CN104327293B - Composite film material based on polymer P RGD and preparation method thereof - Google Patents
Composite film material based on polymer P RGD and preparation method thereof Download PDFInfo
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- CN104327293B CN104327293B CN201410670608.5A CN201410670608A CN104327293B CN 104327293 B CN104327293 B CN 104327293B CN 201410670608 A CN201410670608 A CN 201410670608A CN 104327293 B CN104327293 B CN 104327293B
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Abstract
The present invention relates to a kind of composite film material based on polymer P RGD and preparation method thereof, polylactic acid, polymer P RGD, modifted-nano-hydroxyapatite are proportionally added into dichloromethane to be blended into uniformly, it is stirred at room temperature, then in Teflon mould, film forming obtains the composite film material based on polymer P RGD.The present invention is beneficial to be had technical effect that：1st, composite film material of the present invention introduces RGD by two-step method first and prepares PRGD, improves the cell adhesion of material, cell is preferably grown on material；2nd, the nanometer hydroxyapatite in composite film material of the present invention has good biocompatibility and hydrophilic, while can be with the acid product in neutralization materials degradation process, it is to avoid inflammatory reaction is produced during material degradation.
Description
Technical field
The present invention relates to biological and field of nanocomposite materials, more particularly, to a kind of composite membrane based on polymer P RGD
Material and preparation method thereof.
Background technology
In bio-medical material research field, especially in organizational project, slow releasing carrier of medication and nerve repair material side
Face, Nondegradable material due to exist toxicity it is larger, it is internal discharge difficult, the shortcomings of need second operation, gradually tend to superseded.And
What is received much concern is Biodegradable polymer material.This kind of material can be degraded into by hydrolysis or enzymolysis process in vivo
Small-molecule substance, these small molecules tend to be converted, absorb, discharged by body own metabolism, body are not produced as far as possible
Raw toxic and side effects.In numerous organic materials, due to polylactic acid has good biocompatibility, degradability, biology can
Absorbability and mechanical performance, are widely used in the fields such as organizational project, slow releasing carrier of medication and nerve repair material.Simultaneously because
Polylactic acid cell adhesion is bad, and acid product can be produced in degradation process, limits its application in biomaterial.Therefore
Polylactic acid is modified, adhering polypeptide is introduced in polylactic acid molecule chain, strengthen its bioaffinity, and neutralization acidity
Catabolite is into the emphasis for overcoming the problems referred to above.
In polylactic acid molecule chain, only the end of the chain contains outside hydroxyl and carboxyl, is a large amount of methyl on side chain, lacks reactivity
Group, therefore the grafted maleic anhydride on polylactic acid side chain, increase carboxyl-content, are re-introduced into bioactive molecule polypeptide, are beneficial to
The adhesion and growth of cell, reaches the purpose for building bionical polylactic acid sill.
Adhesive polypeptide (RGD) is minimum aminoacid sequence, can be combined with integrin protein-specific, is effectively facilitated thin
Adhesion of the born of the same parents to biomaterial, therefore RGD is grafted in polylactic acid molecule chain, the biology that can improve material well is living
Property, strengthen the Adhesion property of cell；Nanometer hydroxyapatite (n-HAP) can neutralize poly- breast with good biocompatibility
The acid product that acid degradation is produced, therefore which is combined to poly-lactic acid material, the inflammatory that acid product brings can be solved
Reaction.Therefore available adhering polypeptide (RGD) and modifted-nano-hydroxyapatite (n-KHAP) are modified to polylactic acid, are obtained
A kind of biological composite membrane material of excellent combination property.
The content of the invention
For the problems referred to above that prior art is present, the present invention provide a kind of composite film material based on polymer P RGD and
Its preparation method.
The technical scheme adopted by the solution above-mentioned technical problem of the present invention is as follows：Compound film material based on polymer P RGD
Material, which includes modifted-nano-hydroxyapatite (n-KHAP) 0.05-0.15, polymer P RGD 0.5, polylactic acid 0.5, with weight
Part meter.
