Cellulose

, Volume 21, Issue 1, pp 167–176 | Cite as

SEC-MALLS analysis of TEMPO-oxidized celluloses using methylation of carboxyl groups

  • Ryoya Hiraoki
  • Hayaka Fukuzumi
  • Yuko Ono
  • Tsuguyuki Saito
  • Akira Isogai
Original Paper

Abstract

Two cellouronic acids [sodium (1 → 4)-β-polyglucuronates, CUAs] and one 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-oxidized wood cellulose (TOC) became soluble in 8 % lithium chloride/N,N-dimethylacetamide (LiCl/DMAc) after the methylation of C6 carboxyl groups in these samples using trimethylsilyldiazomethane (TMSD). The obtained solutions were diluted to 1 % LiCl/DMAc and subjected to size-exclusion chromatography combined with multi-angle laser-light scattering (SEC-MALLS). Neither depolymerization nor side reactions took place during methylation; this was confirmed by SEC-MALLS and nuclear magnetic resonance analyses, using CUAs as models. The SEC-MALLS analysis of the original wood cellulose and the carboxyl-methylated TOC prepared from it, using 1 % LiCl/N,N-dimethyl-2-imidazolidinone and 1 % LiCl/DMAc, respectively, as eluents, showed that the weight-average degree of polymerization of the original wood cellulose decreased from 3,100 to 2,210 through TEMPO-mediated oxidation. The molecular-mass distributions of the original wood cellulose and the TOC both consisted of one large peak with a small shoulder, indicating that some of the oxidized hemicelluloses remained in the TOC. The combination of methylation of carboxyl groups in polysaccharides using TMSD and subsequent SEC-MALLS analysis using 1 % LiCl/DMAc as an eluent may be applicable not only to TOCs, but also to other polysaccharides with carboxyl groups, for evaluation of their molecular-mass parameters.

Keywords

TEMPO-oxidized cellulose Cellouronic acid Methyl ester Trimethylsilyldiazomethane SEC-MALLS LiCl/DMAc 

