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2008 Fiscal Year Final Research Report

Studies on functionalities and structures of TEMPO-oxidized polysaccharides

Research Project

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Project/Area Number 18380102
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field 林産科学・木質工学
Research InstitutionThe University of Tokyo

Principal Investigator

IAOGAI Akira  The University of Tokyo, 大学院・農学生命科学研究科, 教授 (40191879)

Co-Investigator(Kenkyū-buntansha) 杉山 淳司  京都大学, 生存圏研究所, 教授
Co-Investigator(Renkei-kenkyūsha) 和田 昌久  東京大学, 大学院・農学生命科学研究科, 准教授
羽生 直人  宇都宮大学, 農学部, 准教授
北岡 卓也  九州大学, 大学院・農学研究院, 准教授
杉山 淳司  京都大学, 生存圏研究所, 教授
和田 昌久  東京大学, 大学院・農学生命科学研究科, 准教授
羽生 直人  宇都宮大学, 農学部, 准教授
北岡 卓也  九州大学, 大学院・農学研究院, 准教授
Project Period (FY) 2006 – 2008
Keywords環境材料 / ナノ材料 / 糖 / 多糖 / 触媒酸化
Research Abstract

2, 2, 6, 6-テトラピペリジニル-1-オキシラジカル(TEMPO)を触媒量用いる水系媒体での、セルロースを含む多糖の酸化改質について詳細に検討した。新しく開発した亜塩素酸ナトリウムを主酸化剤とする弱酸性~中性条件でのTEMPO 触媒酸化を、天然セルロース、レーヨンあるいはセルロースビーズのような再生セルロース、その他の多糖類について適用した。その結果、β脱離反応による低分子化が抑えられるために、天然セルロースの酸化-水中解繊処理では、高分子量でアスペクト比の大きいTEMPO 酸化セルロースナノファイバーが得られた。木材セルロースから得られたナノファイバーは幅が4~5nm で、長さは数ミクロン以上あり、新規TEMPO 酸化セルロースナノファイバーの調製方法として確立することができた。天然セルロースをボールミル粉砕して非晶化した場合には、水溶性のポリウロン酸であるセロウロン酸が得られた。一方、レーヨン繊維の亜塩素酸ナトリウム系TEMPO 触媒酸化でも、水溶性のセロウロン酸が得られたが、その分子量は従来法の6 倍以上となり、化学構造も均一であった。再生セロロースビーズに亜塩素酸ナトリウム系TEMPO 触媒酸化を適用したところ、元の多孔質、ビーズ形状を保ったまま、その表面に高密度でカルボキシル基を導入することができた。そのTEMPO 酸化セルロースビーズは、既存のカルボキシメチル化ビーズよりも、高い金属イオン吸着能、カチオン性高分子吸着能を示し、新しい分離用アニオン性セルロースビーズの開発につながるデータを得ることができた。再生セルロースでもレーヨンのようにセロウロン酸が得られる場合と、セルロースビーズのように固体表面のみにカルボキシル基が導入される場合があり、全く異なるがこれは両者の固体構造を反映している。

  • Research Products

    (75 results)

All 2009 2008 2007 Other

All Journal Article (22 results) Presentation (25 results) Book (3 results) Remarks (3 results) Patent(Industrial Property Rights) (22 results)

  • [Journal Article] Degrees of polymerization (DP) and DP distribution of cellouronic acids prepared from alkali-treated celluloses and ball-milled native celluloses by TEMPO-mediated oxidation2009

    • Author(s)
      Isogai, T., Yanagisawa, M., Isogai, A.
    • Journal Title

      Cellulose 16

      Pages: 117-127

  • [Journal Article] Transparent and high gas barrier films of cellulose nanofibers prepared by TEMPO-mediated oxidation2009

    • Author(s)
      Fukuzumi, H., Saito, T., Kumamoto, Y., Iwata, T., Isogai, A.
    • Journal Title

      Biomacromolecules 10

      Pages: 162-165

  • [Journal Article] Cloning of the Trichloderma reesi cDNA encoding a glucuronan lyase belonging to a novel polysaccharide lyase family2009

