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A novel, mild and selective methylation of carboxyl groups in cellulosic pulps 10th EWLP, Stockholm, Sweden, August 25–28, 2008
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Ivana Tot
Veröffentlicht/Copyright:
15. November 2009
Abstract
A method for selective, fast, and near-quantitative methylation of carboxyl groups in the presence of aliphatic hydroxyl groups of cellulose was developed. The main advantage of the method is the complete maintenance of cellulose integrity; no degradation of cellulose whatsoever during the methylation procedure was observed, making the protocol extremely useful in advanced cellulose analytics. Trimethylsilyl diazomethane (TMS-DAM) was used as the methylation agent. The methylation conditions were pre-optimized by means of carbohydrate model compounds with low-molecular weight, such as derivatives of glucuronic acid and hexenuronic acid, and then re-optimized for methylation of cellulose. The influence of reaction parameters, such as time, temperature, solvents, and concentration, was also determined. The reaction kinetics was monitored by fluorescence labeling of the remaining carboxyl groups according to the common FDAM protocol. A general protocol for the fast methylation of carboxyl groups in pulp samples is presented. The methylation with TMS-DAM is a very fast process, both in comparison to general heterogeneous reactions on cellulosic pulps, and especially in comparison to other methylation approaches. In dissolving and paper grade pulps, methylation of xylan carboxyls proceeded faster than methylation of cellulosic carboxyls. The methylation rate and kinetics are dependent on the pulp type. As application examples, electrokinetic measurements were used to demonstrate the “blocked” reactivity of carboxyl groups in spin-coated films of methylated pulp samples, and ICP-MS was used to demonstrate the drastically decreased metal ion binding capacity of pulp after such methylation.
Keywords: cellulose; chemoselective methylation; electrokinetics; fluorescence labeling; gel permeation chromatography (GPC); hemicellulose; ICP-MS; trimethylsilyl diazomethane
Received: 2008-11-28
Accepted: 2009-3-17
Published Online: 2009-11-15
Published Online: 2009-07-24
Published in Print: 2009-11-01
©2009 by Walter de Gruyter Berlin New York
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Artikel in diesem Heft
- Original Papers
- Effects of selected key chromophores on cellulose integrity upon bleaching 10th EWLP, Stockholm, Sweden, August 25–28, 2008
- A novel, mild and selective methylation of carboxyl groups in cellulosic pulps 10th EWLP, Stockholm, Sweden, August 25–28, 2008
- Effect of salts on the formation and properties of microcrystalline cellulose and chitosan gels 10th EWLP, Stockholm, Sweden, August 25–28, 2008
- Detection of muconic acid type structures in oxidised lignins using 2D NMR spectroscopy 10th EWLP, Stockholm, Sweden, August 25–28, 2008
- Synthesis of a lignin polymer model consisting of only phenolic β-O-4 linkages and testing its reactivity under alkaline conditions 10th EWLP, Stockholm, Sweden, August 25–28, 2008
- HSQC-NMR analysis of lignin in woody (Eucalyptus globulus and Picea abies) and non-woody (Agave sisalana) ball-milled plant materials at the gel state 10th EWLP, Stockholm, Sweden, August 25–28, 2008
- Syringyl-type simple plant phenolics as mediating oxidants in laccase catalyzed degradation of lignocellulosic materials: Model compound studies 10th EWLP, Stockholm, Sweden, August 25–28, 2008
- Titration of free phenolic groups in pulps 10th EWLP, Stockholm, Sweden, August 25–28, 2008
- Interfacial properties of polyelectrolyte complexes incorporating kraft lignin 10th EWLP, Stockholm, Sweden, August 25–28, 2008
- Comparing soluble Trametes pubescens laccase and cross-linked enzyme crystals (CLECs) for enzymatic modification of cellulose 10th EWLP, Stockholm, Sweden, August 25–28, 2008
- Exploring enzymatic treatments for the production of dissolving grade pulp from different wood and non-wood paper grade pulps 10th EWLP, Stockholm, Sweden, August 25–28, 2008
- Effects of commercial cellobiohydrolase treatment on fiber strength and morphology of bleached hardwood pulp 10th EWLP, Stockholm, Sweden, August 25–28, 2008
- Prehydrolysis of Eucalyptus globulus Labill. hemicelluloses prior to pulping and fermentation of the hydrolysates with the yeast Pichia stipitis 10th EWLP, Stockholm, Sweden, August 25–28, 2008
- Activation of thermomechanical pulp by laccases as studied by UV-Vis, UV resonance Raman and FTIR spectroscopy 10th EWLP, Stockholm, Sweden, August 25–28, 2008
- Biological control of sapstain fungi: From laboratory experiments to field trials 10th EWLP, Stockholm, Sweden, August 25–28, 2008
