CN100531807C - Polylactic acid base/nano hydroxyapatite biological material and preparation method thereof - Google Patents
Polylactic acid base/nano hydroxyapatite biological material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a polylactic acid base/nanometer hydroxyl group apatite (NHA) composite material with biological activity and modifying method, which comprises the following steps: guiding active group -NH2 on the surface of polylactic acid base/nanometer hydroxyl group apatite (NHA), fixing through glutaral, grafting active peptide arginine-glycine-aspartate (Arg-Glee-Asp)RGD, possessing excellent cell and biological compatible surface and boundary.
Description
Technical field
The invention belongs to technical field of polymer materials and biomedical engineering technology field, be specifically related to polylactic acid base/nano-hydroxy apatite composite material of a kind of biologically active and preparation method thereof.
Background technology
The outstanding advantage of poly-lactic acid material is to have excellent biological compatibility, degradability and more moderate mechanical performance, also receives publicity in reparation medical science and pharmaceutical field.But because the chemical constitution of poly-lactic acid material itself is simple, the hydrophobicity on surface is strong, poor with cellular affinity, contained chemical active radical is few, more do not have pair cell required in the Tissue Engineering Study cell signal of regulating action that sticks, grown, thereby it can only be used as a kind of inert material of universality in every field.And, wish that timbering material can discern different cells in many field of tissue engineering technology, adsorb some seed cell selectively and can promote the growth, propagation of these cells and to the direction differentiation of hope.For overcoming the above-mentioned shortcoming of polylactic acid, the whole bag of tricks is used to polylactic acid modified.
Cyclic monomer by selecting to contain functional group and lactide (LA) or Acetic acid, hydroxy-, bimol. cyclic ester/lactide (LA/GA) ring opening copolymer can obtain this class new material, and wherein polylactic acid/amino acid copolymer is wherein typically to represent.Langer
[1]And the colleague has done a large amount of work in this respect, they have synthesized the copolymer of poly lactic acid of different aminoacids (aspartic acid, lysine, half peptide propylhomoserin), and confirm by copolymer side functional group grafting active polypeptide arginine-glycine-aspartic acid (Arg-Gly-Asp) (RGD), can promote the adhesion of cell and the identification of different cells.This class will have the biological activity peptide chain of cell recognition signal and introduce high molecular polymer, especially peptide chain being incorporated into poly-('alpha '-hydroxy acids/a-amino acid) class material will be to be used for human tissue engineering to have one of direction of development prospect, but the shortcoming of this class bioactive materials is the synthetic route more complicated, and cost is higher.
Another method is exactly at the polymer surfaces immobilizing biologically active materials.The part biological active substance is protein-based or the polypeptide class, so the fixing of bioactive substance mainly is proteinic fixation problem.Usually divided for three steps at inert polymer surface chemical fixing protein, the first step be the polymer surfaces reactive group as-OH ,-COOH ,-NH
2Deng introducing, second step be the activation of reactive group, the 3rd step was reactive group and proteinic reaction after activating.
The small peptide that the RGD peptide is made up of 3 aminoacid of arginine-glycine-aspartic acid (Arg-Gly-Asp).Molecular formula is:
The application of RGD peptide in oncotherapy is very extensive, effect with direct killing tumor cell and inducing apoptosis of tumour cell, and be the minimum identification short peptide sequence of many extracellular matrix proteins (as collagen etc.), also be the specially interactional recognition site of receptor protein of attachment proteins and cell surface.This short tripeptides is as a kind of important cell recognition site and signal enabling molecule, bringing into play important regulatory function in many vital movements, therefore RGD being grafted to the poly-lactic acid material surface is a kind of fairly simple method of improving the polylactic acid surface bioactive.
Hydroxyapatite (HA) is the crystalline portion of natural bone, and its nontoxic, no teratogenesis and side effect such as carcinogenic have excellent biological compatibility and bone conductibility, can directly form key with bone combines, inducing cell growth and division produce bone matrix collagen, form osseous tissue.But the quality of HA is too crisp, and the material of making is cracked easily, and mechanical performance is not good, does not have enough intensity and tired holding capacity; Polylactic acid and HA is compound, adopt suitable method to prepare bone tissue engineering stent material, polylactic acid based/HA compound support frame material can either improve the mechanical property and the guiding skeletonization characteristic of polylactic acid, can have control action to the biodegradation of HA again, guarantee that the osseous tissue resume speed is consistent with material degradation speed.