By such scheme, the preparation method of described polymer P RGD is：
1) with polylactic acid (PDLLA), maleic anhydride (MA) as raw material, dibenzoyl peroxide (BPO) is initiator, dichloro
Methane is solvent, at room temperature mix homogeneously, and then vacuum drying removes solvent, is then warming up to 80-100 DEG C, leads to nitrogen anti-
5-15h is answered, and product A is obtained with dichloromethane-dehydrated alcohol system dissolving purification；
2) product A is dissolved in dichloromethane and forms solution A, taken polypeptide condensing agent and be dissolved in dichloromethane, stirring
Under be added into solution A, adjust pH, react half an hour under ice-water bath, carboxyl is fully activated；It is subsequently adding and is dissolved in dimethyl Asia
The rgd peptide solution of sulfone, by said mixture in 5 DEG C of reaction 5h stirred below, stopped reaction；Reactant liquor is instilled into excessive distillation
In water, the membranaceous precipitate in collection system, and distilled water wash is used, then it is dried under vacuum to constant weight and obtains polymer P RGD.
By such scheme, the quality of the maleic anhydride is the 5%-20% of polylactic acid, the quality of dibenzoyl peroxide
For the 3%-5% of maleic anhydride.
By such scheme, the polypeptide condensing agent is 1- ethyls-(3- dimethylaminopropyls) carbodiimide hydrochloride
(EDCI) mixed liquor of/I-hydroxybenzotriazole (HOBT).
By such scheme, step 2) the regulation pH be using triethylamine adjust pH to 7-8.
By such scheme, the preparation method of described modifted-nano-hydroxyapatite is：In the mixed of ethanol and deionized water
Gamma-aminopropyl-triethoxy-silane (KH-550) is added in closing solution, nanometer hydroxyapatite is subsequently adding, is adjusted with ammonia
PH9-10, reacts 3-4h, solid matter is recovered by filtration, and is placed in baking oven and heats, then solid matter is washed with dehydrated alcohol again
Wash, gained material lyophilization obtains the modifted-nano-hydroxyapatite that amino is contained on surface.
The preparation method of the described composite film material based on polymer P RGD, it is characterised in that by polylactic acid, polymer
PRGD, modifted-nano-hydroxyapatite are proportionally added into dichloromethane and are blended into uniformly, and 5h is stirred at room temperature, then poly- four
In fluorothene mould, film forming obtains the composite film material based on polymer P RGD, each component modified Nano hydroxyl in parts by weight
Base apatite (n-KHAP) 0.05-0.15, polymer P RGD 0.5, polylactic acid 0.5.
, then there is condensation reaction with the amino on RGD in present invention grafted maleic anhydride first in polylactic acid molecule chain
Rgd peptide is introduced, the biocompatibility and biological activity of polylactic acid is enhanced；Prepare the modified nano hydroxyapatite of amphiphilic coupling agent
Lime stone (n-KHAP), and it is compound with PDLLA, PRGD, prepare the biological composite membrane material of excellent combination property.
The present invention is beneficial to be had technical effect that：
1st, composite film material of the present invention introduces RGD by two-step method first and prepares PRGD, improves the cell adhesion of material
Property, cell is preferably grown on material；
2nd, the nanometer hydroxyapatite in composite film material of the present invention has good biocompatibility and hydrophilic, while
Can be with the acid product in neutralization materials degradation process, it is to avoid during material degradation, produce inflammatory reaction.
Description of the drawings
Fig. 1 is the infared spectrum of polymer P DLLA, PRGD in embodiment 1；
Fig. 2 is the water contact angle picture of composite membrane in embodiment 1；
Fig. 3 is the SEM pictures of composite membrane in embodiment 1；
The SEM pictures that Fig. 4 is grown on composite membrane for cell in embodiment 1.
Specific embodiment
With reference to the accompanying drawings and examples, further detailed description is carried out to the present invention, but this explanation will not be constituted
Limitation of the present invention.
