WO2004000376A1 - Biodegradable and bioabsorbable materials for medical use and process for producing the same - Google Patents
Biodegradable and bioabsorbable materials for medical use and process for producing the same Download PDFInfo
- Publication number
- WO2004000376A1 WO2004000376A1 PCT/JP2002/006330 JP0206330W WO2004000376A1 WO 2004000376 A1 WO2004000376 A1 WO 2004000376A1 JP 0206330 W JP0206330 W JP 0206330W WO 2004000376 A1 WO2004000376 A1 WO 2004000376A1
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- WO
- WIPO (PCT)
- Prior art keywords
- depsipeptide
- medical use
- biodegradable
- bioabsorbable material
- use according
- Prior art date
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Classifications
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/58—Materials at least partially resorbable by the body
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/18—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
Definitions
- the present invention relates to a medical biodegradable polymer that can be used as a biodegradable bioabsorbable material tool such as a suture, a vascular stent, a carrier for living cells, a carrier for drugs, and the like.
- a biodegradable bioabsorbable material tool such as a suture, a vascular stent, a carrier for living cells, a carrier for drugs, and the like.
- the present invention relates to a bioabsorbable material and a method for producing the same.
- bioabsorbable polymers are widely used because they are decomposed and absorbed in the living body, but their mechanical properties such as tensile strength and the decomposition rate for absorption are almost fixed. However, when its mechanical properties are increased, it becomes brittle and the decomposition rate becomes slow. In addition, the mechanical properties decrease when the decomposition speed is increased. Therefore, there is a problem that the purpose of use and the place of use are limited. Disclosure of the invention
- the present invention provides a copolymer obtained by copolymerizing a bioabsorbable polymer and a cyclic peptide to form a ring-opening copolymer of the derivative, whereby the mechanical properties and the degradation rate are adjusted by the content of the depsipeptide. To prevent inflammation and other problems.
- a biodegradable bioabsorbable material for medical use made of a high yield polymer.
- the amount of the depsipeptide added is generally about 2% to 60% in molar ratio.If it is less than 2%, the effect of the addition is not obtained, and if it is more than 60%, the mechanical properties are excessively reduced. Because it becomes.
- bioabsorbable polymers that can be used, and in the case of copolymer bioabsorbable polymers, the addition limit of debseptid is effective depending on the blending amount and addition amount other than the above. In some cases, the above addition ratio is not a confirmed value.
- FIG. 1 is a structural diagram of a depsipeptide
- FIG. 2 is a structural diagram of a terpolymer having a depsipeptide unit
- FIG. 3 is a structural diagram illustrating the synthesis of depsipeptide.
- 4 is a structural diagram of a terpolymer obtained by ring-opening copolymerization of a depsipeptide
- FIG. 5 is a graph showing a 1 H NMR spectrum of the terpolymer
- FIG. 6 contains only a buffer solution
- FIG. 7 is a graph showing the results of a hydrolysis test using a digestion solution
- FIG. 7 is a graph showing the results of the enzymatic degradation characteristics of a terpolymer and each homopolymer by proteinase K.
- FIG. 9 is a graph showing the degradation characteristics of the copolymer
- FIG. 9 is a graph showing the relationship between the amount of depsipeptide and the degradation rate
- FIG. 10 is a graph showing the synthesis conditions of each copolymer and homopolymer, the polymer yield, Molecular weight
- Fig. 11 is a chart showing the thermal properties of the terpolymer and each homopolymer.
- Fig. 12 is a chart showing the mechanical properties (tensile properties) and thermal properties of the terpolymer.
- FIG. 13 is a chart showing the change in various physical properties of the terpolymer before and after degradation by the proteinase K.
- Fig. 14 is a chart showing the amount of debpeptide and the thermal properties. It is a chart showing a relationship.
- Figure 1 shows the structure of the debpeptide.
- the side chain R group is an alkyl group such as a methyl group, an isopropyl group and an isobutyl group
- the side chain R 'group is an alkyl group such as a methyl group and an ethyl group.
- debutipides are debutipeptide synthesized from an amino acid and a hydroxy acid derivative, and hydroxy acid derivatives are cloguchi cetyl chloride, 2-bromopropionyl bromide and 2-bromo-n-butyryl bromide.
