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Functionalization of cellulosic materials by TEMPO-mediated oxidation under aqueous media

Research Project

Project/Area Number 11660160
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field 林産学
Research InstitutionTHE UNIVERSITY OF TOKYO

Principal Investigator

ISOGAI Akira  Graduate School of Agricultural and Life Sciences, Department of Biomaterial Science THE UNIVERSITY OF TOKYO Associate Professor, 大学院・農学生命科学研究科, 助教授 (40191879)

Project Period (FY) 1999 – 2000
Project Status Completed (Fiscal Year 2000)
Budget Amount *help
¥3,500,000 (Direct Cost: ¥3,500,000)
Fiscal Year 2000: ¥1,100,000 (Direct Cost: ¥1,100,000)
Fiscal Year 1999: ¥2,400,000 (Direct Cost: ¥2,400,000)
KeywordsCellulose / Chitin / TEMPO / Biodegradability / Oxidation / Functionalization / Biometabolizability / Polyuronic acid / セロウロン酸 / カルボキシル基 / グルクロン酸
Research Abstract

A.Depolymerization of cellulose during the TEMPO-mediated oxidation must be controlled as possible in order to prepare water-soluble cellouronic acid (β-1, 4-linked polyglucuronic acid) having various molecular weights. Then depolymerization mechanism of cellouronic acid during the oxidation was studied under various conditions by changing combinations of the reagents added. Molecular weights of the products were determined by size exclusion chromatography using aqueous GPC columns and 0.1N NaCl as an eluent. The results showed that some radicals formed in the oxidation medium consisting of TEMPO and NaBrO during the oxidation were likely to bring about remarkable depolymerization. β-Elimination had little influence on the depolymerization.
B.The addition of t-butylphenol as a radical scavenger to the oxidation medium could avoid the depolymerization to some extent, although neither MgCl_2 nor sodium dithonite had the effect.
C.When higher molecular weight regenerated celluloses, such as hollow fibers prepared from linters by cupriammonium solutions, were used as the starting materials for the TEMPO-mediated oxidation, correspondingly higher molecular weight cellouronic acids were prepared.
D.α-Chitin, β-chitin, amylose, amylopectin, curdlan and pullulan were selectively oxidized at their C6 primary hydroxyl groups to give the corresponding water-soluble polyuronic acids quantitatively by the TEMPO-mediated oxidation.
E.Cellouronic acid was hydrolyzed to glucuronic acid by crude cellulase treatments, and thus cellouronic acid had both biodegradability and biometabolizability.

Report

(3 results)
  • 2000 Annual Research Report   Final Research Report Summary
  • 1999 Annual Research Report
  • Research Products

    (21 results)

All Other

All Publications (21 results)

  • [Publications] Kato,Y., et al.: "Biodegradation of β-1,4-linked polyglucuronic acid (cellouronic acid)"Cellulose. 8(in press). (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Kitaoka,T., et al.: "Rosin sizing of pulps modified by TEMPO-mediated oxidation"Nordic Pulp and Paper Research Journal. 15. 177-182 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Kitaoka,T., et al.: "Chemical modification of pulp fibers by TEMPO-mediated oxidation"Norbic Pulp and Paper Research Journal. 14. 274-279 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Isogai,A., et al.: "TEMPO-mediated oxidation of cellulose"Proceedings of the 10^<th> ISWPC. Vo.1. 640-643 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] 磯貝明: "セルロースの材料科学"東京大学出版会. 182 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] 磯貝明(分担執筆): "セルロースの事典"朝倉書店. 580 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Kato, Y., Habu, N., Isogai, A., Shibata, I.and Samejima, M.: "Biodegradation of β-1, 4-linked polyglucuronic acid (cellouronic acid)"Cellulose. 8 (in press). (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Kitaoka, T., Isogai, A.and Onabe, F.: "Rosin sizing of pulps modified by TEMPO-mediated oxidation"Nordic Pulp and Paper Research Journal. 15. 177-182 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Kitaoka, T., Isogai, A.and Onabe, F.: "Chemical modification of pulp fibers by TEMPO-mediated oxidation"Nordic Pulp and Paper Research Journal. 14. 274-279 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Isogai, Kato, Y., Kitaoka, T.and Onabe, F.: "TEMPO-mediated oxidation of cellulose"Proceedings of the 10^<th> ISWPC, Yokohama, June. 640-643 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Isogai, A.: "Material science of cellulose"Tokyo University Press (Tokyo). (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Isogai, A.: ""Encyclopedia of cellulose"(Ed.by Japan Cellulose Society)"Asakura Book Store (Tokyo). (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Kato,Y., et al.: "Biodegradation of β-1,4-linked polyglucuronic acid (cellouronic acid)"Cellulose. 8(in press). (2001)

    • Related Report
      2000 Annual Research Report
  • [Publications] Kitaoka,T., et al.: "Rosin sizing of pulps modified by TEMPO-mediated oxidation"Nordic Pulp and Paper Research Journal. 15. 177-182 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Kitaoka,T., et al.: "Chemical modification of pulp fibers by TEMPO-mediated oxidation"Nordic Pulp and Paper Research Journal. 14. 274-279 (1999)

    • Related Report
      2000 Annual Research Report
  • [Publications] Isogai,A., et al.: "TEMPO-mediated oxidation of cellulose"Proceedings of the 10^<th> ISWPC. Vol.1. 640-643 (1999)

    • Related Report
      2000 Annual Research Report
  • [Publications] 磯貝明: "セルロースの材料科学"東京大学出版会. 182 (2001)

    • Related Report
      2000 Annual Research Report
  • [Publications] 磯貝明(分担執筆): "セルロースの事典"朝倉書店. 580 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Kitaoka, T., Isogai, A.: "Rosin sizing of pulps modified by TEMPO-mediated oxidation"Nordic Pulp and Paper Research Journal. 15(発表予定). (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Kitaoka, T., Isogai, A.: "Chemical modification of pulp fibers by TEMPO-mediated oxidation"Nordic Pulp and Paper Research Journal. 14(4). 274-279 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] 磯貝 明: "安定ニトロキシルラジカル試薬ノセルロース改質ヘノ応用"Cellulose Communications. 5(3). 136-141 (1998)

    • Related Report
      1999 Annual Research Report

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Published: 1999-04-01   Modified: 2016-04-21  

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