CN102872483A - Poly-(Epsilon-caprolactone) drug eluting stent modification method - Google Patents
Poly-(Epsilon-caprolactone) drug eluting stent modification method Download PDFInfo
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- CN102872483A CN102872483A CN2012103556424A CN201210355642A CN102872483A CN 102872483 A CN102872483 A CN 102872483A CN 2012103556424 A CN2012103556424 A CN 2012103556424A CN 201210355642 A CN201210355642 A CN 201210355642A CN 102872483 A CN102872483 A CN 102872483A
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- caprolactone
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- eluting medicament
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Abstract
The invention relates to a poly-(Epsilon-caprolactone) drug eluting stent modification method adopting chitosan. The method comprises the step of melt blending or coating or both. A modified poly-(Epsilon-caprolactone) drug eluting stent is superior in both drug release (particularly early stages of drug release) and degradation to a conventional poly-(Epsilon-caprolactone) drug eluting stent.
Description
Technical field
The present invention relates to a kind of method of modifying of poly-(6-caprolactone) bracket for eluting medicament, specifically, relates to the method for poly-(6-caprolactone) bracket for eluting medicament of poly-(6-caprolactone) modification of a kind of employing chitosan graft.
Background technology
Coronary heart disease is as a kind of common cardiovascular disease, underwent coronary interventional procedure (PCI) is the therapeutic modality of present main flow, it is to get up for base growth in the percutaneous tranluminal coronary angioplasty (PTCA) that Gruentzig in 1977 carries out, and has mainly passed through simple balloon dilatation, level in patients after coronary artery stenting and three developmental stage of bracket for eluting medicament.The brachymedial phase restenosis incidence rate that causes because of vessel wall elasticity retraction and vascellum endometrial hyperplasia after but balloon dilatation and traditional bare metal stent are implanted has seriously restricted the development of PCI up to more than 50%.
In order to suppress and prevent PCI postoperative restenosis, bracket for eluting medicament cover the rack surface Polymer-supported by utilization medicine the breeding hypertrophy of vascular smooth muscle is suppressed, thereby realize the treatment of vascular restenosis.From the Cypher support of Cordis company in 2002 research and development since the listing of Europe, bracket for eluting medicament obtains a wide range of applications in the PCI treatment, it can effectively reduce in-stent restenosis and again get involved problem, brachymedial phase restenosis problem has obtained effectively suppressing, but research finds that bracket for eluting medicament is compared to balloon dilatation and the easier generation of traditional metal bare bracket late period (＞1 year) stent thrombosis problem.In addition, at present the commercialization support substantially based on metal material, and digestion of metallic ion and residual body in caused histocompatibility problem be metal rack platform Main Problems.Although form (such as introducing the elements such as nickel, titanium) by improving metal or it carried out finishing (such as the plated surface oxide layer, adhere to inorganic protective layer etc.) effectively to address the above problem; but because the biological non-biodegradable of matrix itself; when medicine in the support be released complete after; remaining metal rack still is present in the human body, thereby causes the in-stent restenosis problem as the as easy as rolling off a log neointimal hyperplasia that causes of a kind of foreign body implant.
Polyester material is an important component part in the Biodegradable material, such as polylactic acid (PLA), polyglycolic acid (PGA) and poly-(6-caprolactone) (PCL) etc., has been widely used in biomedical sector.Poly-(6-caprolactone) Food and Drug Administration (FDA) approval can be used as biomedical material and uses, and in Europe, PCL has been used as nail clinically; It is clinical that the long-acting implants Capronor of the left ethisterone that PCL makes has finished the II phase in the U.S..In addition, studies show that compared to PLA and PGA, the degradation cycle of PCL is longer, degradation time in vivo is generally 2-4, and along with the increase of molecular weight, soak time in vivo is also just longer.The initial number average molecular weight is that 50,000 PCL needs the time in 3 years could be degradable in the body, therefore can be effective as the mechanics strong point before neovascularization.Secondly, degrade slowly and molecular structure because of it, the inflammatory effector of PCL is also little than the above two.Yet the existing bracket for eluting medicament that is made of PCL still has room for improvement remaining deficiency aspect the degraded of drug release (particularly medicine discharges in earlier stage) and bracket for eluting medicament.
