Abstract
The complexity of the substituent distribution in polysaccharide derivatives is discussed and defined. The challenges regarding analytical characterization that results from various interrelated categories of distributions, including molecular weight, chemical composition, and microstructure, are outlined. Due to these convoluted levels of complexity, results should always be interpreted with carefulness. Various analytical approaches which have been applied to starch and cellulose derivatives are recapped, including enzymatic, mass spectrometric, and chromatographic methods. The relation of heterogeneities of first and second order among and along the polysaccharide chains is addressed. Finally, examples of own analytical work on cellulose ethers are presented, including the MS analysis of methyl cellulose (MC) blends and fractionation studies of fully esterified MC, especially its 4-methoxybenzoates by gradient HPLC on normal phase. Preparative fractionation according to the degree of substitution (DS) allows follow-up analysis in order to get more detailed information on the substituent distribution in such sub-fractions.