The present invention intends by modification is carried out on the surface of polylactic acid base/nano-hydroxy carbon ash stone composite material, at its surface introducing-NH
2The isoreactivity group by at polylactic acid base/nano-hydroxy carbon lime stone composite material surface grafting RGD, makes composite have the cell recognition function then.
[1]Elisseeff?J，Anseth?K，Langer?R，et?al.Synthesis?and?characterization?ofphoto-cross-linked?polymers?based?on?poly(L-lactic?acid-co-L-aspartic?acid)[J].Macromolecules，1997，(30)：2182~2184
Summary of the invention
The object of the present invention is to provide polylactic acid base/nano-hydroxy apatite composite material of a kind of biologically active and preparation method thereof.
The polylactic acid base/nano-hydroxy carbon ash stone composite material of the biologically active that the present invention proposes is to introduce active reactive group-NH by carry out aminolysis at composite material surface
2, fix by glutaraldehyde solution then, last grafting active polypeptide arginine-glycine-aspartic acid (Arg-Gly-Asp) RGD, and the material that obtains with biologic specificity, it has the material surface and the interface of good cell and biocompatibility.
Polylactic acid base/nano-hydroxy apatite composite biological material among the present invention, be (as poly (l-lactic acid) (PLLA) by polylactic acid base polymer, poly-D, L-lactic acid (PDLLA), polylactic acid-glycolic guanidine-acetic acid copolymer (PLGA) a kind of) (hydroxyapatite is for also can be less than 1 according to 100:1～100:30 with a kind of nanometer hydroxyapatite of modification, until being 0, it is 0 o'clock, be pure polylactic acid base polymer) part by weight form, the more excellent weight proportion of polylactic acid base polymer and modified Nano apatite is 100:5-100:25.This composite comprises composite film material and compound support frame material.Composite film material is to prepare by solvent cast-solvent evaporation method, and compound support frame material comprises with particle deposition method, thermally induced phase separation, gas foaming method, supercritical CO
2Methods etc. prepare.
Its weight average molecular weight of the polylactic acid base polymer that relates among the present invention is 50,000～200,000.
The nanometer hydroxyapatite of modification among the present invention; at room temperature prepare by chemical coprecipitation; transmission electron microscope (TEM) result shows that it is that radius is the sphere of 30～50nm; use L-lactide or L-lactide and Acetic acid, hydroxy-, bimol. cyclic ester mixture grafted polylactic acid base polymer in xylene solution then according to mol ratio 75:15～95:5; polymerization temperature is 100～130 ℃; carry out 8～24h under reflux condensation mode, the nitrogen protection, obtain modified Nano hydroxyl carbon lime stone.The nanometer hydroxyapatite of modification because of its surface grafting polylactic acid base polymer, improved of the compatibility of hydroxyl nanometer hydroxyapatite with polylactic acid base polymer, impel the interface compatibility of itself and polylactic acid good, make the stronger interfacial adhesion of generation between hydroxyl carbon lime stone and the polylactic acid base polymer, help hydroxyapatite and in polylactic acid base polymer, disperse.
The preparation method of the polylactic acid base/nano-hydroxy apatite composite biological material that the present invention proposes, concrete steps are as follows:
(1) aqueous solution of preparation polymine (PEI), ethylenediamine or hexamethylene diamine, concentration is 0.1mg/ml～2mg/ml; The aqueous solution of preparation RGD, concentration is 0.1mg/ml～2mg/ml, reconciles RGD solution pH value to 4.5 ~ 4.7;
(2) pretreatment of composite polylactic acid base/nano-hydroxy apatite.Composite at first soaks into 1～20min with 50%～75% ethanol water, uses washed with de-ionized water 5～10min then, drying for standby;
(3) be in PEI, ethylenediamine or the hexamethylene diamine aqueous solution of 0.1mg/ml～2mg/ml with the composite soaking at room temperature in concentration, activation 1～10h, distilled water cleans several times, drying for standby;
(4) with the fixing composite 1～10h of aminolysis of 25% glutaraldehyde solution, distilled water cleans several times, drying for standby;
(5) will put into aqueous solution graft reaction 1～48h of the above-mentioned RGD of 10～50ml with the fixed exsiccant composite of glutaraldehyde;
(6) composite that will react back grafting RGD takes out, and washes with water successively, and dehydrated alcohol is washed, and the vacuum room temperature is dried, and obtains polymer-matrix/nanometer hydroxyapatite composite film material of grafting RGD.
In the said method, the weight average molecular weight of PEI is 400-25000.
