CN110025825A - The modified poly (arylene ether nitrile) bone implant material containing diazanaphthalene terphenyl structure and preparation method thereof in surface - Google Patents
The modified poly (arylene ether nitrile) bone implant material containing diazanaphthalene terphenyl structure and preparation method thereof in surface Download PDFInfo
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- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
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Abstract
The present invention provides a kind of modified poly (arylene ether nitrile) bone implant materials containing diazanaphthalene terphenyl structure and preparation method thereof in surface.A kind of surface has the Phthalazinone poly (arylene ether nitrile) of osteogenic activity coating, prepares functional coating on Phthalazinone poly (arylene ether nitrile) surface, functional coating includes the bone morphogenetic protein layer with osteogenic activity of Electrostatic Absorption.The protein layer with osteogenic activity includes bone morphogenetic protein, collagen, osteopontin, plasma fibrin etc., and albumin layer is fixed to the poly- square ether nitrile surface of Phthalazinone by way of Electrostatic Absorption.The fixed surface of protein includes that protein electrostatic is adsorbed onto the functional group on Phthalazinone poly (arylene ether nitrile) surface or the monolayer of active functional group.Three-dimensional surface structure of the present invention and functional coating can improve the osteogenic activity of poly (arylene ether nitrile).
Description
Technical field
The present invention relates to the modified phthalazones that contains of a kind of medical high polymer implantation material more particularly to a kind of surface to join
Poly (arylene ether nitrile) bone implant material of benzene structure and preparation method thereof.
Background technique
Bone renovating material is one of maximum bio-medical material of clinical demand amount, and bone implant material is as bone renovating material
One kind, be constantly subjected to the attention of people.Macromolecule bone implant material is with its distinctive property and advantage, in bone implant material
Occupy very big specific gravity.Vivo environment is the environment of liquid, macromolecule bone implant material, it is necessary to meet non-toxic, excellent biology
The requirement such as compatibility, chemical stability, suitable physical mechanical property, easy processing molding, preferable property/valence ratio.Wherein, excellent
Biocompatibility and osteogenic activity be most inappeasable, but most important, be that can high molecular material be used for bone implant
The key of material.
Polyether-ether-ketone (PEEK) is widely used as bone as a kind of novel semi-crystalline state aromatic thermoplastic engineering plastics
It is implanted into material.However, the problems such as biocompatibility is not high and osteogenic activity is undesirable is always to influence PEEK implantation body life time
Problem, for the these problems for improving material, researcher carries out surface modification treatment to PEEK, prepares osteoid apatite on surface
Coating and protein layer with osteogenic activity, biocompatibility and osteogenic activity are improved.
The monomer of this full heteroaromatic of diazanaphthalene terphenyl, distortion, non-co-planar structure is introduced into polyarylether molecule
In chain, a series of Phthalazinone type polyarylethers are synthesized, have been the important member in high performance engineering plastics family.Because of its structure
Similar with PEEK, the multiple functions group of Phthalazinone polyarylether can further be modified poly (arylene ether nitrile), and then having can
It can be used as bio-medical material.Phthalazinone polyarylether is that one kind of Dalian University of Technology's independent research is produced with independent intellectual
The novel high-performance thermoplastic resin of power carries out the poly (aryl ether sulfone ketone) containing naphthyridine ketone structure in previous research work
Surface is modified, and the biocompatibility and osteogenic activity of material is greatly improved.The method that the present invention uses is for hydrophobic
Property Phthalazinone poly (arylene ether nitrile) material carry out the modified osteogenic activity to improve material in surface, the surface for improving material is located in advance
Reason process, the prepared coating with osteogenic activity be by electrostatic interaction to the poly- square ether nitrile surface of Phthalazinone at
The protein layer of bone active.
The Phthalazinone poly (arylene ether nitrile) that the present invention uses is a kind of High performance plastic resin haveing excellent performance, mechanical property
Match with the mechanical property of bone.However, its work of the biocompatibility of Phthalazinone poly (arylene ether nitrile) and osteogenic activity lower limit
For the application of bone implant material, the present invention intends synthesizing the coating with osteogenic activity on Phthalazinone poly (arylene ether nitrile) surface, to mention
Its high biocompatibility and osteogenic activity.