- hydroxy acid derivatives are cloguchi cetyl chloride, 2-bromopropionyl bromide and 2-bromo-n-butyryl bromide.
- the obtained depsipeptides are referred to as L-MM ⁇ , L-DMO, and L-MEMO, respectively, in the order of the hydroxy acid derivatives, and all of them are applicable to the present invention.
- the enzymatic degradability of the copolymer by peptide monomer and ⁇ -caprolactone (CL) as a bioabsorbable polymer is determined by proteinase degradation as L-MMO / CL> L-DMO / CL ⁇ L-MEMO The order is / CL.
- depsipeptide synthesized from an amino acid and an oxyacid derivative uses L-alanine, L- (DL- or D-) norin and L-leucine as amino acids, and converts the resulting depsipeptide to amino acid.
- DMO, PM ⁇ ⁇ ⁇ , and BMO are all applicable to the present invention, but the enzymatic degradation of the copolymer by these depsipeptide monomers and ⁇ -force prolacton (CL) is the same as that of proteinase.
- PMOZC L> BMOZC L ⁇ DMOZC L for cholesterol esterase
- Cyclic depsipeptide was added to a copolymer of L-lactide (L-LA), a raw material of polylactic acid, and ⁇ -caprolactone (CL), a raw material of poly ⁇ -caprolactone 3 It was an original copolymer.
- L-LA L-lactide
- CL ⁇ -caprolactone
- FIG. 2 is a structural diagram of a copolymer having a peptide unit obtained by polymerizing the debut peptide.
- U indicates a debut peptide unit.
- cyclic depsipeptide is a cyclic ester amide comprising an ⁇ -amino acid and an ⁇ -hydroxy acid derivative.
- ⁇ L-alanine was used as the amino acid
- DL-2-bromopropionyl bromide a hydroxy-acid derivative
- the product was dissolved in water and 5N HCl was added dropwise so that the pH was about 3, then the water was removed by evaporation. The remaining aqueous solution was slowly acidified with 5 NHC 1 while cooling to give more white product. These resulting white products are The product was purified by soxhlet extraction using ether.
- DMO was purified by recrystallization twice from black-mouthed form.
- cyclic depsipeptide (L-DMO) was synthesized from -amino acid (L-alanine) and ⁇ -hydroxy acid derivative (DL-2-bromopropionylpromide) and then purified.
- L - lactide (L - LA) after recrystallization from TH F, All polymerization operations purified by sublimation (twice) were performed under an argon atmosphere.
- Figure 4 shows the synthesis scheme of the L-DMO / CL / L-LA terpolymer. Preparation of the copolymer was performed as follows.
- Figure 10 shows the synthesis conditions for each copolymer and homopolymer, and the yield and molecular weight of the resulting polymer.
- the composition of the copolymer was determined from the peak integral ratio of the 1 H NMR spectrum measured using a nuclear magnetic resonance apparatus at 400 MHZ (JEOLJ MN-LA 400). In addition, the chain sequence (randomness) of the copolymer was estimated from these spectra.
- the number average molecular weight (M n ) and molecular weight distribution (MwZMn) of the polymer are GPC 800 system manufactured by Toso Corporation ⁇ Column: TSK gel (G 200 H HR + G 300 H HR) + G 4 0 0 H + R + G 5 0 0 0 H HR ), power column temperature 40 ° C, differential refractive index (RI) detector ⁇ , and determined from a calibration curve made with standard polystyrene.
- the eluent used was a chromatographic form, and the flow rate was 1 mL min 1 .
- the thermal properties of the polymer namely the glass transition temperature (T g ), melting point (T m ) and heat of fusion ( ⁇ ) were determined using a differential scanning calorimeter SSC 5100 DSC 22 C manufactured by Seiko Instruments Inc. It was measured. The measurement was performed in a nitrogen atmosphere at a heating rate of 10 ° C / mi ⁇ . The randomness of the copolymer was also estimated from these thermal properties.
- the mechanical properties (tensile strength and elongation at break) of the polymer were measured at a crosshead speed of 50 mm / min using a tensile tester RTC-121OA manufactured by Orientec Co., Ltd. The measurement was performed at least three times and the average value was used.
- the enzymatic degradation test was performed in the same manner as before, but the outline is shown below.