    • Author(s)
      Konno, N., Igarashi, K., Habu, N., Samejima, M., Isogai, A.
    • Journal Title

      Appl. Environ. Microbiol. 75

      Pages: 101-107

  • [Journal Article] Preparation of pure vaterite by simple mechanical mixing of two aqueous salt solutions2009

    • Author(s)
      Mori, Y., Enomae, T., Isogai, A.
    • Journal Title

      Materials Sci. Eng. C 29(in press)

  • [Journal Article] Enzymatic degradation of amylouronate (alpha-(1->4)-linked glucuronan) by alpah-glucuronidase from Paenibacillus sp. TH501b2009

    • Author(s)
      Iihashi, N., Nagayama, J., Habu, N., Konno, N., Isogai, A.
    • Journal Title

      Carbohydr. Polym. (in press)

  • [Journal Article] TEMPOmediated oxidation of (1→3)-beta-D-glucans2009

    • Author(s)
      Tamura, N., Wada, M., Isogai, A.
    • Journal Title

      Carbohydr. Polym. (in press)

  • [Journal Article] TEMPO-mediated oxidation of beta-chitin to prepare individual nanofibrils2009

    • Author(s)
      Fan, Y., Saito, T., Isogai, A.
    • Journal Title

      Carbohydr. Polym. (in press)

  • [Journal Article] Crystal structure of polysaccharide lyase family 20 endo-β-1,4-glucuronan lyase from the filamentous fungus Trichoderma reesei2009

    • Author(s)
      Konno, N., Ishida, T., Igarashi, K., Fushinobu S., Samejima, M., Habu, N., Isogai, A.
    • Journal Title

      FEBS Lett (in press)

  • [Journal Article] TEMPO酸化セルロースナノファイバー2009

    • Author(s)
      磯貝明
    • Journal Title

      高分子 58

      Pages: 90-91

  • [Journal Article] バイオ系ナノファイバーの調成と高機能部材への応用展開2009

    • Author(s)
      磯貝明
    • Journal Title

      繊維学会誌 65

      Pages: P7-P8

  • [Journal Article] Chitin nano-fibers/whiskers prepared by TEMPO-mediated oxidation of alpha-chitin2008

    • Author(s)
      Fan, Y., Saito, T., Isogai, A.
    • Journal Title

      Biomacromolecules 9

      Pages: 192-198

  • [Journal Article] Purification and characterization of exo-type cellouronate lyase2008

    • Author(s)
      Konno, N., Isogai, A., Habu, N., Iihashi, N.
    • Journal Title

      Cellulose 15

      Pages: 453-463

  • [Journal Article] Determination of residual amide content in sequentially solvent-exchanged and vacuum-dried cellulose2008

    • Author(s)
      Ishii, D., Isogai, A.
    • Journal Title

      Cellulose 15

      Pages: 651-658

  • [Journal Article] Degrees of polymerization (DP) and DP distribution of dilute acid-hydrolyzed products of alkali-treated native and regenerated celluloses2008

    • Author(s)
      Isogai, T., Yanagisawa, M., Isogai, A.
    • Journal Title

      Cellulose 15

      Pages: 815-823

  • [Journal Article] Preparation of chitin nanofibers from squid pen beta-chitin by simple mechanical treatment under acid conditions2008

    • Author(s)
      Fan, Y., Saito, T., Isogai, A.
    • Journal Title

      Biomacromolecules 9

      Pages: 1919-1923

  • [Journal Article] Differences in residual lignin properties between Betula verrucosa and Eucalyputus urogradis kraft pulps2008

    • Author(s)
      Hanninen, T. A., Kontturi, E., Isogai, A., Vuorinen, T.
    • Journal Title

      Biopolymers 89

      Pages: 889-893

  • [Journal Article] ナノファイバー技術による新しい文化・産業の創生2008

    • Author(s)
      磯貝明
    • Journal Title

      機能紙研究会誌 46

      Pages: 3-12

  • [Journal Article] パルプ繊維の化学的および機械的改質手法とその効果2008

    • Author(s)
      磯貝明
    • Journal Title

      紙パ技協誌 62

      Pages: 830-838

  • [Journal Article] Size exclusion chromatographic and UV-VIS absorption analyses of softwood unbleached and bleached kraft pulps using LiCl/1, 3-dimethyl-2-imidazolidinone as a solvent2007