Summary of the invention
The object of the present invention is to provide a kind of novel Phthalazinone polyarylethers with osteogenic activity, it is characterised in that miscellaneous
The preparation of naphthalene biphenyl poly (arylene ether nitrile) surface has the coating of osteogenic activity, and coating is included in plane surface to be had by the way that electrostatic interaction is fixed
There is the protein layer of bioactivity.Biologically active protein layer is fixed on Phthalazinone by the method for electrostatic interaction and gathers
Aryl oxide nitrile surface.The biocompatibility and bioactivity of Phthalazinone poly (arylene ether nitrile) can be improved in surface modified coat, and certain
Time in play a role, will assign long-term implant more lasting bioactivity.
Technical solution of the present invention:
A kind of poly (arylene ether nitrile) bone implant material containing diazanaphthalene terphenyl structure that surface is modified, including substrate and painting
Layer, the two are combined as a whole by electrostatic interaction；The substrate is the polyarylether of cyano-containing and diazanaphthalene terphenyl structure
Nitrile, the coating are biologically active protein.
The protein includes bone morphogenetic protein, collagen, osteopontin, plasma fibrin etc..
The poly (arylene ether nitrile) containing diazanaphthalene terphenyl structure, structure expression are as follows:
The glass transition temperature of the poly (arylene ether nitrile) containing diazanaphthalene terphenyl structure is not less than 250 DEG C, and heat is lost
5% decomposition temperature is weighed not less than 480 DEG C, the polyarylether inherent viscosity is 0.1-0.9dL/g；
Wherein, Ar1It is double halogen monomers containing cyano structure for the main structure of double halogen monomers:
Ar2It is any one in having structure or two or more combinations for the main structure of biphenol monomer:
Wherein, R1、R2、R3、R4It is hydrogen, halogenic substituent, phenyl, phenoxy group, the straight chain alkane containing at least one carbon atom
Base, the branched alkyl containing at least one carbon atom or the branched alkoxy containing at least one carbon atom, R1、R2、R3
And R4Structure it is identical or different；
M is positive integer；
N is 0 or positive integer.
The preparation method of the modified poly (arylene ether nitrile) bone implant material containing diazanaphthalene terphenyl structure in surface, step is such as
Under:
The first step, poly (arylene ether nitrile) it is carboxy-modified
The poly (arylene ether nitrile) (PPENK) containing diazanaphthalene terphenyl structure with planar structure or three-dimensional surface structure is set
In the KOH solution of 1~6mol/L, magnetic agitation is condensed back and carried out at 84~105 DEG C, and hydrolysis time is 6 small
When~3 days, after reaction, the material that hydrolysis obtains is placed in hydrochloric acid solution of the concentration less than 2mol/L, is more than after five minutes
Material is washed and is dried, it is spare；
Second step, the surface amination of poly (arylene ether nitrile)
Firstly, using 1- ethyl -3- (3- dimethyl aminopropyl)-carbodiimides (EDC) and n-hydroxysuccinimide
(NHS) surface carboxylic's group of coupling agent activation, activates at least two hour；Wherein, the molar ratio of EDC and NHS is greater than 2:1；
Then after the material that rinsing, drying obtains, the PBS solution for the ethylenediamine that volume fraction is 0.8~2% (v/v) is immersed, room temperature is stirred
It after mixing 12~24 hours, is put into PBS buffer solution (pH=7.4) and washes 5 minutes, then rinsed 3~5 times with clear water, in nitrogen stream
Middle drying；
Third step, heparin are grafted poly (arylene ether nitrile)
By amination poly (arylene ether nitrile) piece immerse the pH=5.6 containing heparin sodium MES buffer solution (in, heparin sodium is in MES
Concentration in buffer solution is 0.5~3mg/mL, further includes EDC and NHS in MES buffer solution, and the concentration of EDC and NHS are
0.1~0.4M after being stirred at room temperature 12~24 hours, is put into the PBS buffer solution of pH=7.4 and washes 5 minutes, then rinsed with clear water
It is 3~5 times, dry in nitrogen stream；
Heparin grafting poly (arylene ether nitrile) is placed in the PBS solution of the pH=7.4 of the protein with osteogenic activity by the 4th step
(0.1M, pH=7.4), magnetic agitation 12 hours~2 days at room temperature, then successively with the sodium tetraborate of 0.125mol/L and
The PBS cleaning solution of the dodecyl sodium sulfate of 0.376mmol/L and deionized water clean, dry after cleaning and are placed in 4 DEG C
Refrigerator is spare.