Embodiment 1
(1) 1g polylactic acid (PDLLA), 0.1g maleic anhydrides (MA) are weighed, 4mg dibenzoyl peroxides (BPO) are in appropriate
Mix homogeneously under room temperature in dichloromethane, is put in vacuum drying oven to be dried under room temperature and removes solvent to constant weight, then in nitrogen
90 DEG C are warming up under protection, room temperature are cooled to after reaction 10h and are obtained crude product, carried with dichloromethane-dehydrated alcohol system dissolving
It is pure to obtain product A；
(2) weigh during 10mg adhesion peptides (RGD) are dissolved in 10ml dimethyl sulfoxide (DMSO) and obtain RGD solution；Weigh 0.12g
1- ethyls-(3- dimethylaminopropyls) carbodiimide hydrochloride (EDCI) and 0.1g1- hydroxybenzotriazoles (HOBT) are dissolved in two
Chloromethanes obtain being condensed agent solution；
(3) weigh during 1g product A are dissolved in dichloromethane and form solution A, take the condensation agent solution that step (2) is obtained, stir
Solution A is added under state, and it is 7 pH to be adjusted with triethylamine, reacts half an hour, carboxyl is fully activated under ice-water bath；Then
Addition is dissolved in the rgd peptide solution of dimethyl sulfoxide, by said mixture in 5 DEG C of reaction 5h stirred below, stopped reaction；Will be anti-
Drop is answered to enter in excessive distilled water, the membranaceous precipitate in collection system, and distilled water wash is used, then it is dried under vacuum to constant weight
Obtain polymer P RGD；
(4) in the mixed solution of ethanol and deionized water, (volume ratio is 9:1, Unit/mL) middle addition three second of γ-aminopropyl
TMOS (KH-550), is stirred at room temperature 30min, is subsequently adding nanometer hydroxyapatite, and ultrasonic 3min stirs 3h under room temperature,
Then pH to 9-10 being adjusted with ammonia, continuing reaction 3-4h, solid matter is recovered by filtration, room temperature is dried, and solid matter is placed in
Heat in 130 degree of baking ovens 1.5 hours, then again by solid matter absolute ethanol washing 5 times, removing is not bonded in n-HAP
The silane coupler on surface, finally by gained material lyophilization, obtains the modifted-nano-hydroxyapatite that amino is contained on surface
(n-KHAP)；
(5) polymer P RGD, 0.05g step (4) that 0.5g polylactic acid (PDLLA), 0.5g steps (3) are obtained is obtained
Modifted-nano-hydroxyapatite (n-KHAP) adds 30mL dichloromethane to mix to uniform, and 5h is stirred at room temperature, then poly-
In Teflon mold, film forming obtains n-KHAP/PRGD/PDLLA composite film materials.
The infrared spectrogram of the polymer P RGD formed according to above-mentioned condition is shown in Fig. 1, and PRGD is different as can be seen from Figure 1
In the characteristic absorption peak position of PDLLA.The contact angle of the composite membrane n-KHAP/PRGD/PDLLA formed according to above-mentioned condition,
The growth conditions of surface topography and cell on composite membrane are shown in Fig. 2,3,4 respectively.Composite membrane is significantly hydrophilic as can be seen from Figure 2
Property；Composite film surface contains micropore as can be seen from Figure 3, beneficial to the growth of cell；Cell is grown on film as can be seen from Figure 4
It is in good condition.
Embodiment 2
(1) 1g polylactic acid (PDLLA), 0.05g maleic anhydrides (MA) are weighed, 2mg dibenzoyl peroxides (BPO) are dissolved in suitable
Mix homogeneously under room temperature in amount dichloromethane, is put into be dried under room temperature in vacuum drying oven and removes solvent to constant weight, then in nitrogen
80 DEG C are warming up under gas shielded, room temperature are cooled to after reaction 5h and are obtained crude product, carried with dichloromethane-dehydrated alcohol system dissolving
It is pure to obtain product A；
(2) weigh during 10mg adhesion peptides (RGD) are dissolved in 10ml dimethyl sulfoxide (DMSO) and obtain RGD solution；Weigh 0.12g
1- ethyls-(3- dimethylaminopropyls) carbodiimide hydrochloride (EDCI) and 0.1g I-hydroxybenzotriazoles (HOBT) are dissolved in
Dichloromethane obtains being condensed agent solution；
(3) weigh during 1g A are dissolved in dichloromethane and form solution A, take the condensation agent solution that step (2) is obtained, stirring
Under be added into solution A, with triethylamine adjust pH be 8, react half an hour under ice-water bath, carboxyl is fully activated；It is subsequently adding
The rgd peptide solution of dimethyl sulfoxide is dissolved in, by said mixture in 5 DEG C of reaction 5h stirred below, stopped reaction；By reactant liquor
Instill in excessive distilled water, the membranaceous precipitate in collection system, and use distilled water wash, be then dried under vacuum to constant weight and obtain
Polymer P RGD；
(4) in the mixed solution of ethanol and deionized water, (volume ratio is 9:1, Unit/mL) middle addition three second of γ-aminopropyl
TMOS (KH-550), is stirred at room temperature 30min, is subsequently adding nanometer hydroxyapatite, and ultrasonic 3min stirs 3h under room temperature,
Then pH to 9-10 being adjusted with ammonia, continuing reaction 3-4h, solid matter is recovered by filtration, room temperature is dried, and solid matter is placed in
Heat in 130 degree of baking ovens 1.5 hours, then again by solid matter absolute ethanol washing 5 times, removing is not bonded in n-HAP
The silane coupler on surface, finally by gained material lyophilization, obtains the modifted-nano-hydroxyapatite that amino is contained on surface
(n-KHAP)；
(5) modified receive what PRGD, 0.1g step (4) that 0.5g polylactic acid (PDLLA), 0.5g steps (3) are obtained was obtained
Rice hydroxyapatite (n-KHAP) mixes to uniform in adding 30mL dichloromethane, 5h is stirred at room temperature, then in polytetrafluoro
In ethylene mould, film forming obtains n-KHAP/PRGD/PDLLA composite film materials.