    • Author(s)
      Yanagisawa, M., Isogai, A.
    • Journal Title

      Holzforschung 61

      Pages: 236-241

  • [Journal Article] Cellulose Nanofibers Prepared by TEMPOMediated Oxidation of Native Cellulose2007

    • Author(s)
      Saito, T., Kimura, S., Nishiyama, Y., Isogai, A.
    • Journal Title

      Biomacromolecules 8

      Pages: 2492-2496

  • [Journal Article] 天然セルロースのTEMPO触媒酸化によるセルロースシングルミクロフィブリルの調製2007

    • Author(s)
      斉藤継之, 磯貝明
    • Journal Title

      Cellulose Commun. 14

      Pages: 62-66

  • [Journal Article] セルロースナノファイバーの調製と包装分野への応用の可能性2007

    • Author(s)
      磯貝明
    • Journal Title

      日本包装学会誌 16

      Pages: 185-190

  • [Presentation] Individualization of nanosized plant cellulose fibrils achieved by TEMPO-mediated oxidation under neutral conditions2009

    • Author(s)
      Saito, T., Hirota, M., Tamura, N., Fukuzumi, H., Isogai, A.
    • Organizer
      ACS National Meeting
    • Place of Presentation
      Salt Lake City, USA
    • Year and Date
      20090000
  • [Presentation] TEMPO-mediated oxidation of cellulose and other polysaccharides2009

    • Author(s)
      Isogai, A.
    • Organizer
      ACS National Meeting
    • Place of Presentation
      Salt Lake City, USA
    • Year and Date
      20090000
  • [Presentation] Properties of TEMPO-oxidized cellulose nanofiber film2009

    • Author(s)
      Fukuzumi, H., Saito, T., Isogai, A.
    • Organizer
      ACS National Meeting
    • Place of Presentation
      Salt Lake City, USA
    • Year and Date
      20090000
  • [Presentation] Degree of polymerization (DP) of cellouronic acid prepared from ball-milled native celluloses by TEMPOmediated oxidation2009

    • Author(s)
      Isogai, T., Isogai, A.
    • Organizer
      ACS National Meeting
    • Place of Presentation
      Salt Lake City, USA
    • Year and Date
      20090000
  • [Presentation] Mechanical properties of cellulose single nanofiber measured by atomic force microscopy2009

    • Author(s)
      Iwamoto, S., Weihua, K., Iwata, T., Isogai, A.
    • Organizer
      ACS National Meeting
    • Place of Presentation
      Salt Lake City, USA
    • Year and Date
      20090000
  • [Presentation] Oxidation of polysaccharides by TEMPO/NaClO_2/NaClO2009

    • Author(s)
      Tamura, N., Hirota, M., Isogai, A.
    • Organizer
      ACS National Meeting
    • Place of Presentation
      Salt Lake City, USA
    • Year and Date
      20090000
  • [Presentation] Preparation of cellulose single nanofibers by TEMPO-mediated oxidation of native celluloses : Fundamentals and applications2008

    • Author(s)
      Isogai, A.
    • Organizer
      ACS National Meeting
    • Place of Presentation
      New Orleans
    • Year and Date
      20080400
  • [Presentation] Chitin nanocrystals prepared by TEMPO-mediated oxidation of alpha-and beta-chitin2008

    • Author(s)
      Fan, Y., Saito, T., Isogai, A.
    • Organizer
      ACS National Meeting
    • Place of Presentation
      New Orleans
    • Year and Date
      20080400
  • [Presentation] Characterization of cellouronate lyase from Trichoderma reesei2008

    • Author(s)
      Konno, N., Igarashi, K., Samejima, M., Isogai, A.
    • Organizer
      ACS National Meeting
    • Place of Presentation
      New Orleans
    • Year and Date
      20080400
  • [Presentation] Hybridization of cellulose nanofibers and vaterite form calcium carbonate2008