Summary of the invention
The present inventor finds through extensively reaching deep research: adopt existing (6-caprolactone) bracket for eluting medicament that gathers of poly-(6-caprolactone) modification of chitosan graft, poly-(6-caprolactone) bracket for eluting medicament of the modification of gained all is better than existing poly-(6-caprolactone) bracket for eluting medicament in the performance aspect the degraded of drug release (particularly medicine discharges in earlier stage) and bracket for eluting medicament.
The object of the invention is, a kind of method of modifying of poly-(6-caprolactone) bracket for eluting medicament is provided, and the key step of described method of modifying is:
To comprise that poly-(6-caprolactone) of poly-(6-caprolactone), chitosan graft and medicine through the melt-processed molding, obtain object (modification gathers (6-caprolactone) bracket for eluting medicament);
Or,
To comprise that at first poly-(6-caprolactone) and medicine are through the melt-processed molding, obtain bracket for eluting medicament A, then with poly-(6-caprolactone) fusion coating of chitosan graft on the surface of resulting bracket for eluting medicament A, obtain object (modification gathers (6-caprolactone) bracket for eluting medicament);
Or,
To comprise that at first poly-(6-caprolactone) of poly-(6-caprolactone), chitosan graft and medicine are through the melt-processed molding, obtain bracket for eluting medicament B, then with poly-(6-caprolactone) fusion coating of chitosan graft on the surface of resulting bracket for eluting medicament B, obtain object (modification gathers (6-caprolactone) bracket for eluting medicament);
Wherein, the acetyl degree distribution of used chitosan is 81%～100%, and its viscosity-average molecular weight is 1.03 * 10
5～10.35 * 10
5, poly-(6-caprolactone) of used chitosan graft is 1 with the mass ratio (total amount) of used poly-(6-caprolactone): (1～10).
Description of drawings
Cross section and the section surface sweeping Electronic Speculum figure of the configuration of surface of Fig. 1 bracket for eluting medicament I (by embodiment 1 preparation),
Wherein, (a)-the cross section surface sweeping Electronic Speculum figure of the configuration of surface of bracket for eluting medicament I,
(b)-the section surface sweeping Electronic Speculum figure of the configuration of surface of bracket for eluting medicament I.
The drug release curve chart of Fig. 2 bracket for eluting medicament I～IV (by embodiment 1～4 preparation) and bracket for eluting medicament 1～2 (by Comparative Examples 1～2 preparation).
The specific embodiment
In preferred technical scheme of the present invention, in poly-(6-caprolactone) of used chitosan graft, 6～30 (6-caprolactone) repetitives of chitosan repetitive grafting, its structural representation formula is as follows:
Wherein, R
1～R
4Independently be selected from respectively: H or
A kind of in (repetitive of poly-(6-caprolactone), the curve mark is the grafting end), and R
1～R
4Be not H simultaneously.
Preferred technical scheme is: 6～20 (6-caprolactone) repetitives of chitosan repetitive grafting.
Best technical scheme is: 9～18 (6-caprolactone) repetitives of chitosan repetitive grafting.
In another preferred technical scheme of the present invention, poly-(6-caprolactone) of used chitosan graft is 1 with the mass ratio (total amount) of used poly-(6-caprolactone): (1～4).
In a further preferred technical solution of the present invention, take the gross weight of the described bracket for eluting medicament of preamble as 100%, its Chinese medicine accounts for 0.1wt%～10wt% (1wt%～5wt%) more preferably.
Wherein, described medicine can be that paclitaxel is or/and aspirin.
In sum, the method for poly-(6-caprolactone) bracket for eluting medicament of modification provided by the invention comprises the following steps:
Poly-(6-caprolactone) melt blending that will comprise poly-(6-caprolactone) and chitosan graft, add paclitaxel again or/and aspirin (the feed molar ratio row of each material are identical as mentioned before) and appropriate amount of drug goes up acceptable auxiliary agent (such as Polyethylene Glycol and/or glycerol etc.) and stirs in the rear ascending pipe mould, the pressure recession that applies certain hour removes, and obtains after cooling object.
Or,
At first will comprise poly-(6-caprolactone) and paclitaxel or/and aspirin and appropriate amount of drug go up acceptable auxiliary agent (such as Polyethylene Glycol and/or glycerol etc.) through the melt-processed molding, obtain bracket for eluting medicament Aa, then poly-(6-caprolactone) fusion coating with chitosan graft obtains object on the surface of resulting bracket for eluting medicament Aa;
Wherein, the feed ratio of each material is identical as mentioned before.
