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Solid-state NMR studies of methyl celluloses. Part 2: Determination of degree of substitution and O-6 vs. O-2/O-3 substituent distribution in commercial methyl cellulose samples

Karrasch, Andrea, Jäger, Christian, Saake, Bodo, Potthast, Antje, Rosenau, Thomas
Cellulose 2009 v.16 no.6 pp. 1159-1166
chromatography, hydrolysis, methylcellulose, nuclear magnetic resonance spectroscopy, spinning
Solid state NMR spectroscopy was applied to determine the overall degree of substitution (DS) and the degrees of substitution at C-6 (DSC₋₆) and C-2/3 (DSC₋₂/₃). Four commercial methyl cellulose samples were used, having a DS between 0.51 and 1.96 as determined by wet-chemical analysis. The strategy and optimization of the NMR data acquisition as well as the data evaluation procedures are explained in detail. Optimization of the approach mainly comprised (a) maximizing the signal by choice of NMR probe, MAS spinning frequency and B ₀ field, (b) minimizing the measurement time by a Torchia-type experiment and (c) suppressing probe background by rotor-synchronized echo detection. Data evaluation used simply the integration of three different spectral ranges in the ¹³C NMR spectrum. The results of the experiments were in good agreement with the wet-chemical data. The NMR approach takes about the same analysis time as the conventional hydrolysis/chromatography analysis. However, it is a generally applicable and simple alternative without need for an extended sample preparation which is most useful if wet-chemical/chromatographic analyses are undesired or unavailable. Further studies have to concentrate on the validation of the analytical method and application to a larger sample array.