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Long-Term In Virto Hydrolytic Degradation Behavior and Mechanism of Biodegradable Poly(L-lactic acid)

Research Project

Project/Area Number 16500291
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Biomedical engineering/Biological material science
Research InstitutionToyohashi University of Technology

Principal Investigator

TSUJI Hideto  Toyohashi University of Technology, Faculty of Engineering, Associate Professor, 工学部, 助教授 (60227395)

Project Period (FY) 2004 – 2006
Project Status Completed (Fiscal Year 2006)
Budget Amount *help
¥3,600,000 (Direct Cost: ¥3,600,000)
Fiscal Year 2006: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 2005: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 2004: ¥2,100,000 (Direct Cost: ¥2,100,000)
Keywordspoly(L-lactic acid) / poly(L-lactide) / biodegradable polyesters / biodegradable polymers / scaffolds for tissue regeneration / biomedical materials / crystalline residues / hydrolytic degradation / ポリ(L-ラクチ
Research Abstract

The purpose of this project is to elucidate the long-term in vitro hydrolytic degradation behavior and mechanism of PLLA crystalline residues (extended chain crystallites). For this purpose, PLLA crystalline residues were prepared by crystallization of PLLA films and subsequent accelerated hydrolytic degradation at 97℃ for 40 hours and the obtained crystalline residues were hydrolytically degraded at different conditions at pH 7.4 and different temperatures of 37, 50, 70, and 97℃ up to 512 days, at 37℃ at different pH of-0.9, 0.2, 7.4,11.7, and 12.8, and at pH8.6 and 37℃ in the presence of proteinase K. Also, the hydrolytic degradation behavior of L-lactic acid copolymers of poly(L-lactide-co-glycolide) (81:19) [P(LLA-GA)], poly(L-lactide-ε-caprolactone) (77/23) [P(LLA-CL)],and poly(L-lactide-co-D-lactide)] (77:23) (98.8:1.2) [P(LLA-DLA)] and their crystalline residues formed during hydrolytic degradation was monitored. The formation and hydrolytic degradation of the crystalline residu … More es were traced by gel permeation chromatography (GPC) and differential scanning calorimetry (DSC). The following results were obtained. (1) For all conditions, the crystalline residues are hydrolytically degraded linearly with degradation time from the chain terminals at the folding surface; (2) The activation energy for hydrolytic degradation (ΔE_h) of the crystalline residues at pH 7.4 was estimated to be 75.2 kJ mol^<-1>. This is much higher than 50.9 kJ mol^<-1> of ΔE_h reported for PLLA in the melt and indicates that higher hydrolytic degradation-resistance of the crystalline residues; (3) Acidic and alkaline conditions as well as high temperature enhanced the hydrolytic degradation of the crystalline residues, whereas proteinase K has no catalytic effect, revealing that the insignificant enzymatic activity of proteinase K for the PLLA chains neighboring on the crystalline regions. (4) The crystalline residues were formed and hydrolytically degraded in P(LLA-GA) and P(LLA-CL) films within the periods of 24 weeks, whereas in the case of PLLA and P(LLA-DLA) (98.8:1.2) films, neither formation nor hydrolytic degradation of crystalline residues took place within the degradation period of 50 weeks. Less

Report

(4 results)
  • 2006 Annual Research Report   Final Research Report Summary
  • 2005 Annual Research Report
  • 2004 Annual Research Report
  • Research Products

    (29 results)

All 2007 2006 2005 2004

All Journal Article (26 results) Book (3 results)

  • [Journal Article] Enzymatic Degradation of Poly (L-lactic acid) Fibers : Effects of Small Drawing2007

    • Author(s)
      H.Tsuji, Y.Kidokoro, M.Mochizuki
    • Journal Title

      Journal of Applied Polymer Science 103・3

      Pages: 2065-2071

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Enzymatic Degradation of Poly(L-lactic acid) Fibers : Effects of Small Drawing2007

    • Author(s)
      H.Tsuji, Y.Kidokoro, M.Mochizuki
    • Journal Title

      Journal of Applied Polymer Science Vol. 103, No. 3

      Pages: 2064-2071

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Degradation of Poly(lactide)-Based Biodegradable Materials2007

    • Author(s)
      H.Tsuji
    • Journal Title

      Nova Science Publishers

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Enzymatic Degradation of Poly(L-lactic acid) Fibers : Effects of Small Drawing2007