Embodiment 3
(1) 1g polylactic acid (PDLLA), 0.2g maleic anhydrides (MA) are weighed, 6mg dibenzoyl peroxides (BPO) are dissolved in suitable
Mix homogeneously under room temperature in amount dichloromethane, is put into be dried under room temperature in vacuum drying oven and removes solvent to constant weight, then in nitrogen
100 DEG C are warming up under gas shielded, room temperature are cooled to after reaction 15h and are obtained crude product, with dichloromethane-dehydrated alcohol system dissolving
Purification obtains product A；
(2) 10mg adhesion peptides (RGD) are weighed it is dissolved in 10ml dimethyl sulfoxide (DMSO) and obtains RGD solution；Weigh 0.12g1-
Ethyl-(3- dimethylaminopropyls) carbodiimide hydrochloride (EDCI) and 0.1g I-hydroxybenzotriazoles (HOBT) are dissolved in two
Chloromethanes obtain being condensed agent solution；
(3) weigh during 1g A are dissolved in dichloromethane and form solution A, take the condensation agent solution that step (2) is obtained, stirring
Under be added into solution A, with triethylamine adjust pH be 7.5, react half an hour under ice-water bath, carboxyl is fully activated；Then plus
Enter to be dissolved in the rgd peptide solution of dimethyl sulfoxide, by said mixture in 5 DEG C of reaction 5h stirred below, stopped reaction；Will reaction
Drop enters in excessive distilled water, the membranaceous precipitate in collection system, and uses distilled water wash, is then dried under vacuum to constant weight and obtains
To polymer P RGD；
(4) in the mixed solution of ethanol and deionized water, (volume ratio is 9:1, Unit/mL) middle addition three second of γ-aminopropyl
TMOS (KH-550), is stirred at room temperature 30min, is subsequently adding nanometer hydroxyapatite, and ultrasonic 3min stirs 3h under room temperature,
Then pH to 9-10 being adjusted with ammonia, continuing reaction 3-4h, solid matter is recovered by filtration, room temperature is dried, and solid matter is placed in
Heat in 130 degree of baking ovens 1.5 hours, then again by solid matter absolute ethanol washing 5 times, removing is not bonded in n-HAP
The silane coupler on surface, finally by gained material lyophilization, obtains the modifted-nano-hydroxyapatite that amino is contained on surface
(n-KHAP)；
(5) modified receive what PRGD, 0.15g step (4) that 0.5g polylactic acid (PDLLA), 0.5g steps (3) are obtained was obtained
Rice hydroxyapatite (n-KHAP) mixes to uniform in adding 30mL dichloromethane, 5h is stirred at room temperature, then in polytetrafluoro
In ethylene mould, film forming obtains n-KHAP/PRGD/PDLLA composite film materials.
