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Critical re-investigation of the alditol acetate method for analysis of substituent distribution in methyl cellulose

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Abstract

The alditol acetate method is a common procedure for sugar analysis, also applied to determine the substituent distribution in monomer units of polysaccharide ethers like methyl cellulose by gas liquid chromatography. Consisting of several preparation and work-up steps this procedure is both time consuming and prone to side reactions that promote discrimination of single constituents, especially when no peralkylation step is performed prior to hydrolysis. As a consequence results scatter in dependence on individual treatment and conditions. In the context of this work these critical points were overcome by strict but simplified work-up procedures and using acid instead of alkaline catalyzed acetylation. Under the acidic conditions the tedious removal of borate is no longer necessary and a reduced time requirement was achieved as well as good reproducibility. Comparison with independent reference methods excluded a systematic error of the method and confirmed the results obtained. Without peralkylation, i.e. in the presence of free hydroxyl groups, another fast modification of the method using DMSO as solvent, no removal of borate, and 1-methylimidazole as catalyst for acetylation was found to produce a systematic error.

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Abbreviations

AAM:

Alditol acetate method

AGU:

Anhydro glucose unit

ATR-IR:

Attenuated total reflection infra red

BSTFA:

N,O–bis(trimethylsilyl)-trifluoroacetamide

c i :

i-fold substituted monomer units

DMSO:

Dimethyl sulfoxide

DS:

Degree of substitution

ECR:

Effective carbon response

ESI:

Electrospray ionization

FID:

Flame ionization detector

GLC:

Gas liquid chromatography

HMF:

Hydroxymethylfurfural

MC:

Methyl cellulose

MEC:

Methyl ethyl cellulose

MS:

Mass spectrometry

MWCO:

Molecular weight cut off

n:

Number of experiments

r. t.:

Room temperature

s i :

Molar fraction of monomers substituted at O-i

TES:

Triethylsilyl/triethylsilane

TFA:

Trifluoroacetic acid

TMS:

Trimethylsilyl/trimethylsilane

x i :

Partial degree of substitution in position i

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Acknowledgments

Financial support of the WoodWisdom-Net and the Bundesministerium für Bildung und Forschung (BMBF FKZ 0330837A) and of Dow Wolff Cellulosics GmbH (Dow), Germany, is gratefully acknowledged.

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Correspondence to Petra Mischnick.

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Voiges, K., Adden, R., Rinken, M. et al. Critical re-investigation of the alditol acetate method for analysis of substituent distribution in methyl cellulose. Cellulose 19, 993–1004 (2012). https://doi.org/10.1007/s10570-012-9663-y

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  • DOI: https://doi.org/10.1007/s10570-012-9663-y

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