Abstract
Two commercial carboxymethyl celluloses (CMC) with degree of substitution (DS) 0.75 and 0.77, respectively, have been submitted to exhaustive methanolysis until the amount of the insoluble residue did not further decrease. Dissolved and insoluble material were determined gravimetrically and further analyzed with respect to their substituent distribution in the glucosyl units by capillary electrophoresis, and by size exclusion chromatography. While the substitution of the soluble fraction was slightly above the average DS and in accordance with a random distribution (Spurlin), unsubstituted glucose was steadily enriched in the retained solid material (10 and 20 mol%), resulting in a final DS of 0.46 and 0.42, respectively. An “excess” of unsubstituted glucose is mainly responsible for the heterogeneity of this portion, since deviation from the Spurlin model could be minimized by reducing the molar fraction of glucosyl units. Estimation of the DS/DP-distribution profile of the insoluble residue from molar mass and substituent distribution data, and comparison with the profile of the original CMC (DS 0.75) showed that roughly only about half of the residue could be covered by sequences of the original CMC if random substitution is assumed. This indicates that there is a certain portion of unsubstituted domains in a low substituted heterogeneous part of the CMC. By this procedure, low or unsubstituted areas as a minor part of the CMC material can be concentrated and heterogeneity detected with higher sensitivity.
Graphical abstract
Similar content being viewed by others
References
Adden R, Müller R, Brinkmalm G, Ehrler R, Mischnick P (2006a) Comprehensive analysis of the substituent distribution in hydroxyethyl celluloses by quantitative MALDI-ToF-MS. Macromol Biosci 6:435–444
Adden R, Niedner W, Müller R, Mischnick P (2006b) Comprehensive analysis of the substituent distribution in the glucosyl Units and along the polymer chain of hydroxyethylmethyl celluloses and statistical evaluation. Anal Chem 78:1146–1157
Adden R, Müller R, Mischnick P (2006c) Analysis of the substituent distribution in the glucosyl units and along the polymer chain of hydroxypropylmethyl celluloses and statistical evaluation. Cellulose 13:459
Arisz PW, Kauw HJJ, Boon JJ (1995) Substituent distribution along the cellulose backbone in O-methylcelluloses using GC and FAB-MS for monomer and oligomer analysis. Carbohydr Res 271:1–14
Baar A, Kulicke W-M, Szablikowski K, Kiesewetter R (1994) Nuclear magnetic resonance spectroscopic characterization of carboxymethylcellulose. Macromol Chem Phys 195:1483–1492
Bol M, Sakellaris CN, Jacob CR, Mischnick P (2017) Differences in the complexation of sodium with methyl esterified carboxymethyl/methoxyacetyl-O-glucans in electrospray ionization-mass spectrometry. Int J Mass Spectrom 419:20–28
Casaburi A, Montoya Rojo Ú, Cerrutti P, Vázquez A, Foresti ML (2018) Carboxymethyl cellulose with tailored degree of substitution obtained from bacterial cellulose. Food Hydrocoll 75:147–156
Chambers RE, Clamp JR (1971) An assessment of methanolysis and other factors used in the analysis of carbohydrate-containing materials. Biochem J 125:1009–1018
Cuers J, Unterieser I, Burchard W, Adden R, Rinken M, Mischnick P (2012) Simultaneous determination of substituent patterns in partially acid hydrolyzed O-Me/O-Me-d 3-cellulose and quantification of the obtained oligomers by HPLC-ESI-MS. Carbohydr Res 348:55–63
Cuers J, Rinken M, Adden R, Mischnick P (2013) Critical investigation of the substituent distribution in the polymer chains of hydroxypropyl methylcelluloses by (LC-)ESI-MS. Anal Bioanal Chem 405:9021–9032
Dogsa I, Tomšič M, Orehek J, Benigar E, Jamnik A, Stopar D (2014) Amorphous supramolecular structure of carboxymethyl cellulose in aqueous solution at different pH values as determined by rheology, small angle X-ray and light scattering. Carbohydr Polym 111:492–504
Enebro J, Momcilovic D, Siika-Aho M, Karlsson S (2007) A new approach for studying correlations between the chemical structure and the rheological properties in carboxymethyl cellulose. Biomacromol 8:3253–3257
Enebro J, Momcilovic D, Siika-Aho M, Karlsson S (2009a) Investigation of endoglucanase selectivity on carboxymethyl cellulose by mass spectrometric techniques. Cellulose 16:271–280
Enebro J, Momcilovic D, Siika-Aho M, Karlsson S (2009b) Liquid chromatography combined with mass spectrometry for the investigation of endoglucanase selectivity on carboxymethyl cellulose. Carbohydr Res 344:2173–2181
Gelman RA (1982) Characterization of carboxymethylcellulose: distribution of substituent groups along the chain. J Appl Polym Sci 27:2957–2964
Heinze T, Liebert T (2001) Unconventional methods in cellulose functionalization. Prog Polym Sci 26:1689–1762
Heinze T, Erler U, Nehls I, Klemm D (1994) Determination of the substituent pattern of heterogeneously and homogeneously synthesized carboxymethyl cellulose by using high-performance liquid chromatography. Angew Makromol Chem 215:93–106
Heinze T, Liebert T, Klüfers P, Meister F (1999) Carboxymethylation of cellulose in unconventional media. Cellulose 6:153–165