To comprise that at first poly-(6-caprolactone) of poly-(6-caprolactone), chitosan graft and paclitaxel are or/and aspirin and appropriate amount of drug go up acceptable auxiliary agent (such as Polyethylene Glycol and/or glycerol etc.) through the melt-processed molding, obtain bracket for eluting medicament Bb, then poly-(6-caprolactone) fusion coating with chitosan graft obtains object on the surface of resulting bracket for eluting medicament Bb;
Wherein, the feed ratio of each material is identical as mentioned before.
In the present invention, used poly-(6-caprolactone) and chitosan are commercially available product, and poly-(6-caprolactone) of chitosan graft is to prepare by document (Carbohydrate Polymers 2010 (80) 498-503).
Compared with prior art, the present invention has following advantage:
(1) chitosan and polycaprolactone material all have good biocompatibility, and can be degraded to micromolecule and get rid of by the kidney organ.The hydrophobicity of pure polycaprolactone support is stronger, and drug release is slow, has improved the hydrophilicity of pure support behind the introducing graft polymers, realizes the Stable Release of medicine.
(2) preparation technology is relatively simple, and mould is simple and easy to system and material source is abundant.
Below by embodiment the present invention is further elaborated, its purpose only is better to understand content of the present invention.Should be understood that protection scope of the present invention is not limited by the cases cited.
In the following example, used poly-(6-caprolactone) provided by the lucky chemical industry company limited of upper seamount, and used chitosan is provided by ZHEJIANG AOXING BIOTECHNOLOGY CO., LTD.
Embodiment 1
Being averaged mole is 80; 9 of grafting gather (6-caprolactone) as the matrix material of support on 000 poly-(6-caprolactone) and each the chitosan unit; both mass ratioes are 3: 1; with its blend and be heated to 150 ℃; add the paclitaxel rear injection mould (internal diameter of mould is 1mm, and external diameter is 2mm) that stirs, withdraw from after applying 1 minute with 5MPa power at 150 ℃; the demoulding in the demoulding or the immersion dehydrated alcohol obtains bracket for eluting medicament I after the cooling.
Embodiment 2
Being averaged mole is 80; 16 of grafting gather (6-caprolactone) as the matrix material of support on 000 poly-(6-caprolactone) and each the chitosan unit; both mass ratioes are 4: 1; its blend is heated to 150 ℃; adding paclitaxel and aspirin stir, and (internal diameter of mould is 1mm to the above-mentioned mould of rear injection; external diameter is 2mm); withdraw from after applying 1 minute with 5MPa power at 150 ℃; the demoulding in the demoulding or the immersion dehydrated alcohol obtains bracket for eluting medicament II after the cooling.
Embodiment 3
At first being averaged mole is 80,000 poly-(6-caprolactone) is as the matrix material of support, this polymer is heated to 80 ℃, the adding paclitaxel stirs, and (internal diameter of mould is 1mm to rear injection mould, external diameter is 2mm), withdraw from after applying 1 minute with 5MPa power at 100 ℃, the demoulding or immerse the demoulding in the dehydrated alcohol after the cooling obtains bracket for eluting medicament Aa-1;
Then; the polymer of grafting on each chitosan unit 18 poly-(6-caprolactones) is heated to 150 ℃ of meltings; and be coated on the bracket for eluting medicament Aa-1 (can in the mould of external diameter 2mm, form the coating of surface uniform densification); the demoulding in cooling and demolding or the immersion dehydrated alcohol (poly-(6-caprolactone) is 4: 1 with the mass ratio of chitosan graft poly-(6-caprolactone)) obtains bracket for eluting medicament III.
Embodiment 4
Being averaged mole is 80,9 of grafting gather (6-caprolactone) as the matrix material of support on 000 poly-(6-caprolactone) and each the chitosan unit, both mass ratioes are 3: 1, add stir rear blend and be heated to and inject mould after 120 ℃ (internal diameter of mould is 1mm of paclitaxel, external diameter is 2mm), withdraw from after applying 1 minute with 5MPa power, the demoulding or immerse the demoulding in the dehydrated alcohol after the cooling obtains support Bb-1;
Then; the polymer of grafting on each chitosan unit 9 poly-(6-caprolactones) is heated to 150 ℃ of meltings; and be coated on the support Bb-1 (can in the mould of external diameter 2mm, form the coating of surface uniform densification); the demoulding in cooling and demolding or the immersion dehydrated alcohol (total poly-(6-caprolactone) is 10: 1 with the mass ratio of chitosan graft poly-(6-caprolactone)) obtains bracket for eluting medicament IV.