The method of Phthalazinone poly (arylene ether nitrile) of the another kind preparation surface with carboxylic acid group is to utilize corona treatment
Device is surface-treated Phthalazinone poly (arylene ether nitrile) product, introduces function perssad carboxylate on surface.
The KOH solution is 4mol/L.
The hydrolysis time is 24 hours.
The protein layer thickness has osteogenic activity less than 1 μm.
The ethylenediamine solution is the PBS solution that volume ratio is 1% (v/v).
The concentration of the heparin sodium aqua is 2mg/mL.
The concentration of the EDC and NHS are 0.4mol/LEDC and 0.1mol/LNHS.
The concentration of the protein solution with osteogenic activity is 100ng/mL.
Beneficial outcomes of the invention:
(1) Phthalazinone poly (arylene ether nitrile) preparation method of the surface with osteogenic activity coating is not necessarily to equipment, at low cost, can be right
It is modified that the bone implant part of complicated shape carries out surface.
(2) modified coating prepared by the present invention have osteogenic activity protein layer, have preferable biocompatibility and
Osteogenic activity, under the premise of not influencing poly (arylene ether nitrile) mechanical property, can improve poly (arylene ether nitrile) material biocompatibility and
Osteogenic activity has broad application prospects in terms of bone implant material.
(3) compared with physical absorption protein, by can in poly (arylene ether nitrile) substrate material surface Electrostatic Absorption protein layer
Control the excessive release of protein layer.Compared with chemical bonding protein, the structure of bone morphogenetic protein, Neng Goubao are not changed
The bioactivity of protein is held, biggish biological action can be played in middle or short term.
Detailed description of the invention
Fig. 1 is PPENK, PPENK-NH2, PPENK-Heparin and PPENK-BMP-2 print surface contact angle
Fig. 2 is the standard curve of alanine concentration.
Fig. 3 is the standard curve of semicystinol concentration.
Fig. 4 is the standard curve of heparin content.
Fig. 5 is mtt assay detection and the modified print leaching liquor culture cell survival rate of BMP-2.
Specific embodiment
Below in conjunction with attached drawing and technical solution, a specific embodiment of the invention is further illustrated.
One the present invention is further elaborated in conjunction with specific embodiments.
PPENK structural formula is as follows:
Embodiment one
The first step is successively cleaned with deionized water, ethyl alcohol, acetone and deionized water after PPENK powder hot forming
PPENK plate, is dried for standby.PPENK piece is put into the KOH solution of 4mol/L, is condensed back at 102 DEG C and carries out magnetic force and stirred
It mixes, the reaction time is 24 hours, after reaction, product HPPENK piece is put into the hydrochloric acid solution of 1mol/L, more than 5 minutes
Material is washed and dried afterwards, it is spare；
HPPENK is put into 10mL water by second step, the EDC and 0.1151gNHS of 0.7668g is added, at room temperature magnetic force
Stirring 2 hours, to activate the carboxyl of HPPENK sample surface, after having reacted, with deionized water by sample clean three times.It will pass through
The PBS solution that the HPPENK piece of surface active immerses the ethylenediamine that volume fraction is 1% (v/v) is put after being stirred at room temperature 24 hours
Enter and washed in PBS buffer solution (pH=7.4) 5 minutes, then is rinsed 3~5 times with clear water, it is dry in nitrogen stream；
Third step, heparin are grafted poly (arylene ether nitrile)
Amination poly (arylene ether nitrile) piece is immersed in the MES buffer solution (0.1M, pH=5.6) containing heparin sodium, heparin sodium
The concentration of solution is 2mg/mL, further includes 0.4M EDC and 0.1M NHS in solution, and after being stirred at room temperature 24 hours, it is slow to be put into PBS
It rushes in solution (pH=7.4) and washes 5 minutes, then rinsed 3~5 times with clear water, it is dry in nitrogen stream；
Heparin grafting poly (arylene ether nitrile) is placed in PBS solution (0.1M, the pH=of the protein with osteogenic activity by the 4th step
7.4), magnetic agitation 24 hours at room temperature, then with the sodium tetraborate of 0.125M (include successively 0.066%w/v dodecyl sulphur
Sour sodium) PBS cleaning solution and deionized water it is spare cleaning, being dried after cleaning and being placed in 4 DEG C of refrigerators.