- a polymer tube (thickness: approx. 100 ⁇ m, number: 10 mg) enclosed in a polyethylene sheet mesh (mesh: approx. IX lmm) is placed in a sample vial containing enzyme and buffer (50 ml). Degradation was performed by incubating at 37 ° C. The enzyme concentration was 1 international unit (IU) per mg of polymer sample.
- the enzyme-containing buffer solution (decomposed solution) was replaced with a new decomposed solution approximately every 40 hours in consideration of the decrease in oxygen activity and the contamination and growth of microorganisms in the air.
- Degradability was evaluated based on changes in polymer weight and physical properties (molecular weight, composition, thermal properties) before and after decomposition.
- Proteinase K (derived from Tritirachiuma 1 bum, manufactured by Wako Pure Chemical Industries, Ltd., having an activity of 20 I UZmg), which is a kind of protease, is used as a buffer for Tridine (pH). 8.0) was used.
- FIG. 10 shows the results of polymerization of the L-DMO / CL / L-LA terpolymer and each homopolymer obtained from the above test.
- the copolymer composition indicates that the reactivity of L-LA is high under the copolymerization conditions.
- FIG. 11 shows the thermal characteristics of the obtained terpolymer and each homopolymer.
- P 0 1 y (CL) is T g, T m pixels respectively located in flexibility about a 6 0 and 6 0 ° C, but a low melting crystalline polymers one , Poly (L-LA) have T g and T m of about 60 and It is a hard, brittle crystalline polymer with a high melting point of 180 ° C, and poly (L-DMO) is an amorphous glass-like polymer.
- FIG. 5 shows the 1 H NMR spectrum of the L-DMOZC LZL-LA (8:13:79) terpolymer.
- This figure also confirms that the terpolymer is random. That is, the ⁇ - and ⁇ -methylene proton peaks (f, i) in the CL unit are sensitive to adjacent comonomer units, and each of these peaks is split into two (the high f, i The peak on the magnetic field side corresponds to the homosequence of CL-CL, and the peak on the low and high magnetic field side corresponds to the peak based on the heterosequence of L-LA-CL and L-DM ⁇ -CL.) The polymer was found to be a random copolymer.
- this unit is accurately introduced into the copolymer because of the high reactivity of L-LA This is because polymerization of (Tm is about 95 ° C.) occurs first, and L-DMO (and / or CL) is ring-opened by this active growing end and is randomly incorporated into the copolymer.
- Figure 12 shows the mechanical properties (tensile properties) and thermal properties of the terpolymer.
- the terpolymer in the figure was newly synthesized on a large scale to measure these physical properties. (Mainly synthesized by changing the amount of CL in order to improve the flexibility of the polymer.) All with a molecular weight (M n ) of 100,000 or more (100.2 to 158,000) To the physical properties The effect of the molecular weight on this need not be taken into account much.
- the tensile properties show that the strength decreases as the CL content increases, that is, decreases as the L-LA content decreases, but the elongation increases sharply when the CL content is 20 m 0 1% or more, and the flexibility of the copolymer increases. Q that shows improvement
- the tensile strength of these terpolymers is higher than that of general-purpose plastic, polyethylene (PE), and is higher than that of polypropylene (PP). In addition, it has a higher tensile strength than biodegradable plastics such as bionole (Bolibutylene succinate (PBSU), manufactured by Showa Polymer Co., Ltd.) and Biopol CP (3HB-c0-3HV), manufactured by Nippon Monsanto Co., Ltd.) The strength is great.
- PBSU Bobutylene succinate
- Biopol CP 3HB-c0-3HV
- the elongation at break was much larger in samples with a CL content of 20 mol 1% or more than in bioballs, and was equal to or greater than that of PE, PP and bionore.
- the thermal properties of the terpolymer are Tm, ⁇
- the L-DMO / CL / L-LA (4:20:76) terpolymer having a CL content of 20 mo 1% or more is a good balance of physical properties.
- poly (L-LA) is decomposed to some extent, while P ly (CL), which is more decomposable from the viewpoint of thermal properties, shows almost weight loss within 200 hours.
- P ly (CL) which is more decomposable from the viewpoint of thermal properties, shows almost weight loss within 200 hours.
