohol and obtain solid sample powder, be dried in vacuo under 65 C, product is denoted as Tb-
HL-MOF。
Finally, poly- (lactic acid-glycolide-trimethylene carbonate) terpolymer (90/5/5) of 10 g is dissolved in 100
mL CH2Cl2In solvent.0.5 g rare earth MOF nano particle of the surface after modified is added in polyester copolymer solution, is led to
Cross magnetic agitation and ultrasonic treatment be mixed uniformly after be transferred in quartzy box natural volatile dry, be dried in vacuo under room temperature
To constant weight to get arrive degradable polyester/rare earth MOF composite material.
Fig. 6 is the transmission electron microscope figure of Tb-HL-MOF nano particle.As seen from the figure, Tb-MOF nano particle is equal
Even sphere, average grain diameter are 50 nm.
The excitation and transmitting fluorescence spectra that Fig. 7 is Tb-HL-MOF.As seen from the figure, materials show rare earth terbium ion
Green light characteristic emission peak illustrates that the nano material has green light imaging function.
Embodiment 3
A kind of polyester/nano combined bone renovating material of fluorescent rare earth MOF, prepares according to the following steps:
Firstly, by 0.17g H2IPA and 0.45 g Eu (NO3)3·6H2O is dissolved in 6 mL dimethylformamides (DMF) and 24 mL
In the mixed solution of water, the polyvinylpyrrolidone-K30(PVP, K30 of 0.6 g is added) it is used as surfactant.Reactant exists
At a temperature of 100 DEG C, 10 min of oil bath agitating and heating is dried in vacuo at room temperature after filtering, obtains product Eu-MOF nano particle.
Secondly, 1g dried Eu-MOF nano particle and 0.09 g lactic acid (HL) are added in ethanol solution, stir
12 h of back flow reaction is mixed, is filtered, is washed repeatedly with ethyl alcohol and obtain solid sample powder, be dried in vacuo under 65 C, product is denoted as Eu-
HL-MOF。
Finally, poly- (lactic acid-glycolide-trimethylene carbonate) terpolymer (90/5/5) of 10 g is dissolved in 100
mL CH2Cl2In solvent.0.2 g rare earth MOF nano particle of the surface after modified is added in polyester copolymer solution, is led to
Cross magnetic agitation and ultrasonic treatment be mixed uniformly after be transferred in quartzy box natural volatile dry, the last vacuum under room temperature
Drying arrives degradable polyester/rare earth MOF composite material to constant weight.
Fig. 8 is pure terpolymer PLTG and adds the stress of the composite material of the Eu-HL-MOF nano particle of 2% content
Strain curve.As seen from the figure, after the novel inorganic nano particle for adding 2% content, the mechanical property of composite material is purer
Polyester copolymer increased, tensile strength, and Young's modulus and elongation at break are respectively 33.9 MPa, 1.46 MPa and
245.1%, purer PLTG has been respectively increased 23.3%, 33.1% and 22.6%.
Embodiment 4
A kind of polyester/nano combined bone renovating material of fluorescent rare earth MOF, prepares according to the following steps:
Firstly, by 0.17g H2IPA and 0.45 g Eu (NO3)3·6H2O is dissolved in 6 mL dimethylformamides (DMF) and 24 mL
In the mixed solution of water, the polyvinylpyrrolidone-K30(PVP, K30 of 0.6 g is added) it is used as surfactant.Reactant exists
At a temperature of 100 DEG C, 10 min of oil bath agitating and heating is dried in vacuo at room temperature after filtering, obtains product Eu-MOF nano particle.
Secondly, 1g dried Eu-MOF nano particle and 0.09 g lactic acid (HL) are added in ethanol solution, stir
12 h of back flow reaction is mixed, is filtered, is washed repeatedly with ethyl alcohol and obtain solid sample powder, be dried in vacuo under 65 C, product is denoted as Eu-
HL-MOF。
Finally, poly- (lactic acid-glycolide-trimethylene carbonate) terpolymer (90/5/5) of 10 g is dissolved in 100
mL CH2Cl2In solvent.1 g rare earth MOF nano particle of the surface after modified is added in polyester copolymer solution, is passed through
Magnetic agitation and ultrasonic treatment are transferred to natural volatile dry in quartzy box after being mixed uniformly, finally vacuum is dry under room temperature
It is dry to constant weight to get arrive degradable polyester/rare earth MOF composite material.