    • Author(s)
      Mori, Y., Isogai, A.
    • Organizer
      ACS National Meeting
    • Place of Presentation
      New Orleans
    • Year and Date
      20080400
  • [Presentation] Cellulose single nanofibers prepared from TEMPO-mediated oxidation of native cellulose-Fundamentals and applications2008

    • Author(s)
      Isogai, A., Saito, T., Fukuzumi, H., Okita, Y.
    • Organizer
      TAPPI Int. Conf. Pulping Paper Biotechnol.
    • Place of Presentation
      Nanjing, China
    • Year and Date
      20080000
  • [Presentation] Preparation of bi-nanofibers from natural materials2008

    • Author(s)
      Fan, Y., Saito, T., Isogai, A.
    • Organizer
      TAPPI Int. Conf. Pulping Paper Biotechnol.
    • Place of Presentation
      Nanjing, China
    • Year and Date
      20080000
  • [Presentation] Individualized cellulose nanofibers : Preparation from native cellulose by TEMPO-mediated oxidation2007

    • Author(s)
      Saito, T., Kimura, S., Nishiyama, Y., Isogai, A.
    • Organizer
      Int. Cellulose Conf.
    • Place of Presentation
      Tokyo
    • Year and Date
      20071000
  • [Presentation] Application of TEMPO-mediated oxidation to chitin2007

    • Author(s)
      Fan, Y., Saito, T., Isogai, A.
    • Organizer
      Int. Cellulose Conf.
    • Place of Presentation
      Tokyo
    • Year and Date
      20071000
  • [Presentation] Purification and characterization of enzymes responsible for the degradation of polyuronates2007

    • Author(s)
      Iihashi, N., Habu, N., Konno, N., Isogai, A.
    • Organizer
      Int. Cellulose Conf.
    • Place of Presentation
      Tokyo
    • Year and Date
      20071000
  • [Presentation] Cellouronate lyase from Trichoderma reesei : Cloning and characterization2007

    • Author(s)
      Konno, N., Igarashi, K., Habu, N., Samejima, M., Isogai, A.
    • Organizer
      Int. Cellulose Conf.
    • Place of Presentation
      Tokyo
    • Year and Date
      20071000
  • [Presentation] Structural analysis and gelation mechanism of cellulose in LiCl-DMAc2007

    • Author(s)
      Ishii, D., Tatsumi, D., Murata, K., Hayashi, H., Yoshitani, H., Isogai, A., Matsumoto, T.
    • Organizer
      Int. Cellulose Conf.
    • Place of Presentation
      Tokyo
    • Year and Date
      20071000
  • [Presentation] SEC-MALLS analysis of cellouronic acid-The effect of leveling-off DP of celluloses on molecular mass of cellouronic acid-2007

    • Author(s)
      Isogai, T., Yanagisawa, M., Isogai, A.
    • Organizer
      Int. Cellulose Conf.
    • Place of Presentation
      Tokyo
    • Year and Date
      20071000
  • [Presentation] tructural analysis of cellulosic microfibrils prepared by TEMPO-mediated oxidation2007

    • Author(s)
      Okita, Y., Saito, T., Isogai, A.
    • Organizer
      Int. Cellulose Conf.
    • Place of Presentation
      Tokyo
    • Year and Date
      20071000
  • [Presentation] Nanofiber films prepared by TEMPO-mediated oxidation of Native Cellulose2007

    • Author(s)
      Fukuzumi, H., Saito, T., Isogai, A.
    • Organizer
      Int. Cellulose Conf.
    • Place of Presentation
      Tokyo
    • Year and Date
      20071000
  • [Presentation] Cellulose nanofibers prepared by TEMPO-mediated oxidation of native cellulose2007

    • Author(s)
      Isogai, A.
    • Organizer
      Int. Academy Wood Sci. Annual Meeting
    • Place of Presentation
      Tokyo
    • Year and Date
      20071000
  • [Presentation] Cellulose and Chitin Nanofibers Prepared by TMPO-mediated Oxidation2007

    • Author(s)
      Isogai, A.
    • Organizer
      European-Japanese Workshop Cellulose Functional Polysaccharides
    • Place of Presentation
      Tokyo
    • Year and Date
      20071000
  • [Presentation] Biodegradation of cellouronate by Trichoderma reesei2007