Above-mentioned composite is introduced active reactive group-NH by aminolysis
2, to fix by glutaraldehyde solution then, last grafting active polypeptide arginine-glycine-aspartic acid (Arg-Gly-Asp) is (RGD).When composite was complex stephanoporate bracket, step (2)-(6) were carried out in a vacuum and are fed nitrogen.In the time of specifically can in alcoholic solution, polyamines solution, glutaraldehyde solution, RGD solution, water, handling, all need test tube to be sealed with the rubber closure of band syringe needle, evacuation, to 10mPa, logical then nitrogen 10～20min, repeatedly several times, purpose is to make these solution can enter composite porous support material inside, thereby the interface in the material hole also can fully be reacted, improve the amount of material surface grafting RGD.
Subordinate list 1-4 is the performance comparison before and after composite of the present invention (membrane material and timbering material) aminolysis and the grafting RGD.By table as seen, the composite property behind aminolysis and grafting RGD improves a lot.
The specific embodiment
The aqueous solution of embodiment 1, preparation PEI (25000), concentration is 1mg/ml; Solvent casting method prepares the PLGA/HA film, treat solvent evaporates after, vacuum drying 24h desolvates to remove fully.The PLGA/HA film is cut into 2 * 2cm
2Lamellar, and with its thickness of slide gauge amount, record, standby; Ethanol water with 75%, ultrasonic cleaning PLGA/HA planar film 20min uses deionized water rinsing 10min then, and nitrogen dries up standby; PLGA/HA film surface grafting-NH
2: the planar film soaking at room temperature is activated 10h in the PEI (25000) of 1mg/ml aqueous solution, distilled water cleans several times, and nitrogen dries up standby; The fixing PLGA/HA composite film material 4h of aminolysis of glutaraldehyde solution with 25%; The concentration of aqueous solution of preparation RGD is 0.1mg/ml, reconciles RGD solution pH value to about 4.5 ~ 4.7 with the HCl weak solution; With putting into the beaker that fills a certain amount of RGD solution, place the tetrad magnetic stirring apparatus constantly to vibrate, reaction 48h with the fixed exsiccant PLGA/HA film of glutaraldehyde; Take out diaphragm from beaker, wash 1h successively with water, dehydrated alcohol is washed 1h, washes 1h again, and 3-4 time repeatedly, take out diaphragm then, place surface plate, the oven dry of vacuum room temperature obtains the PLGA/HA composite film material of grafting RGD.
The aqueous solution of embodiment 2, preparation PEI (25000), concentration is 1mg/ml; Solvent casting method prepares the PLLA/HA film, treat solvent evaporates after, vacuum drying 20h desolvates to remove fully.The PLLA/HA film is cut into 2 * 2cm
2Lamellar, and with its thickness of slide gauge amount, record, standby; Ethanol water with 75%, ultrasonic cleaning PLLA/HA planar film 25min uses deionized water rinsing 10min then, and nitrogen dries up standby; PLLA/HA film surface grafting-NH
2: the planar film soaking at room temperature is activated 5h in the PEI25000 of 1mg/ml aqueous solution, distilled water cleans several times, and nitrogen dries up standby; The fixing PLLA/HA composite film material 2h of aminolysis of glutaraldehyde solution with 25%; The aqueous solution 0.5mg/ml of preparation RGD reconciles RGD solution pH value to about 4.5 ~ 4.7 with the hydrochloric acid weak solution; With putting into the beaker that fills a certain amount of RGD solution, place the tetrad magnetic stirring apparatus constantly to vibrate, reaction 30h with the fixed exsiccant PLGA/HA film of glutaraldehyde; Take out diaphragm from beaker, wash 50 minutes successively with water, dehydrated alcohol was washed 50 minutes, washed again 50 minutes, and 3-4 time repeatedly, take out diaphragm then, place surface plate, the oven dry of vacuum room temperature obtains the PLLA/HA composite film material of grafting RGD.