Fig. 9 is pure terpolymer (PLTG) prepared by embodiment 4 and the Eu-HL-MOF nanometer for adding 10% content
The stress-strain diagram of the composite material (PLTG/10%MOF) of grain.As seen from the figure, it is received in the novel inorganic for adding 10% content
After rice grain, the purer polyester copolymer of the mechanical property of composite material be increased, tensile strength, Young's modulus and fracture
Elongation is respectively 34.9 MPa, and 1.64 MPa and 209.1%, purer PLTG have been respectively increased 26.9%, 34.3% and 4.6%.
Claims (6)
1. a kind of polyester/fluorescent rare earth MOF nano combined bone renovating material preparation method, which is characterized in that with terephthaldehyde
Acid and lactic acid construct a kind of preparation of luminescence generated by light MOF nano material using luminescence rare earth ion as metal unit for organic ligand
Method, comprising the following steps:
1) preparation of Rare Earth Europium organic frame (Eu-MOF) nano particle
By terephthalic acid (TPA) (H2IPA it) is dissolved in the mixed solution of dimethylformamide (DMF) and water with europium salt, the H2IPA
It is 1/10 ~ 1/1 with the molar ratio of europium salt, micro polyvinylpyrrolidone (PVP, K30) is added as surfactant, 100
5 ~ 30 min are stirred in DEG C oil bath, after filtering, are dried in vacuo at room temperature, are obtained product Eu-MOF nano particle；
2) surface of Eu-MOF nano particle is modified
Dried Eu-MOF nano particle and lactic acid (HL) are added in ethanol solution, the Eu-MOF nano particle
Molar ratio with HL is 1/1 ~ 2/1, stirs lower 6 ~ 48 h of back flow reaction, filters, washed repeatedly with ethyl alcohol and obtain solid sample powder
End is dried in vacuo at 65 DEG C, and product is denoted as Eu-HL-MOF；
3) degradable polyester/rare earth MOF composite material preparation
Terpolymer polyester is dissolved in CH first2Cl2In solvent, polyester copolymer solution is obtained；Secondly, being by additive amount
Eu-MOF nano particle after the surface of 1-20 wt% is modified is added in polyester copolymer solution, by magnetic agitation and is surpassed
Sonication is transferred to natural volatile dry in quartzy box after being mixed uniformly, constant weight is finally dried under vacuum under room temperature, i.e.,
Obtain degradable polyester/rare earth MOF composite material.
2. polyester/fluorescent rare earth MOF nano combined bone renovating material preparation method, feature exist according to claim 1
In the europium salt is europium nitrate, or terbium nitrate, ytterbium nitrate, thulium nitrate have in the rare earth nitrades of fluorescent characteristic
One kind.
3. polyester according to claim 1 or claim 2/fluorescent rare earth MOF nano combined bone renovating material preparation method, feature
It is, the volume ratio of the mixed solution of the DMF and water is 1/4.
4. polyester/fluorescent rare earth MOF nano combined bone renovating material preparation method, feature exist according to claim 1
In the terpolymer polyester concentration be 5 ~ 20 w/v%.
5. according to claim 1 or 4 polyester/fluorescent rare earth MOF nano combined bone renovating material preparation method, feature
It is that the terpolymer polyester is poly- (lactic acid-glycolide-trimethylene carbonate) terpolymer.
6. polyester/fluorescent rare earth MOF nano combined bone renovating material preparation method, feature exist according to claim 5
In poly- (lactic acid-glycolide-trimethylene carbonate) terpolymer, molar ratio lactide/second of three kinds of monomers
Lactide/trimethylene carbonate is 98/1/1 ~ 80/10/10.
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| CN111978559A (en) * | 2020-09-08 | 2020-11-24 | 四川大学 | High strength self-setting composite bone implant with MOF structure and preparation thereof |
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Application publication date: 20191115 |