- Study of the sorption-desorption properties of pine wood at the initial stage of decay by wood-rot fungi 10th EWLP, Stockholm, Sweden, August 25–28, 2008
- Decay susceptibility of Amazon wood species from Brazil against white rot and brown rot decay fungi 10th EWLP, Stockholm, Sweden, August 25–28, 2008
- Relations between chemical changes and mechanical properties of thermally treated wood 10th EWLP, Stockholm, Sweden, August 25–28, 2008
- Kinetics of SO2-ethanol-water pulping of spruce 10th EWLP, Stockholm, Sweden, August 25–28, 2008
- Study on desorption of Mn, Fe, and Mg from TMP and evaluation of the complexing strength of different chelating agents using side reaction coefficients 10th EWLP, Stockholm, Sweden, August 25–28, 2008
- Short Note
- Determination of self-diffusion coefficient and hydrodynamic radius of xylan by NMR diffusometry (NMRd) 10th EWLP, Stockholm, Sweden, August 25–28, 2008
- Meetings
- Meetings
- Contents Volume 63
- Contents Volume 63 (2009)
- Subject index
- Subject index
- Species index (scientific names)
- Species index (scientific names)
- Author index
- Author index
- Acknowledgement
- Acknowledgement
Schlagwörter für diesen Artikel
cellulose;
chemoselective methylation;
electrokinetics;
fluorescence labeling;
gel permeation chromatography (GPC);
hemicellulose;
ICP-MS;
trimethylsilyl diazomethane
Artikel in diesem Heft
- Original Papers
- Effects of selected key chromophores on cellulose integrity upon bleaching 10th EWLP, Stockholm, Sweden, August 25–28, 2008
- A novel, mild and selective methylation of carboxyl groups in cellulosic pulps 10th EWLP, Stockholm, Sweden, August 25–28, 2008
- Effect of salts on the formation and properties of microcrystalline cellulose and chitosan gels 10th EWLP, Stockholm, Sweden, August 25–28, 2008
- Detection of muconic acid type structures in oxidised lignins using 2D NMR spectroscopy 10th EWLP, Stockholm, Sweden, August 25–28, 2008
- Synthesis of a lignin polymer model consisting of only phenolic β-O-4 linkages and testing its reactivity under alkaline conditions 10th EWLP, Stockholm, Sweden, August 25–28, 2008
- HSQC-NMR analysis of lignin in woody (Eucalyptus globulus and Picea abies) and non-woody (Agave sisalana) ball-milled plant materials at the gel state 10th EWLP, Stockholm, Sweden, August 25–28, 2008
- Syringyl-type simple plant phenolics as mediating oxidants in laccase catalyzed degradation of lignocellulosic materials: Model compound studies 10th EWLP, Stockholm, Sweden, August 25–28, 2008
- Titration of free phenolic groups in pulps 10th EWLP, Stockholm, Sweden, August 25–28, 2008
- Interfacial properties of polyelectrolyte complexes incorporating kraft lignin 10th EWLP, Stockholm, Sweden, August 25–28, 2008
- Comparing soluble Trametes pubescens laccase and cross-linked enzyme crystals (CLECs) for enzymatic modification of cellulose 10th EWLP, Stockholm, Sweden, August 25–28, 2008
- Exploring enzymatic treatments for the production of dissolving grade pulp from different wood and non-wood paper grade pulps 10th EWLP, Stockholm, Sweden, August 25–28, 2008
- Effects of commercial cellobiohydrolase treatment on fiber strength and morphology of bleached hardwood pulp 10th EWLP, Stockholm, Sweden, August 25–28, 2008
- Prehydrolysis of Eucalyptus globulus Labill. hemicelluloses prior to pulping and fermentation of the hydrolysates with the yeast Pichia stipitis 10th EWLP, Stockholm, Sweden, August 25–28, 2008
- Activation of thermomechanical pulp by laccases as studied by UV-Vis, UV resonance Raman and FTIR spectroscopy 10th EWLP, Stockholm, Sweden, August 25–28, 2008
- Biological control of sapstain fungi: From laboratory experiments to field trials 10th EWLP, Stockholm, Sweden, August 25–28, 2008
- Study of the sorption-desorption properties of pine wood at the initial stage of decay by wood-rot fungi 10th EWLP, Stockholm, Sweden, August 25–28, 2008
- Decay susceptibility of Amazon wood species from Brazil against white rot and brown rot decay fungi 10th EWLP, Stockholm, Sweden, August 25–28, 2008
- Relations between chemical changes and mechanical properties of thermally treated wood 10th EWLP, Stockholm, Sweden, August 25–28, 2008
- Kinetics of SO2-ethanol-water pulping of spruce 10th EWLP, Stockholm, Sweden, August 25–28, 2008
- Study on desorption of Mn, Fe, and Mg from TMP and evaluation of the complexing strength of different chelating agents using side reaction coefficients 10th EWLP, Stockholm, Sweden, August 25–28, 2008
- Short Note
- Determination of self-diffusion coefficient and hydrodynamic radius of xylan by NMR diffusometry (NMRd) 10th EWLP, Stockholm, Sweden, August 25–28, 2008
- Meetings
- Meetings
- Contents Volume 63
- Contents Volume 63 (2009)
- Subject index
- Subject index
- Species index (scientific names)
- Species index (scientific names)
- Author index
- Author index
- Acknowledgement
- Acknowledgement