- This present enzyme poly mer ⁇ Lac Bok I le groups here having an alkyl chain length is short and the side chains between ester bonds [- ⁇ - CH (CH 3) - CO - ] that have a po 1 y (L-LA) ⁇ , but the ethylene chain between the ester bonds is relatively linear and relatively long p 0 1 y (It seems that CD has no specificity.
- the degradability increases greatly with the increase of the L-DMO unit content as compared with P o 1 y (L-LA).
- P o 1 y L-LA
- One of the major factors is that the L-DMO unit that has it also shows substrate specificity.
- the L-DMOZC LZL-LA terpolymer has improved enzymatic degradation by proteinase K while relatively maintaining the thermal and mechanical properties of po 1 y (L-LA) .
- the thermal properties (T m , ⁇ H m) of the polymer increase with the progress of decomposition. Therefore, as described above, the decomposition of the amorphous hydrophilic part containing a large amount of L-DMO unit has priority. Then you can see what happens.
- the obtained copolymer was found to be a random copolymer from the results of NMR (nuclear magnetic resonance measurement) and thermal properties measurement.
- FIG. 7 shows the enzymatic degradation characteristics of the copolymer having the depsipeptide unit.
- lactide was described as L-lactide, but L-lactide and its enantiomer, D-lactide, are combined and polymerized to form a stereocomplex, which results in heat such as melting point. Target characteristics can be improved.
- free forming ability can be imparted by changing the glass transition temperature.
- a binary copolymer in which depsipeptide and L-lactide are copolymerized to form a ring-opening polymer of depsipeptide may be used.
- L-lactide and its enantiomer, D-lactide are combined and copolymerized to form a stereocomplex lactide to form debutiptide. It may be a stereocomplex of a ring-opened copolymer.
- Fig. 1 shows the structure of a copolymer having a peptide unit when copolymerized with ⁇ -force prolactone, a raw material of poly ⁇ -force prolactone, to obtain a copolymer in which ring opening polymerization of debutpeptide is obtained. See Figure 2.
- U indicates a deb-type dump.
- FIG. 8 shows the decomposition characteristics of the copolymer having debutpeptide.
- the decomposition characteristics are in the order of methyl group >> isopropyl group> isobutyl group, and it can be seen that the decomposability decreased as the bulk of the side chain increased.
- Fig. 14 shows the relationship between the thermal characteristics and Fig. 9 shows the relationship between the decomposition rates.
- the glass transition temperature ( ⁇ g ) increases as the amount of depsipeptide increases, and the melting point (T m) and heat of fusion (AH m) are observed when the ⁇ -force prolactone amount is less than 20 m 0 1%. And have crystallinity Was.
- the decomposition rate increased with the increase in the amount of debutpeptide.
- poly- ⁇ -force prolactone and polylactic acid have been described as examples of bioabsorbable polymers.
- the polymer may be a polymer, for example, boridioxanone, trimethylene carbonate, and a copolymer of two or more thereof.
- a bioabsorbable polymer is copolymerized with a cyclic peptide to form a copolymer having debutitunitite, whereby the mechanical properties and the degradation properties are adjusted for a medical product.
- This has the effect of making it a degradable bioabsorbable material.
- modification of the peptide unit with an alkyl group has the effect of adjusting the mechanical properties and the decomposition properties.