    • Author(s)
      H.Tsuji, Y.Kidokoro, M.Mochizuki
    • Journal Title

      Journal of Applied Polymer Science 103・3

      Pages: 2065-2071

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Enzymatic, Alkaline, and Autocatalytic Degradation of Poly(L-lactic acid) : Effects of Biaxial Orientation2006

    • Author(s)
      H.Tsuji, M.Ogiwara, S.K.Saha, T.Sakaki
    • Journal Title

      Biomacromolecules 7・1

      Pages: 380-387

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary 2005 Annual Research Report
  • [Journal Article] Effects of Molecular Weight and Small Amounts of D-lactide Units on Hydrolytic Degradation of Poly (L-lactic acid)s2006

    • Author(s)
      S.K.Saha, H.Tsuji
    • Journal Title

      Polymer Degradation and Stability 91・8

      Pages: 1665-1673

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Hydrolytic Degradation of Amorphous-Made Films of L-Lactide Copolymers with Glycolide and D-Lactide2006

    • Author(s)
      S.K.Saha, H.Tsuji
    • Journal Title

      Macromolecular Materials and Engineering 291・4

      Pages: 357-368

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary 2005 Annual Research Report
  • [Journal Article] Effects of Rapid Crystallization on Hydrolytic Degradation and Mechanical Properties of Poly (L-lactide-co-ε-caprolactone)2006

    • Author(s)
      S.K.Saha, H.Tsuji
    • Journal Title

      Reactive and Functional Polymer 66・11

      Pages: 1362-1372

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Enzymatic, Alkaline, and Autocatalytic Degradation of Poly(L-lactic acid) : Effects of Biaxial Orientation2006

    • Author(s)
      H.Tsuji, M.Ogiwara, S.K.Saha, T.Sakaki
    • Journal Title

      Biomacromolecules Vol. 7, No. 1

      Pages: 380-387

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Effects of Molecular Weight and Small Amounts of D-lactide Units on Hydrolytic Degradation of Poly(L- lactic acid)2006

    • Author(s)
      S.K.Saha, H.Tsuji
    • Journal Title

      Polymer Degradation and Stability Vol. 91, No. 8

      Pages: 1665-1673

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Hydrolytic Degradation of Amorphous-Made Films of L-Lactide Copolymers with Glycolide and D-Lactide2006

    • Author(s)
      S.K.Saha, H.Tsuji
    • Journal Title

      Macromolecular Materials and Engineering Vol. 291, No. 4

      Pages: 357-368

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Effects of Rapid Crystallization on Hydrolytic Degradation and Mechanical Properties of Poly(L-lactide-co-ε- caprolactone)2006

    • Author(s)
      S.K.Saha, H.Tsuji
    • Journal Title

      Reactive and Functional Polymers Vol. 66, No. 11

      Pages: 1362-1372

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Effects of Rapid Crystallization on Hydrolytic Degradation and Mechanical Properties of Poly(L-lactide-co-ε-caprolactone)2006

    • Author(s)
      S.K.Saha, H.Tsuji
    • Journal Title

      Reactive and Functional Polymer 66・11

      Pages: 1362-1372

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Effects of Molecular Weight and Small Amounts of D-lactide Units on Hydrolytic Degradation of Poly(L-lactic acid)s2006

    • Author(s)
      S.K.Saha, H.Tsuji
    • Journal Title

      Polymer Degradation and Stability 91・8

      Pages: 1665-1673

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Poly (L-lactide) : XII. Formation, Growth, and Morphology of Crystalline Residues as Extended-Chain Crystallites through Hydrolysis of Poly(L-lactide) Films2004

    • Author(s)
      H.Tsuji, K.Ikarashi, N.Fukuda
    • Journal Title

      Polymer Degradation and Stability 84・3

      Pages: 515-523

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] In Vitro Hydrolysis of Poly(L-lactide) Crystalline Residues as Extended-Chain Crystallites : I. Long-Term Hydrolysis in Phosphate-Buffered Solution at 37℃2004

    • Author(s)
      H.Tsuji, K.Ikarashi
    • Journal Title

      Biomaterials 25・24

      Pages: 5449-5455

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] In Vitro Hydrolysis of Poly(L-lactide) Crystalline Residues as Extended-Chain Crystallites : II. Effects of Hydrolysis Temperature2004