References

  1. Bailey WF, Bobbitt JM (2007) Mechanism of the oxidation of alcohols by oxoammonium cations. J Org Chem 72:4504–4509CrossRefGoogle Scholar
  2. Bohrn R, Potthast A, Schiehser S, Rosenau T, Sixta H, Kosma P (2006) The FDAM method: determination of carboxyl profiles in cellulosic materials by combining group-selective fluorescence labeling with GPC. Biomacromolecules 7:1743–1750CrossRefGoogle Scholar
  3. Bragd PL, van Bekkum H, Besemer AC (2004) TEMPO-mediated oxidation of polysaccharides: survey of methods and applications. Top Catal 27:49–66CrossRefGoogle Scholar
  4. Ciucanu I, Kerek F (1984) A simple and rapid method for the permethylation of carbohydrates. Carbohydr Res 131:209–217CrossRefGoogle Scholar
  5. Da Silva Perez D, Montanari S, Vignon MR (2003) TEMPO-mediated oxidation of cellulose III. Biomacromolecules 4:1417–1425CrossRefGoogle Scholar
  6. de Nooy AEJ, Besemer C, van Bekkum H (1995) Highly selective nitroxyl radical-mediated oxidation of primary alcohol groups in water-soluble glucans. Carbohydr Res 269:89–98CrossRefGoogle Scholar
  7. Dupont AL (2003) Cellulose in lithium chloride/N,N,-dimethylacetamide, optimisation of a dissolution method using paper substrates and stability of the solutions. Polymer 44:4117–4126CrossRefGoogle Scholar
  8. Fujisawa S, Isogai T, Isogai A (2010) Temperature and pH stability of cellouronic acid. Cellulose 17:607–615CrossRefGoogle Scholar
  9. Fujisawa S, Okita Y, Fukuzumi H, Saito T, Isogai A (2011) Preparation and characterization of TEMPO-oxidized cellulose nanofibril films with free carboxyl groups. Carbohydr Polym 84:579–583CrossRefGoogle Scholar
  10. Fukuzumi H, Saito T, Isogai A (2010) Thermal stabilization of TEMPO-oxidized cellulose. Polym Degrad Stabil 95:1502–1508CrossRefGoogle Scholar
  11. Hashimoto N, Aoyama T, Shioiri T (1981) New methods and reagents in organic synthesis. 14. A simple efficient preparation of methyl esters with trimethylsilyl diazomethane (TMSCHN2) and its application to gas chromatographic analysis of fatty acids. Chem Pharm Bull 29:1475–1478CrossRefGoogle Scholar
  12. Henninges U, Okubayashi S, Rosenau T, Potthast A (2012) Irradiation of cellulosic pulps: understanding its impact on cellulose oxidation. Biomacromolecules 13:4171–4178Google Scholar
  13. Hirota M, Tamura N, Saito T, Isogai A (2009) Oxidation of regenerated cellulose with NaClO2 catalyzed by TEMPO and NaClO under acid-neutral conditions. Carbohydr Polym 78:330–335CrossRefGoogle Scholar
  14. Hirota M, Furihata K, Saito T, Kawada T, Isogai A (2010) Glucose/glucuronic acid alternating co-polysaccharides prepared from TEMPO-oxidized native celluloses by surface peeling. Angew Chem Int Ed 49:7670–7672CrossRefGoogle Scholar
  15. Isogai A, Kato Y (1998) Preparation of polyuronic acid from cellulose by TEMPO-mediated oxidation. Cellulose 5:153–164CrossRefGoogle Scholar
  16. Isogai T, Yanagisawa M, Isogai A (2009) Degrees of polymerization (DP) and DP distribution of cellouronic acids prepared from alkali-treated celluloses and ball-milled native celluloses by TEMPO-mediated oxidation. Cellulose 16:117–127CrossRefGoogle Scholar
  17. Isogai A, Saito T, Fukuzumi H (2011) TEMPO-oxidized cellulose nanofibers. Nanoscale 3:71–85CrossRefGoogle Scholar
  18. Iwamoto S, Weihua K, Isogai A, Iwata T (2009) Elastic modulus of single cellulose microfibrils from tunicate measured by atomic force microscopy. Biomacromolecules 10:2571–2576CrossRefGoogle Scholar
  19. Kühnel E, Laffan DDP, Lloyd-Jones GC, Martinez del Campo T, Shepperson IR, Slaughter JL (2007) Mechanism of methyl esterification of carboxylic acids by trimethylsilyldiazomethane. Angew Chem Int Ed 46:7075–7078CrossRefGoogle Scholar
  20. Milanovic J, Schiehser S, Milanovic P, Potthast A, Kostic M (2013) Molecular weight distribution and functional group profiles of TEMPO-oxidized lyocell fibers. Carbohydr Polym 98:444–450CrossRefGoogle Scholar
  21. Okita Y, Saito T, Isogai A (2010) Cellulose nanofibers prepared by TEMPO-mediated oxidation of native cellulose. Biomacromolecules 11:1696–1700CrossRefGoogle Scholar