Claims (6)
1. the composite film material based on polymer P RGD, which includes modifted-nano-hydroxyapatite (n-KHAP) 0.05-0.15, poly-
Compound PRGD 0.5, polylactic acid 0.5, in parts by weight；The preparation method of described polymer P RGD is：
1) with polylactic acid, maleic anhydride as raw material, dibenzoyl peroxide is initiator, and dichloromethane is solvent, at room temperature
Mix homogeneously, then vacuum drying remove solvent, be then warming up to 80-100 DEG C, lead to nitrogen reaction 5-15h, with dichloromethane-
The dissolving purification of dehydrated alcohol system obtains product A；
2) product A is dissolved in dichloromethane and forms solution A, taken polypeptide condensing agent and be dissolved in dichloromethane, will under stirring
Which adds solution A, adjusts pH, reacts half an hour, carboxyl is fully activated under ice-water bath；It is subsequently adding and is dissolved in dimethyl sulfoxide
Rgd peptide solution, by said mixture in 5 DEG C of reaction 5h stirred below, stopped reaction；Reactant liquor is instilled into excessive distilled water
In, the membranaceous precipitate in collection system, and distilled water wash is used, then it is dried under vacuum to constant weight and obtains polymer P RGD.
2. the composite film material based on polymer P RGD according to claim 1, it is characterised in that the maleic anhydride
Quality is the 5%-20% of polylactic acid, and the quality of dibenzoyl peroxide is the 3%-5% of maleic anhydride.
3. the composite film material based on polymer P RGD according to claim 1, it is characterised in that the polypeptide condensing agent
For the mixed liquor of 1- ethyls-(3- dimethylaminopropyls) carbodiimide hydrochloride/I-hydroxybenzotriazole.
4. the composite film material based on polymer P RGD according to claim 1, it is characterised in that step 2) regulation
PH is to adjust pH to 7-8 using triethylamine.
5. the composite film material based on polymer P RGD according to claim 1, it is characterised in that described modified Nano
The preparation method of hydroxyapatite is：Gamma-aminopropyl-triethoxy-silane is added in the mixed solution of ethanol and deionized water,
Nanometer hydroxyapatite is subsequently adding, pH9-10 is adjusted with ammonia, react 3-4h, solid matter is recovered by filtration, is placed in baking oven
Heating, then again by solid matter absolute ethanol washing, gained material lyophilization, obtains surface and contains the modified of amino receiving
Rice hydroxyapatite.
6. the preparation method of the composite film material based on polymer P RGD described in claim 1, it is characterised in that by polylactic acid,
Polymer P RGD, modifted-nano-hydroxyapatite are proportionally added into dichloromethane and are blended into uniformly, 5h are stirred at room temperature, then
In Teflon mould, film forming obtains the composite film material based on polymer P RGD, and each component is modified in parts by weight
Nanometer hydroxyapatite (n-KHAP) 0.05-0.15, polymer P RGD 0.5, polylactic acid 0.5.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104910410A (en) * | 2015-06-05 | 2015-09-16 | 武汉理工大学 | Preparation method of RGD polypeptide grafted poly(maleic anhydride-hexamethylendiamine-DL-lactic acid)/modified hydroxyapatite porous composite material |
| CN105255853B (en) * | 2015-11-10 | 2018-03-06 | 河南工业大学 | A kind of preparation method of magnetic hydroxylapatite immobilized lipase and the application in edible oil and fat processing |
| CN105688272B (en) * | 2016-02-02 | 2019-05-24 | 武汉理工大学 | A kind of compound orientation macropore bracket of polymer P RGD/ polylactic acid/HAP-PEG and preparation method thereof |
| CN106366304A (en) * | 2016-10-09 | 2017-02-01 | 湖南科技大学 | Preparation method of ethylenediamine and RGD polypeptide modified MPLGA with high anhydride content |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1562383A (en) * | 2004-03-16 | 2005-01-12 | 武汉理工大学 | Aretificial nerve canula material of slow operating complex type poly lactic acid and preparation method |
| CN1919360A (en) * | 2006-09-14 | 2007-02-28 | 同济大学 | Polylactic acid base/nano hydroxyapatite biological material and preparation method thereof |
| CN101301489A (en) * | 2008-06-23 | 2008-11-12 | 中国科学院长春应用化学研究所 | Method for preparing nano hydroxylapatite hybridized material with surface grafting polypeptide |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1562383A (en) * | 2004-03-16 | 2005-01-12 | 武汉理工大学 | Aretificial nerve canula material of slow operating complex type poly lactic acid and preparation method |
| CN1919360A (en) * | 2006-09-14 | 2007-02-28 | 同济大学 | Polylactic acid base/nano hydroxyapatite biological material and preparation method thereof |
| CN101301489A (en) * | 2008-06-23 | 2008-11-12 | 中国科学院长春应用化学研究所 | Method for preparing nano hydroxylapatite hybridized material with surface grafting polypeptide |
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