The aqueous solution of embodiment 3, preparation PEI (423), concentration is 2mg/ml; Solvent casting method prepares the PLGA/HA film, treat solvent evaporates after, vacuum drying 28h desolvates to remove fully.The PLGA/HA film is cut into 2 * 2cm
2Lamellar, and with its thickness of slide gauge amount, record, standby; Ethanol water with 75%, ultrasonic cleaning PLGA/HA planar film 20min uses deionized water rinsing 10min then, and nitrogen dries up standby; PLGA/HA film surface grafting-NH
2: the planar film soaking at room temperature is activated 8h in the PEI (423) of 1mg/ml aqueous solution, distilled water cleans several times, and nitrogen dries up standby; The fixing PLGA/HA composite film material 4h of aminolysis of glutaraldehyde solution with 25%; The aqueous solution of preparation RGD, concentration is 1mg/ml, reconciles RGD solution pH value to about 4.5 ~ 4.7 with the HCl weak solution; With putting into the beaker that fills a certain amount of RGD solution, place the tetrad magnetic stirring apparatus constantly to vibrate, reaction 40h with the fixed exsiccant PLGA/HA film of glutaraldehyde; Take out diaphragm from beaker, wash 70 minutes successively with water, dehydrated alcohol was washed 60 minutes, washed again 50 minutes, and 3-4 time repeatedly, take out diaphragm then, place surface plate, the oven dry of vacuum room temperature obtains the PLGA/HA composite film material of grafting RGD.
The aqueous solution of embodiment 4, preparation PEI (25000), concentration is 1mg/ml, the aqueous solution of RGD, concentration is 0.1mg/ml, reconciles RGD solution pH value to about 4.5 ~ 4.7 with the hydrochloric acid weak solution; The PLGA/HA complex stephanoporate bracket is put into test tube, put into a certain amount of ethanol then, test tube is sealed with the rubber closure of band syringe needle, oil pump evacuation 20min, logical then nitrogen 20min is then with the support centrifugalize, to remove the ethanol of internal stent; The PLGA/HA compound rest is immersed in the aqueous solution of PEI (25000) of 1mg/ml and activate 10h, evacuation, logical nitrogen guarantee that the solution of polyamines enters internal stent repeatedly, the PLGA/HA support are directly taken out drying; It is 2.5% glutaraldehyde solution that PLGA/HA compound rest behind the aminolysis is immersed concentration, the method for evacuation, logical nitrogen repeatedly, reaction 10h; Take out, use deionized water rinsing, also want evacuation in the time of flushing, logical nitrogen is to remove unreacted glutaraldehyde, the vacuum normal temperature drying; To soak 24h in the fixed exsiccant PLGA/HA support immersion RGD solution of glutaraldehyde, evacuation is got rid of the gas that may exist in the support simultaneously; Take out support, wash 1h successively with water, ethanol is washed 1h, washes 1h again, and 3-4 time repeatedly, vacuum room temperature is dried, seal standby, the PLGA/HA compound support frame material of grafting RGD.
The aqueous solution of embodiment 5, preparation PEI (423), concentration is 1mg/ml, the aqueous solution of RGD, concentration is 0.1mg/ml, reconciles RGD solution pH value to about 4.5 ~ 4.7 with the hydrochloric acid weak solution; The PLGA/HA complex stephanoporate bracket is put into test tube, put into a certain amount of ethanol then, test tube is sealed with the rubber closure of band syringe needle, oil pump evacuation 25min, logical then nitrogen 20min is then with the support centrifugalize, to remove the ethanol of internal stent; The PLGA/HA compound rest is immersed in the aqueous solution of PEI (423) of 1mg/ml and activate 10h, evacuation, logical nitrogen guarantee that the solution of polyamines enters internal stent repeatedly, the PLGA/HA support are directly taken out drying; It is 2.5% glutaraldehyde solution that PLGA/HA compound rest behind the aminolysis is immersed concentration, the method for evacuation, logical nitrogen repeatedly, reaction 10h; Take out, use deionized water rinsing, also want evacuation in the time of flushing, logical nitrogen is to remove unreacted glutaraldehyde, the vacuum normal temperature drying; To soak 48h in the fixed exsiccant PLGA/HA support immersion RGD solution of glutaraldehyde, evacuation is got rid of the gas that may exist in the support simultaneously; Take out support, wash 1h successively with water, ethanol is washed 1h, washes 1h again, and 3-4 time repeatedly, vacuum room temperature is dried, seal standby, the PLGA/HA compound support frame material of grafting RGD.
The contact angle of PLGA and PLGA/HA membrane material before and after table 1 aminolysis
The contact angle of PLGA membrane material behind the table 2 grafting RGD
The water absorbing capacity of table 3 PLGA support
The water holding capacity of table 4 PLGA support
1) water absorbing capacity
Following formula is used for calculating the water absorbing capacity of support:
N
Water absorption rate=(W
Suction back weight-W
Dry weight)/W
Dry weight* 100%.
2) water holding capacity:
Following formula is used for calculating the water holding capacity of support:
N
Water retention=(W
Suction back weight-W
Dry weight)/W
Dry weight* 100%.