The hydrophilic and hydrophobic that sample surfaces are characterized by water contact angle measuring instrument, using x-ray photoelectron spectroscopy (XPS) point
The situation of change of essential element content after analysing the surface PPENK before modified.Pass through the loading efficiency and release in vitro efficiency of BMP-2
Determine the content of surface BMP-2.Material is characterized as test cell using MC3T3-E1 mice embryonic pre-osteoblast
Biocompatibility and osteogenic activity.
The surface of above method preparation has the PPENK piece of osteogenic activity protein, and performance is as follows:
Test case one
X-ray photoelectron spectroscopic analysis is carried out to PPENK-BMP-2 print, the content of carbon, nitrogen, oxygen element is obtained, with PPENK
And the PPENK of amination, heparin grafting is compared, spectrogram is as shown in table 1.By modification, the element for the material that every step obtains
Content has significant change, while after heparin Electrostatic Absorption BMP-2, and the value of O/C is significantly raised, illustrates that BMP-2 passes through electrostatic
Suction-operated is successfully fixed to material surface.
Table 1 respectively walks modified print constituent content and ratio
Test case two
It is that test liquid measures PPENK, PPENK-NH respectively with water2, PPENK-Heparin and PPENK-BMP-2 print
Surface contact angle, detect its hydrophily.As shown in Figure 1, modified through BMP-2, surface connects the surface contact angle of four samples
Feeler reduces, hydrophily enhancing.
Test case three
Using alanine as standard items, the alanine solution of various concentration is prepared, is measured after being reacted with ninhydrin working solution
Absorbance value, using amino group concentration as abscissa, absorbance is ordinate, draws standard curve, related coefficient 0.9972.Pass through
Absorbance test to experimental material, the surface amino groups content that ninhydrin method measures are 3.745 μm of ol/cm2。
In addition, the cysteine solution of various concentration is prepared using cysteine as standard items, after reacting with BCA working solution
Absorbance value is measured, using semicystinol concentration as abscissa, absorbance is ordinate, draws standard curve, and related coefficient is
0.9954.By the absorbance test to experimental material, the surface amino groups content that ITL/BCA method measures is 7.672 μm of ol/cm2。
The amino content that two methods measure is identical on the order of magnitude, and method is simple, and repeatability is strong, the number measured
According to genuine and believable.
