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Formation and stability of cellulose–copper–NaOH crystalline complex

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Abstract

We investigated the crystal structure of alkali-celluloses, Na-cellulose IIA and II(Cu), formerly known as Na-cellulose IIB, by synchrotron X-ray diffraction. Na-cellulose IIA, formed from cellulose I by high-concentration NaOH treatment, has a fiber repeat of 15 Å and a threefold-like helical conformation. Na-cellulose II(Cu), prepared by treating cellulose I with copper-saturated alkali solution, also has a fiber repeat of 15 Å with threefold helical symmetry. Incorporation of Cu(II) ions into cellulose was confirmed by multiwavelength anomalous diffraction. Monitoring by X-ray diffraction revealed that the formation of this complex from cellulose I is remarkably slow, probably because of the involvement of copper ion. The stability of alkali-cellulose II(Cu) was tested to estimate the influence of the presence of copper in the crystal. Na-cellulose II(Cu) characteristically dissolved in aqueous ammonia solution, indicating strong coordination of copper ion to cellulose.

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References

  • Alexander LE (1979) X-ray Diffraction Methods. In: E. Robert (Ed) Polymer Science Kreiger, New York, pp 423–424

  • Hendrickson W (1991) Determination of macromolecular structures from anomalous diffraction of synchrotron radiation. Science 254:52–58

    Article  Google Scholar 

  • Langan P, Nishiyama Y, Chanzy H (2001) X-ray structure of mercerized cellulose II at 1 Å resolution. Biomacromolecules 2:410–416

    Article  CAS  Google Scholar 

  • Miyamoto I, Inamoto M, Matsui T, Saito M, Okajima K (1995) Studies on structure of cuprammonium cellulose 1. A circular dichroism study on the dissolved state of cellulose in cuprammonium solution. Polym J 27:1113–1122

    Article  CAS  Google Scholar 

  • Nishimura H, Sarko A (1991) Mercerization of cellulose IV. Crystal and molecular-structure of Na-cellulose IV. Macromolecules 24:771–778

    Article  CAS  Google Scholar 

  • Nishimura H, Okano T, Sarko A (1991) Mercerization of cellulose V. Crystal and molecular-structure of Na-cellulose I. Macromolecules 24:759–770

    Article  CAS  Google Scholar 

  • Nishiyama Y, Okano T (1998) Morphological changes of ramie fiber during mercerization. J Wood Sci 44:310–313

    Article  CAS  Google Scholar 

  • Nishiyama Y, Kuga S, Okano T (2000) Mechanism of mercerization revealed by X-ray diffraction. J Wood Sci 46:452–457

    Article  CAS  Google Scholar 

  • Nishiyama Y, Langan P, Chanzy H (2002) Crystal structure and hydrogen-bonding system in cellulose 1β from synchrotron X-ray and neutron fiber diffraction. J Am Chem Soc 124:9074–9082

    Article  CAS  Google Scholar 

  • Nishiyama Y, Sugiyama J, Chanzy H, Langan P (2003) Crystal structure and hydrogen bonding system in cellulose Iα, from synchrotron X-ray and neutron fiber diffraction. J Am Chem Soc 125:14300–14306

    Article  CAS  Google Scholar 

  • Nishiyama Y, Wada M, Hanson L, Langan P (2010) Time-resolved X-ray diffraction microprobe studies of the conversion of cellulose I to ethylenediamine-cellulose I. Cellulose 17:735–745

    Article  CAS  Google Scholar 

  • Okano T, Sarko A (1984) Mercerization of cellulose. I. X-ray diffraction evidence for intermediate structures. J Appl Polym Sci 29:4175–4182

    Article  CAS  Google Scholar 

  • Okano T, Kim NH, Sugiyama J (1989) Supermolecular structure of alkali-swollen cellulose. Cellulose, structural and functional aspects, Ellis Horwood, London, pp 93–96

  • Porro F, Bédué O, Chanzy H, Heux L (2007) Solid-state 13C NMR study of Na-cellulose complexes. Biomacromolecules 8:2586–2593

    Article  CAS  Google Scholar 

  • Reeves RE (1944) The optical rotation of cellulose and glucosides in cuprammonium hydroxide solution. Science 99:148–149

    Article  CAS  Google Scholar 

  • Schweizer E (1857) Das Kupferoxyd-Ammoniak, ein Auflösungsmittel für die Pflanzenfaser. J Prakt Chem 72:109–111

    Article  Google Scholar 

  • Sobue H, Kiessig H, Hess K (1939) Das system cellulose—Natriumhydroxyd-Wasser in Abhaeugigkeit von der Temeratur. Z Phys Chem B43:309–328

    CAS  Google Scholar 

  • Su X, Kimura S, Wada M, Kuga S (2011) Stoichiometry and stability of cellulose-hydrazine complexes. Cellulose 18:531–537

    Article  CAS  Google Scholar 

  • Wada M, Nishiyama Y, Langan P (2006) X-ray structure of ammonia-cellulose I: New insight into the conversion of cellulose I to cellulose IIII. Macromolecules 39:2947–2952

    Google Scholar 

  • Whitaker PM, Nieduszynski IA, Atkins EDT (1974) Structural aspects of soda-cellulose II. Polymer 15:125–127

    Google Scholar 

Download references

Acknowledgments

The authors thank the Japan Synchrotron Research Institute (JASRI) for provision of BL40B2 beam time at SPring-8 (2012A1549). We thank Dr. Y. Nishiyama for valuable discussions and comments during the writing of this work. This study was supported by a grant-in-aid for JSPS fellows (no. 23-2362).

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Authors and Affiliations

  1. Department of Biomaterials Sciences, Graduate School of Agricultural and Life Sciences, The University of Tokyo, Yayoi 1-1-1, Bunkyo-ku, Tokyo, 113-8657, Japan

    Yu Ogawa, Hitomi Hidaka, Satoshi Kimura, Shigenori Kuga & Masahisa Wada

  2. Research Fellow of the Japan Society for the Promotion of Science, Tokyo, Japan

    Yu Ogawa

  3. Department of Plant and Environmental New Resources, College of Life Sciences, Kyung Hee University, 1, Seocheon-dong, Giheung-ku, Yongin-si, 446-701, Gyeonggi-do, Korea

    Satoshi Kimura, Ung-Jin Kim & Masahisa Wada

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  1. Yu Ogawa
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  2. Hitomi Hidaka
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  3. Satoshi Kimura
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  4. Ung-Jin Kim
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  5. Shigenori Kuga
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  6. Masahisa Wada
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Correspondence to Yu Ogawa.

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Ogawa, Y., Hidaka, H., Kimura, S. et al. Formation and stability of cellulose–copper–NaOH crystalline complex. Cellulose 21, 999–1006 (2014). https://doi.org/10.1007/s10570-013-9977-4

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  • DOI: https://doi.org/10.1007/s10570-013-9977-4

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