  22. Potthast A, Rosenau T, Kosma P (2006) Analysis of oxidized functionalities in cellulose. Polysaccharides II 205:1–48CrossRefGoogle Scholar
  23. Presser A, Hüfner A (2004) Trimethylsilyldiazomethane: a mild and efficient reagent for the methylation of carboxylic acids and alcohols in natural products. Monatsh Chem 135:1015–1022CrossRefGoogle Scholar
  24. Röhring J, Lange T, Potthast A, Rosenau T, Sixta H, Kosma P (2001) Novel methods to determine carbonyl functions in cellulosic substances. In: Proceedings of the post-symposium 11th international symposium on wood pulping chemistry, Grenoble, June 18–49, pp 94–97Google Scholar
  25. Saito T, Isogai A (2004) TEMPO-mediated oxidation of native cellulose. The effect of oxidation conditions on chemical and crystal structures of the water-insoluble fractions. Biomacromolecules 5:1983–1989CrossRefGoogle Scholar
  26. Saito T, Yanagisawa M, Isogai A (2005) TEMPO-mediated oxidation of native cellulose: SEC-MALLS analysis of water-soluble and -insoluble fractions in the oxidized products. Cellulose 12:305–315CrossRefGoogle Scholar
  27. Saito T, Nishiyama Y, Putaux JL, Vignon M, Isogai A (2006) Homogeneous suspensions of individualized microfibrils from TEMPO-catalyzed oxidation of native cellulose. Biomacromolecules 7:1687–1691CrossRefGoogle Scholar
  28. Saito T, Kimura S, Nishiyama Y, Isogai A (2007) Cellulose nanofibers prepared by TEMPO-mediated oxidation of native cellulose. Biomacromolecules 8:2485–2491CrossRefGoogle Scholar
  29. Saito T, Kuramae R, Wohlert J, Berglund LA, Isogai A (2013) An ultrastrong nanofibrillar biomaterial: the strength of single cellulose nanofibrils revealed via sonication-induced fragmentation. Biomacromolecules 14:248–253CrossRefGoogle Scholar
  30. Schult T, Hjerde T, Optun OI, Kleppe PJ, Moe S (2002) Characterization of cellulose by SEC-MALLS. Cellulose 9:149–158CrossRefGoogle Scholar
  31. Shibata I, Yanagisawa M, Saito T, Isogai A (2006) SEC-MALS analysis of cellouronic acid prepared from regenerated cellulose by TEMPO-mediated oxidation. Cellulose 13:73–80CrossRefGoogle Scholar
  32. Shinoda R, Saito T, Okita Y, Isogai A (2012) Relationship between length and degree of polymerization of TEMPO-oxidized cellulose nanofibrils. Biomacromolecules 13:842–849CrossRefGoogle Scholar
  33. Smith DK, Bampton RF, Alexander W (1963) Use of new solvents for evaluating chemical cellulose for the viscose process. J Ind Eng Chem Process Des Dev 2:57–62CrossRefGoogle Scholar
  34. Striegel AM (1993) Theory and applications of DMAc/LiCl in the analysis of polysaccharides. Carbohydr Polym 34:267–274CrossRefGoogle Scholar
  35. Tot I, Müller Y, Werner C, Rosenau T, Potthast A (2009) A novel, mild and selective methylation of carboxyl groups in cellulosic pulps. Holzforschung 63:657–663CrossRefGoogle Scholar
  36. Yamamoto M, Kuramae R, Yanagisawa M, Ishii D, Isogai A (2011) Light-scattering analysis of native wood holocelluloses totally dissolved in LiCl–DMI solutions: high probability of branched structures in inherent cellulose. Biomacromolecules 12:3982–3988CrossRefGoogle Scholar
  37. Yanagisawa M, Isogai A (2005) SEC-MALS-QELS study on the molecular conformation of cellulose in LiCl/amide solutions. Biomacromolecules 6:1258–1265CrossRefGoogle Scholar
  38. Yanagisawa M, Isogai A (2007) Size exclusion chromatographic and UV–vis absorption analyses of unbleached and bleached softwood kraft pulps using LiCl/1,3-dimethyl-2-imidazolidinon as a solvent. Holzforschung 61:236–241CrossRefGoogle Scholar
  39. Yanagisawa M, Shibata I, Isogai A (2005) SEC-MALLS analysis of softwood kraft pulp using LiCl/1,3-dimethyl-2-imidazolidinone as an eluent. Cellulose 12:151–158CrossRefGoogle Scholar
  40. Yang D, Kumar V (2012) Preparation and characterization of novel oxidized cellulose acetate methyl esters. Carbohydr Polym 90:1486–1493CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media Dordrecht 2013

Authors and Affiliations

  • Ryoya Hiraoki
    • 1
  • Hayaka Fukuzumi
    • 1
  • Yuko Ono
    • 1
  • Tsuguyuki Saito
    • 1
  • Akira Isogai
    • 1
  1. 1.Graduate School of Agricultural and Life SciencesUniversity of TokyoTokyoJapan

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