Test case four
Using heparin sodium as standard items, the heparin sodium aqua of various concentration is prepared, is measured after being reacted with toluidine blue solution
Absorbance value, using heparin concentration as abscissa, absorbance is ordinate, draws standard curve, related coefficient 0.9967.Pass through
Absorbance test to experimental material, the heparin content for the surface grafting that toluidines blue laws measures are 53.21 μ g/cm2
Test case five
PPENK powder is hydrolyzed according to identical experiment condition, after obtaining HPPENK, is dissolved with the ratio of 1%w/v
In chloroform, it is then spin coated onto silicon chip surface.It will be incubated for by EDC/NHS solution in room temperature environment containing HPPENK layers of silicon wafer
45 minutes.Then BMP-2 albumen is connected to material surface, with PBS solution cleaning silicon chip surface 2 times.Each print uses rabbit
Anti- BMP-2 polyclonal antibody (1:100 dilution) is incubated for 1 hour, is cleaned three times with PBS.It is more with the goat-anti rabbit of biotin labeling again
Clonal antibody (1:250 dilution) is incubated for 1 hour, is cleaned three times with PBS.Again with streptavidin-alkaline phosphatase conjugate (1:
100 dilutions) it is incubated for 45 minutes, it is cleaned three times with PBS.Finally silicon wafer is dyed with Fast-red-staining kit.It uses5000 3D measure laser capture microdissection sem observation staining conditions.Using the method for histochemical stain.Comparing Si piece can
To observe by the way that after the fixed BMP-2 of heparin electrostatic adsorption, dyestuff is evenly distributed on Si piece surface, illustrates that BMP-2 is fixed
Effect is preferable.
Test case six
Using bright BMP-2 kit, the load efficiency of the obtained material BMP-2 of testing example one.
The fixed efficiency of BMP-2 in embodiment one: loading BMP-2 in a manner of heparin electrostatic interaction, when BMP-2 solution
Concentration 100ng/mL when fixed efficiency be 72.36%
Test case six
Cytotoxicity experiment is carried out to the obtained material of embodiment one using mtt assay, material is immersed in cell culture
In base, after obtaining the leaching liquor of material, using the leaching liquor of various concentration and mouse preosteoblast co-incubation one day, as a result
As shown in Figure 5.
Cytotoxicity the results show that the obtained material of embodiment one, cell reach with respect to appreciation rate 100% with
On, meet requirement of the national standard ISO 10993 to cytotoxicity, obtained material is non-toxic.
Claims (10)
1. a kind of modified poly (arylene ether nitrile) bone implant material containing diazanaphthalene terphenyl structure in surface, which is characterized in that this is poly-
Aryl oxide class bone implant material includes substrate and coating, and the two is combined as a whole by electrostatic interaction；The substrate is containing phenodiazine
The poly (arylene ether nitrile) of miscellaneous naphthalenone biphenyl structural, the coating are the protein with osteogenic activity；
The protein includes bone morphogenetic protein, collagen, osteopontin and plasma fibrin；
The poly (arylene ether nitrile) containing diazanaphthalene terphenyl structure, structure expression are as follows:
Wherein, Ar1It is double halogen monomers containing cyano structure for the main structure of double halogen monomers:
Ar2It is any one in having structure or two or more combinations for the main structure of biphenol monomer:
Wherein, R1、R2、R3、R4It is hydrogen, halogenic substituent, phenyl, phenoxy group, the straight chained alkyl containing at least one carbon atom, contains
There are the branched alkyl of at least one carbon atom or the branched alkoxy containing at least one carbon atom, R1、R2、R3And R4
Structure it is identical or different；
M is positive integer；
N is 0 or positive integer.