    • Author(s)
      Konnno, N., et al.
    • Organizer
      10th Int. Congress on Biotechnology in the Pulp and Paper Industry
    • Place of Presentation
      Madison, USA
    • Year and Date
      20070600
  • [Presentation] Preparation of cellulose single microfibrils by TEMPO-mediated oxidation of native cellulose-Fundamentals and applications-2007

    • Author(s)
      Isogai, A.
    • Organizer
      Int. Nanofiber Symp.
    • Place of Presentation
      Tokyo
    • Year and Date
      20070600
  • [Presentation] Cellulose nanofibers obtained by TEMPO-mediated oxidation of wood cellulose2007

    • Author(s)
      Saito, T., Isogai, A.
    • Organizer
      Int. Nanofiber Symp.
    • Place of Presentation
      Tokyo
    • Year and Date
      20070600
  • [Book] "Integrated sizeexclusion chromatography (SEC) analysis of cellulose and its derivatives" in"Characterization of lignocellulosic materials"2008

    • Author(s)
      Yanagisawa, M., Isogai, A.
    • Publisher
      Ed by Hu, T. Q., Blackwell, New York
  • [Book] セルロース利用の最先端 れ : 第IV編、第3章セルロースナノファイバー新素材2008

    • Author(s)
      斉藤継之, 磯貝明
    • Total Pages
      278-288
    • Publisher
      シーエムシー
  • [Book] ウッドケミカルスの新展開第6章1セルロース改質技術の現状2007

    • Author(s)
      磯貝明
    • Total Pages
      131-141
    • Publisher
      シーエムシー
  • [Remarks] 化学工業日報にセルロースナノファイバーの記事掲載(2009-2-13)

  • [Remarks] 日刊工業新聞にキチンナノファイバーの記事掲載(2009-3-20)

  • [Remarks] 日刊工業新聞にセルロースナノファイバーの記事掲載(2009-3-30)

  • [Patent(Industrial Property Rights)] キチンナノファイバーとその製造方法、キチンナノファイバー分散液、ナノフィブリル構造体、及びキチン複合体2009

    • Inventor(s)
      磯貝明, 齋藤継之, 范一民
    • Industrial Property Number
      特願2009-024286
    • Filing Date
      20090000
  • [Patent(Industrial Property Rights)] セルロース繊維の懸濁液とその製造方法2009

    • Inventor(s)
      向井健太, 熊本吉晃, 磯貝明
    • Industrial Property Number
      特願2009-025916
    • Filing Date
      20090000
  • [Patent(Industrial Property Rights)] セルロース繊維の親水性化処理方法、親水性セルロース繊維、処理剤、及び繊維製品2008

    • Inventor(s)
      磯貝明, 斉藤継之, 平野昌一, 由井美也, 田中千晶
    • Industrial Property Number
      特願2008-042406
    • Filing Date
      20080000
  • [Patent(Industrial Property Rights)] セルロースの改質方法、改質セルロース、セロウロン酸、セルロース微結晶2008

    • Inventor(s)
      磯貝明, 齋藤継之, 田村直之, 廣田真之
    • Industrial Property Number
      特願2008-051351
    • Filing Date
      20080000
  • [Patent(Industrial Property Rights)] 機能性セルロースビーズの製造方法、及び機能性セルロースビーズ2008

    • Inventor(s)
      磯貝明, 齋藤継之, 田村直之, 廣田真之
    • Industrial Property Number
      特願2008-051352
    • Filing Date
      20080000
  • [Patent(Industrial Property Rights)] セロウロン酸およびその製造方法2008

    • Inventor(s)
      磯貝明, 磯貝拓也
    • Industrial Property Number
      特願2008-157042
    • Filing Date
      20080000
  • [Patent(Industrial Property Rights)] 製紙用添加剤及びそれを含有する紙2008

    • Inventor(s)
      宮脇正一, 勝川志穂, 阿部裕, 飯嶋夕子, 磯貝明
    • Industrial Property Number
      特願2008-091333
    • Filing Date
      20080000
  • [Patent(Industrial Property Rights)] セルロースナノファイバーの製造方法2008