    • Author(s)
      H.Tsuji, K.Ikarashi
    • Journal Title

      Biomacromolecules 5・3

      Pages: 1021-1028

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] In Vitro Hydrolysis of Poly(L-lactide) Crystalline Residues as Extended-Chain Crystallites : III. Effects of pH and Enzyme2004

    • Author(s)
      H.Tsuji, K.Ikarashi
    • Journal Title

      Polymer Degradation and Stability 85・1

      Pages: 647-656

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Poly(L-lactide) : Xll. Formation, Growth, and Morphology of Crystalline Residues as Extended- Chain Crystallites through Hydrolysis of Poly(L-lactide) Films2004

    • Author(s)
      H.Tsuji, K.Ikarashi, N.Fukuda
    • Journal Title

      Polymer Degradation and Stability Vol. 84, No. 3

      Pages: 515-523

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] In Vitro Hydrolysis of Poly(L-lactide) Crystalline Residues as Extended-Chain Crystallites : l. Long- Term Hydrolysis in Phosphate-Buffered Solution at 37°C2004

    • Author(s)
      H.Tsuji, K.Ikarashi
    • Journal Title

      Biomaterials Vol. 25, No. 24

      Pages: 5449-5455

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] In Vitro Hydrolysis of Poly(L-lactide) Crystalline Residues as Extended-Chain Crystallites : ll. Effects of Hydrolysis Temperature2004

    • Author(s)
      H.Tsuji, K.Ikarashi
    • Journal Title

      Biomacromolecules Vol. 5, No. 3

      Pages: 1021-1028

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] In Vitro Hydrolysis of Poly(L-lactide) Crystalline Residues as Extended-Chain Crystallites : lll. Effects of pH and Enzyme2004

    • Author(s)
      H.Tsuji, K.Ikarash
    • Journal Title

      Polymer Degradation and Stability Vol. 85, No. 1

      Pages: 647-656

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Poly(L-lactide) : XII. Formation, Growth, and Morphology of Crystalline Residues as Extended-Chain Crystallites through Hydrolysis of Poly(L-lactide) Films2004

    • Author(s)
      H.Tsuji, K.Ikarashi, N.Fukuda
    • Journal Title

      Polymer Degradation and Stability 84(3)

      Pages: 515-523

    • Related Report
      2004 Annual Research Report
  • [Journal Article] In Vitro Hydrolysis of Poly(L-lactide) Crystalline Residues as Extended-Chain Crystallites : I Long-Term Hydrolysis in Phosphate-Buffered Solution at 372004

    • Author(s)
      H.Tsuji, K.Ikarashi
    • Journal Title

      Biomaterials 25(24)

      Pages: 5449-5455

    • Related Report
      2004 Annual Research Report
  • [Journal Article] In Vitro Hydrolysis of Poly(L-lactide) Crystalline Residues as Extended-Chain Crystallites : II Effects of Hydrolysis Temperature2004

    • Author(s)
      H.Tsuji, K.Ikarashi
    • Journal Title

      Biomacromolecules 5(3)

      Pages: 1021-1028

    • Related Report
      2004 Annual Research Report
  • [Journal Article] In Vitro Hydrolysis of Poly(L-lactide) Crystalline Residues as Extended-Chain Crystallites : III. Effects of pH and Enzyme2004

    • Author(s)
      H.Tsuji, K.Ikarashi
    • Journal Title

      Polymer Degradation and Stability 85(1)

      Pages: 647-656

    • Related Report
      2004 Annual Research Report
  • [Book] Polymer Degradation and Stability Research Trends2007

    • Author(s)
      H.Tsuji et al.
    • Publisher
      Nova Science Publishers (未定(印刷中))
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Book] ポリ乳酸グリーンプラスチックの開発と応用-植物系樹脂の実用化2005

    • Author(s)
      辻 秀人 他
    • Total Pages
      231
    • Publisher
      フロンティア出版
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Book] 高分子材料と複合材料の耐久性(大澤善次郎監修)2005

    • Author(s)
      辻 秀人 他
    • Total Pages
      435
    • Publisher
      シーエムシー出版
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary

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Published: 2004-04-01   Modified: 2016-04-21  

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