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Abstract
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Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2004515461A JPWO2004000376A1 (en) | 2002-06-25 | 2002-06-25 | Biodegradable bioabsorbable material for medical use and manufacturing method thereof |
PCT/JP2002/006330 WO2004000376A1 (en) | 2002-06-25 | 2002-06-25 | Biodegradable and bioabsorbable materials for medical use and process for producing the same |
KR10-2003-7007426A KR20050013186A (en) | 2002-06-25 | 2002-06-25 | Biodegradable bio-absorbable material for clinical practice and method for producing the same |
CA002428640A CA2428640A1 (en) | 2002-06-25 | 2002-06-25 | Biodegradable bioabsorbable material for clinical practice and method for producing the same |
US11/020,535 US20050163822A1 (en) | 2002-06-25 | 2004-12-22 | Biodegradable bio-absorbable material for clinical practice and method for producing the same |
US11/025,807 US20050271617A1 (en) | 2002-06-25 | 2004-12-29 | Biodegradable bio-absorbable material for clinical practice |
Applications Claiming Priority (1)
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PCT/JP2002/006330 WO2004000376A1 (en) | 2002-06-25 | 2002-06-25 | Biodegradable and bioabsorbable materials for medical use and process for producing the same |
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US11/020,535 Continuation US20050163822A1 (en) | 2002-06-25 | 2004-12-22 | Biodegradable bio-absorbable material for clinical practice and method for producing the same |
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PCT/JP2002/006330 WO2004000376A1 (en) | 2002-06-25 | 2002-06-25 | Biodegradable and bioabsorbable materials for medical use and process for producing the same |
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JP (1) | JPWO2004000376A1 (en) |
KR (1) | KR20050013186A (en) |
CA (1) | CA2428640A1 (en) |
WO (1) | WO2004000376A1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006068168A1 (en) * | 2004-12-24 | 2006-06-29 | Goodman Co., Ltd. | Biodegradable and bioresorbable material for medical use |
JP2007503226A (en) * | 2003-08-22 | 2007-02-22 | スミス アンド ネフュー インコーポレーテッド | Tissue repair and replacement |
JP2009543598A (en) * | 2006-07-13 | 2009-12-10 | アボット カーディオヴァスキュラー システムズ インコーポレイテッド | Stereocomplex-forming composition and implantable medical device including the same |
US8298466B1 (en) | 2008-06-27 | 2012-10-30 | Abbott Cardiovascular Systems Inc. | Method for fabricating medical devices with porous polymeric structures |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0086613A1 (en) * | 1982-02-08 | 1983-08-24 | Ethicon, Inc. | Copolymers of p-dioxanone and 2,5-morpholinediones and surgical devices formed therefrom having accelerated absorption characteristics |
EP0322154A2 (en) * | 1987-12-23 | 1989-06-28 | Pfizer Inc. | Bioabsorbable polydepsipeptides, their preparation and use |
-
2002
- 2002-06-25 JP JP2004515461A patent/JPWO2004000376A1/en active Pending
- 2002-06-25 KR KR10-2003-7007426A patent/KR20050013186A/en not_active Application Discontinuation
- 2002-06-25 WO PCT/JP2002/006330 patent/WO2004000376A1/en not_active Application Discontinuation
- 2002-06-25 CA CA002428640A patent/CA2428640A1/en not_active Abandoned
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0086613A1 (en) * | 1982-02-08 | 1983-08-24 | Ethicon, Inc. | Copolymers of p-dioxanone and 2,5-morpholinediones and surgical devices formed therefrom having accelerated absorption characteristics |
EP0322154A2 (en) * | 1987-12-23 | 1989-06-28 | Pfizer Inc. | Bioabsorbable polydepsipeptides, their preparation and use |
Non-Patent Citations (2)
Title |
---|
SHIRAHAMA H. ET AL.: "Highly biodegradable copolymers composed of chiral depsipeptide and L-lactide units with favorable physical properties", JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY, vol. 40, no. 3, 2001, pages 302 - 316, XP002956696 * |
SHIRAHAMA H. ET AL.: "Synthesis and enzymatic degradation of optically active depsipeptide copolymers", JOURNAL OF BIOMATERIALS SCIENCE, POLYMER EDITION, vol. 10, no. 6, 1999, pages 621 - 639, XP002956695 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007503226A (en) * | 2003-08-22 | 2007-02-22 | スミス アンド ネフュー インコーポレーテッド | Tissue repair and replacement |
WO2006068168A1 (en) * | 2004-12-24 | 2006-06-29 | Goodman Co., Ltd. | Biodegradable and bioresorbable material for medical use |
JP2006175153A (en) * | 2004-12-24 | 2006-07-06 | Goodman Co Ltd | Biodegradable bio-absorbable material for clinical practice |
JP2009543598A (en) * | 2006-07-13 | 2009-12-10 | アボット カーディオヴァスキュラー システムズ インコーポレイテッド | Stereocomplex-forming composition and implantable medical device including the same |
US8298466B1 (en) | 2008-06-27 | 2012-10-30 | Abbott Cardiovascular Systems Inc. | Method for fabricating medical devices with porous polymeric structures |
Also Published As
Publication number | Publication date |
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KR20050013186A (en) | 2005-02-03 |
CA2428640A1 (en) | 2003-12-25 |
JPWO2004000376A1 (en) | 2005-10-20 |
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