Ho FFL, Klosiewicz DW (1980) Proton nuclear magnetic resonance spectrometry for determination of substituents and their distribution in carboxymethylcellulose. Anal Chem 52:913–916
Hoogendam CW, de Keizer A, Cohen Stuart MA, Bijsterbosch BH, Smit JAM, van Dijk JAPP, van der Horst PM, Batelaan JG (1998) Persistence length of carboxymethyl cellulose as evaluated from size exclusion chromatography and potentiometric titrations. Macromolecules 31:6297–6309
Käuper P, Kulicke W-M, Horner S, Saake B, Puls J, Kunze J, Fink H-P, Heinze U, Heinze T, Klohr E-A, Thielking H, Koch W (1998) Development and evaluation of methods for determining the pattern of functionalization in sodium carboxymethylcelluloses. Angew Makromol Chem 260:53–63
Klemm D, Heinze T, Wagenknecht W (1996) Properties of regioselectively substituted anionic cellulose polyelectrolytes. Ber Bunsenges Phys Chem 100:730–733
Kono H, Oshima K, Hashimoto H, Shimizu Y, Tajima K (2016) NMR characterization of sodium carboxymethyl cellulose. Substituent distribution and mole fraction of monomers in the polymer chains. Carbohydr Polym 146:1–9
Kragten EA, Kamerling JP, Vliegenthart JFG (1992) Composition analysis of carboxymethylcellulose by high-pH anion-exchange chromatography with pulsed amperometric detection. J Chromatogr A 623:49–53
Lazik W, Heinze T, Pfeiffer K, Albrecht G, Mischnick P (2002) Starch derivatives of high degree of functionalization 6. Multi step carboxy-methylation. J Appl Polym Sci 86:743–752
Mischnick P, Kühn G (1996) Model studies on methyl amyloses: correlation between reaction conditions and primary structure. Carbohydr Res 290:199–207
Mischnick P, Momcilovic D (2010) Chemical structure analysis of starch and cellulose derivatives. Adv Carbohydr Chem Biochem 64:117–210
Mischnick P, Unterieser I, Voiges K, Cuers J, Rinken M, Adden R (2013) A new method for the analysis of the substitution pattern of hydroxyethyl(methyl)-celluloses along the polysaccharide chain. Macromol Chem Phys 214:1363–1374
Niemelä K, Sjöström E (1988) Identification of the products of hydrolysis of carboxymethylcellulose. Carbohydr Res 180:43–52
Pritchard DG, Todd CW (1977) Gas chromatography of methyl glycosides as their trimethylsilyl ethers. The methanolysis and Re-N-acetylation steps. J Chromatrogr 133:133–139
Ramos LA, Frollini E, Heinze T (2005) Carboxymethylation of cellulose in the new solvent dimethyl sulfoxide/tetrabutylammonium fluoride. Carbohydr Polym 60:259–267
Reuben J, Conner HT (1983) Analysis of the carbon-13 n.m.r. spectrum of hydrolyzed O-(carboxymethyl)cellulose. Monomer composition and substitution patterns. Carbohydr Res 115:1–13
Saake B, Horner S, Kruse T, Puls J, Liebert T, Heinze T (2000) Detailed investigation on the molecular structure of carboxymethyl cellulose with unusual substitution pattern by means of an enzyme-supported analysis. Macromol Chem Phys 201:1996–2002
Saake B, Horner S, Puls J, Heinze T, Koch W (2001) A new approach in the analysis of the substituent distribution of carboxymethyl celluloses. Cellulose 8:59–67
Sammon C, Bajwa G, Timmins P, Melia CD (2006) The application of attenuated total reflectance Fourier transform infrared spectroscopy to monitor the concentration and state of water in solutions of a thermally responsive cellulose ether during gelation. Polymer 47:577–584
Schulz L, Seger B, Burchard W (2000) Structures of cellulose in solution. Macromol Chem Phys 201:2008–2022
Shakun M, Heinze T, Radke W (2015) Characterization of sodium carboxymethyl cellulose by comprehensive two-dimensional liquid chromatography. Carbohydr Polym 130:77–86
Spurlin HM (1939) Arrangement of substituents in cellulose derivatives. J Am Chem Soc 61:2222–2227
Tüting W, Albrecht G, Volkert B, Mischnick P (2004) Structure analysis of carboxymethyl starch by capillary electrophoresis and enzymic degradation. Starch/Stärke 56:315–321
Voiges K, Lämmerhardt N, Distelrath C, Mischnick P (2017a) Substituent effects on the kinetics of acid-catalyzed hydrolysis of methyl cellulose. Cellulose 24:555–569
Voiges K, Lämmerhardt N, Mischnick P (2017b) Kinetic studies of acid-catalyzed hydrolysis of mixed cellulose ethers. Cellulose 24:627–639
Wirick MG (1968) A study of the enzymic degradation of CMC and other cellulose ethers. J Polym Sci Polm Chem 6:1965–1974
Wüstenberg T (2015) Cellulose and cellulose derivatives in the food industry: fundamentals and applications, 1st edn. Wiley, Weinheim
Zeller SG, Griesgraber GW, Gray GR (1991) Analysis of positions of substitution of O-carboxymethyl groups in partially O-carboxymethylated cellulose by the reductive-cleavage method. Carbohydr Res 211:41–45
Acknowledgments
This work was funded by the Deutsche Forschungsgemeinschaft (DFG, Mi 398/16-1). We thank Franziska Steingaß for technical assistance.
Author information
Authors and Affiliations
Corresponding author
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Bol, M., Dobos, M.A., Lebioda, S. et al. Methanolysis of carboxymethyl cellulose: a comprehensive study. Cellulose 26, 383–397 (2019). https://doi.org/10.1007/s10570-018-2089-4
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10570-018-2089-4