Comparative Examples 1
Being averaged mole is 80; 000 poly-(6-caprolactone) is as the matrix material of support; be heated to 80 ℃; the adding paclitaxel stirs, and (internal diameter of mould is 1mm to rear injection mould; external diameter is 2mm); withdraw from after applying 1 minute with 5MPa power at 100 ℃, the demoulding or immerse the demoulding in the dehydrated alcohol after the cooling obtains bracket for eluting medicament 1.
Comparative Examples 2
Being averaged mole is 80; 000 poly-(6-caprolactone) is as the matrix material of support; with it to 100 ℃; adding paclitaxel and aspirin stir, and (internal diameter of mould is 1mm to the above-mentioned mould of rear injection; external diameter is 2mm); withdraw from after applying 1 minute with 5MPa power at 150 ℃, the demoulding or immerse the demoulding in the dehydrated alcohol after the cooling obtains bracket for eluting medicament 2.
Under identical condition, the medicine-releasing performance of testing drug FirebirdTM I～IV and bracket for eluting medicament 1～2, it the results are shown in Figure 2.
As shown in Figure 2, the drug release of bracket for eluting medicament I～IV (particularly medicine discharges in earlier stage) performance obviously is better than bracket for eluting medicament 1～2.
Claims (10)
1. the method for poly-(6-caprolactone) bracket for eluting medicament of a modification is characterized in that the key step of described method is:
To comprise that poly-(6-caprolactone) of poly-(6-caprolactone), chitosan graft and medicine through the melt-processed molding, obtain object;
Or,
To comprise that at first poly-(6-caprolactone) and medicine through the melt-processed molding, obtain bracket for eluting medicament A, then poly-(6-caprolactone) fusion coating with chitosan graft obtains object on the surface of resulting bracket for eluting medicament A;
Or,
To comprise that at first poly-(6-caprolactone) of poly-(6-caprolactone), chitosan graft and medicine are through the melt-processed molding, obtain bracket for eluting medicament B, then poly-(6-caprolactone) fusion coating with chitosan graft obtains object on the surface of resulting bracket for eluting medicament B;
Wherein, the acetyl degree distribution of used chitosan is 81%～100%, and its viscosity-average molecular weight is 1.03 * 10
5～10.35 * 10
5, poly-(6-caprolactone) of used chitosan graft is 1 with the mass ratio of used poly-(6-caprolactone): (1～10).
2. the method for claim 1 is characterized in that, wherein in poly-(6-caprolactone) of used chitosan graft, and 6～30 6-caprolactone repetitives of chitosan repetitive grafting.
3. method as claimed in claim 2 is characterized in that, wherein in poly-(6-caprolactone) of used chitosan graft, and 6～20 6-caprolactone repetitives of chitosan repetitive grafting.
4. method as claimed in claim 3 is characterized in that, wherein in poly-(6-caprolactone) of used chitosan graft, and 9～18 6-caprolactone repetitives of chitosan repetitive grafting.
5. such as claim 1 or 4 described methods, it is characterized in that wherein poly-(6-caprolactone) of used chitosan graft is 1 with the mass ratio of used poly-(6-caprolactone): (1～4).
6. the method for claim 1 is characterized in that, wherein take the gross weight of described bracket for eluting medicament as 100%, medicine accounts for 0.1wt%～10wt%.
7. method as claimed in claim 6 is characterized in that, wherein take the gross weight of described bracket for eluting medicament as 100%, medicine accounts for 1wt%～5wt%.
8. such as claim 6 or 7 described methods, it is characterized in that wherein said medicine is that paclitaxel is or/and aspirin.
9. method as claimed in claim 5 is characterized in that, wherein take the gross weight of described bracket for eluting medicament as 100%, medicine accounts for 1wt%～5wt%.
10. method as claimed in claim 9 is characterized in that, wherein said medicine is that paclitaxel is or/and aspirin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210355642.4A CN102872483B (en) | 2012-09-19 | 2012-09-19 | Poly-(Epsilon-caprolactone) drug eluting stent modification method |
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|---|---|---|---|
| CN201210355642.4A CN102872483B (en) | 2012-09-19 | 2012-09-19 | Poly-(Epsilon-caprolactone) drug eluting stent modification method |
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| CN102872483A true CN102872483A (en) | 2013-01-16 |
| CN102872483B CN102872483B (en) | 2015-02-18 |
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