    • Inventor(s)
      宮脇正一, 勝川志穂, 阿部裕, 飯嶋夕子, 磯貝明
    • Industrial Property Number
      特願2008-094050
    • Filing Date
      20080000
  • [Patent(Industrial Property Rights)] 加工用紙用原紙2008

    • Inventor(s)
      宮脇正一, 勝川志穂, 阿部 裕, 飯嶋夕子, 磯貝明
    • Industrial Property Number
      特願2008-093496
    • Filing Date
      20080000
  • [Patent(Industrial Property Rights)] 化粧品組成物2008

    • Inventor(s)
      磯貝明, 角英行, 後居洋介
    • Industrial Property Number
      特願2008-197848
    • Filing Date
      20080000
  • [Patent(Industrial Property Rights)] スプレー用組成物およびそれを用いたスプレー噴霧装置2008

    • Inventor(s)
      磯貝明, 角英行, 後居洋介
    • Industrial Property Number
      特願2008-197849
    • Filing Date
      20080000
  • [Patent(Industrial Property Rights)] ゲル状組成物2008

    • Inventor(s)
      磯貝明, 角英行, 後居洋介
    • Industrial Property Number
      特願2008-197847
    • Filing Date
      20080000
  • [Patent(Industrial Property Rights)] セルロース及びキチンナノファイバーとアモルファス炭酸塩及びリン酸塩の複合材料、その製造方法2008

    • Inventor(s)
      磯貝明, 齋藤継之, 加藤隆史, 西村達也, 緒明佑哉
    • Industrial Property Number
      特願2008-206488
    • Filing Date
      20080000
  • [Patent(Industrial Property Rights)] セルロースナノファイバーの製造方法2007

    • Inventor(s)
      磯貝明, 沖田祐介, 斉藤継之
    • Industrial Property Number
      特願2007-160604
    • Filing Date
      20070000
  • [Patent(Industrial Property Rights)] 可溶性多糖の製造方法2007

    • Inventor(s)
      磯貝明, 和田昌久, 田村直之
    • Industrial Property Number
      特願2007-260608
    • Filing Date
      20070000
  • [Patent(Industrial Property Rights)] 酸素バリア用材料2007

    • Inventor(s)
      磯貝明, 熊本吉晃
    • Industrial Property Number
      2007-205087
    • Filing Date
      20070000
  • [Patent(Industrial Property Rights)] 水蒸気バリア用材料2007

    • Inventor(s)
      磯貝明, 熊本吉晃
    • Industrial Property Number
      2007-205088
    • Filing Date
      20070000
  • [Patent(Industrial Property Rights)] ベータキチンナノファイバーとその製造方法、ベータキチンナノファイバー分散液、ナノフィブリル構造体、及びキチン複合体2007

    • Inventor(s)
      范一民, 斉藤継之, 磯貝明
    • Industrial Property Number
      特願2007-277923
    • Filing Date
      20070000
  • [Patent(Industrial Property Rights)] セルロースナノファイバーとその製造方法、セルロースナノファイバー分散液2007

    • Inventor(s)
      斉藤継之, 磯貝 明
    • Industrial Property Number
      特願2007-304411
    • Filing Date
      20070000
  • [Patent(Industrial Property Rights)] セルロースナノファイバーの製造方法及びセルロースの酸化触媒2007

    • Inventor(s)
      宮脇正一, 阿部 裕, 飯嶋夕子, 磯貝 明
    • Industrial Property Number
      特願2007-340371
    • Filing Date
      20070000
  • [Patent(Industrial Property Rights)] セルロースの酸化方法、セルロースナノファイバーの製造方法2007

    • Inventor(s)
      宮脇正一, 阿部 裕, 飯嶋夕子, 磯貝 明
    • Industrial Property Number
      特願2007-340441
    • Filing Date
      20070000
  • [Patent(Industrial Property Rights)] ガスバリア用材料

    • Inventor(s)
      熊本吉晃, 向井健太, 宇賀神徹, 前澤貴浩, 本棒直樹, 磯貝明
    • Industrial Property Number
      WO 2009/020239 A1

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Published: 2010-06-10   Modified: 2016-04-21  

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