Claims (5)
1, a kind of polylactic acid base/nano-hydroxy apatite composite biological material, it is characterized in that by polylactic acid base polymer with form by 100:1～100:30 part by weight through the nanometer hydroxyapatite of modification, active group-NH is introduced through aminolysis in its surface
2, fix by glutaraldehyde solution then, again grafting RGD and obtaining; Wherein its weight average molecular weight of polylactic acid base polymer is 50,000～200,000, the nanometer hydroxyapatite of modification is that radius is the sphere of 30～50nm, obtain through the above-mentioned polylactic acid base polymer of surface grafting by nanometer hydroxyapatite, the steps include: to use L-lactide or L-lactide and the Acetic acid, hydroxy-, bimol. cyclic ester mixture grafted polylactic acid base polymer in xylene solution according to mol ratio 75:15～95:5, polymerization temperature is 100～130 ℃, carries out 8～24h under reflux condensation mode, the nitrogen protection; Here RGD is the active polypeptide arginine-glycine-aspartic acid.
2, polylactic acid base/nano-hydroxy apatite composite biological material according to claim 1 is characterized in that described polylactic acid base polymer is poly (l-lactic acid), poly-D, L-lactic acid, polylactic acid-glycolic guanidine-acetic acid copolymer a kind of.
3, polylactic acid base/nano-hydroxy apatite composite biological material according to claim 1 is characterized in that described composite is composite film material or compound support frame material.
4, a kind of preparation method of polylactic acid base/nano-hydroxy apatite composite biological material as claimed in claim 1 is characterized in that concrete steps are as follows:
(1) aqueous solution of preparation polymine, ethylenediamine or hexamethylene diamine, concentration is 0.1mg/ml～2mg/ml; The aqueous solution of preparation RGD, concentration is 0.1mg/ml～2mg/ml, reconciles RGD solution pH value to 4.5 ~ 4.7;
(2) composite polylactic acid based/through the pretreatment of the nanometer hydroxyapatite of modification, composite at first soaks into 1～20min with 50%～75% ethanol water, uses washed with de-ionized water 5～10min then, drying for standby; Part by weight polylactic acid based and through the nanometer hydroxyapatite of modification is 100:1-100:30 in the composite;
(3) be in polymine, ethylenediamine or the hexamethylene diamine aqueous solution of 0.1mg/ml～2mg/ml with the composite soaking at room temperature in concentration, activation 1～10h, distilled water cleans several times, drying for standby;
(4) with the fixing composite 1～10h of aminolysis of 25% glutaraldehyde solution, distilled water cleans several times, drying for standby;
(5) will put into the water of the RGD of 10～50ml, solution graft copolymerization reaction 1～48h with the fixed exsiccant composite of glutaraldehyde;
(6) composite that will react back grafting RGD takes out, and washes with water successively, and dehydrated alcohol is washed, and the vacuum room temperature is dried, and obtains polymer-matrix/nanometer hydroxyapatite composite film material of grafting RGD.
5, the preparation method of polylactic acid base/nano-hydroxy apatite composite biological material according to claim 4 is characterized in that for compound support frame material, and carry out in a vacuum step (2)-(6), and feeds nitrogen.
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| CN102028951B (en) * | 2009-09-29 | 2012-11-21 | 上海中医药大学 | RGDfK-modified oridonin polylactic acid medicament-carrying nanoparticles and preparation method thereof |
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| CN102716513B (en) * | 2012-05-02 | 2014-12-24 | 清华大学 | Method for modifying RGD on Ca-P ceramic material surface |
| CN104327293B (en) * | 2014-11-21 | 2017-03-29 | 武汉理工大学 | Composite film material based on polymer P RGD and preparation method thereof |
| CN105412983A (en) * | 2016-01-12 | 2016-03-23 | 河南工程学院 | Preparation method and application of nano-hydroxyapatite with surface grafted with RGD peptide |
| CN105536057A (en) * | 2016-01-12 | 2016-05-04 | 河南工程学院 | Preparation method and application of polylactic acid-glycolic acid grafted RGD peptide |
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| CN106432623A (en) * | 2016-10-09 | 2017-02-22 | 湖南科技大学 | Method for preparing ethidene diamine and RGD polypeptide modified high molecular weight polylactide-glycolide |
| CN109172874A (en) * | 2018-09-18 | 2019-01-11 | 福建师范大学 | A method of preparing the polylactic acid microsphere of gelatin surface graft modification |
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| CN114773649B (en) * | 2022-05-11 | 2024-01-05 | 向蕾 | Waterproof degradable PLA plastic packaging film and preparation method thereof |
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