2. poly (arylene ether nitrile) bone implant material according to claim 1, which is characterized in that the thickness of the coating is less than 1 μ
m。
3. a kind of preparation method of the modified poly (arylene ether nitrile) bone implant material containing diazanaphthalene terphenyl structure in surface, feature
It is, steps are as follows:
The first step, poly (arylene ether nitrile) it is carboxy-modified
The poly (arylene ether nitrile) containing diazanaphthalene terphenyl structure with planar structure or three-dimensional surface structure is placed in 1~6mol/L
KOH solution in, be condensed back and carry out magnetic agitation at 84~105 DEG C, hydrolysis time is 6 hours~3 days, reaction
After, the material that hydrolysis obtains is placed in hydrochloric acid solution of the concentration less than 2mol/L, is more than that water is carried out to material after five minutes
It washes and 37 DEG C or less dries, it is spare；
Second step, the surface amination of poly (arylene ether nitrile)
Firstly, being coupled using 1- ethyl -3- (3- dimethyl aminopropyl)-carbodiimides EDC and n-hydroxysuccinimide NHS
Surface carboxylic's group of agent activation, reacts 2~24 hours；Wherein, the molar ratio of EDC and NHS is greater than 2:1；Then it rinses, is dry
After dry obtained material, the PBS solution for the ethylenediamine that volume fraction is 0.8~2% is immersed, after being stirred at room temperature 12~24 hours,
It is put into the PBS buffer solution of pH=7.4 and washes 5 minutes, then rinsed 3~5 times with clear water, it is dry in nitrogen stream；
Third step, heparin are grafted poly (arylene ether nitrile)
Amination poly (arylene ether nitrile) piece is immersed in the MES buffer solution containing heparin sodium, heparin sodium is dense in MES buffer solution
Degree is 0.5~3mg/mL, further includes EDC and NHS in MES buffer solution, and the concentration of EDC and NHS are 0.1~0.4M, room temperature
It after stirring 24 hours, is put into the PBS buffer solution of pH=7.4 and washes 5 minutes, then rinsed 3~5 times with clear water, in nitrogen stream
It is dry；Wherein, the pH=5.6 of MES buffer solution；
Heparin grafting poly (arylene ether nitrile) is placed in the PBS solution of biologically active protein by the 4th step, and magnetic force stirs at room temperature
It mixes 12 hours~2 days, then successively with the PBS cleaning solution comprising sodium tetraborate and dodecyl sodium sulfate and deionized water come clear
It washes, dried after cleaning and is placed in 4 DEG C of refrigerators and is spare；Wherein, PBS solution pH=7.4；In PBS cleaning solution, sodium tetraborate
Concentration is 0.125mol/L, the concentration of dodecyl sodium sulfate is 0.376mmol/L.
4. a kind of preparation method of the modified poly (arylene ether nitrile) bone implant material containing diazanaphthalene terphenyl structure in surface, feature
Be, first step poly (arylene ether nitrile) it is carboxy-modified, poly (arylene ether nitrile) is surface-treated using plasma processing apparatus, in table
Face introduces function perssad carboxylate.
5. preparation method according to claim 3 or 4, which is characterized in that the protein with osteogenic activity is molten
The concentration of liquid is 100ng/mL.
6. preparation method according to claim 3 or 4, which is characterized in that in second step, volume fraction be 1% second two
The PBS solution of amine.
7. preparation method according to claim 5, which is characterized in that in second step, ethylenediamine that volume fraction is 1%
PBS solution.
8. according to preparation method described in claim 3,4 or 7, which is characterized in that in second step, the heparin sodium is in MES
Concentration in buffer solution is 2mg/mL.
9. preparation method according to claim 5, which is characterized in that in second step, the heparin sodium buffers molten in MES
Concentration in liquid is 2mg/mL.
10. preparation method according to claim 6, which is characterized in that in second step, the heparin sodium is buffered in MES
Concentration in solution is 2mg/mL.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110585482A (en) * | 2019-08-02 | 2019-12-20 | 大连理工大学 | Heteronaphthalene biphenyl poly (arylene ether nitrile) with antibacterial property and surface modification method thereof |
| CN115068689A (en) * | 2022-06-17 | 2022-09-20 | 北京邦塞科技有限公司 | Bone filling capsular bag and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110585482A (en) * | 2019-08-02 | 2019-12-20 | 大连理工大学 | Heteronaphthalene biphenyl poly (arylene ether nitrile) with antibacterial property and surface modification method thereof |
| CN110585482B (en) * | 2019-08-02 | 2022-03-01 | 大连理工大学 | Heteronaphthalene biphenyl poly (arylene ether nitrile) with antibacterial property and surface modification method thereof |
| CN115068689A (en) * | 2022-06-17 | 2022-09-20 | 北京邦塞科技有限公司 | Bone filling capsular bag and preparation method and application thereof |
| CN115068689B (en) * | 2022-06-17 | 2024-01-19 | 北京邦塞科技有限公司 | Bone filling bag, and preparation method and application thereof |
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| CN110025825B (en) | 2021-09-24 |
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