Position-Specific Substitution in Cellulose Ethers Studied by DNP Enhanced Solid-State NMR Spectroscopy.

Ethyl hydroxyethyl cellulose (EHEC) and methyl ethyl hydroxyethyl cellulose (MEHEC) are hydrophilic cellulose ethers commonly employed as rheology modifiers in diverse industrial applications. The performance of these polymers, and their resistance to degradation by various cellulase enzymes, depends on their intricate molecular structure. Distribution of the etherifying groups, within the anhydroglucose units and along the polymer chain, is the key property to control. However, characterizing such structural properties is challenging, necessitating the development of novel analysis methods. In this study, we demonstrate the application of solid-state nuclear magnetic resonance (NMR) spectroscopy, enhanced by dynamic nuclear polarization (DNP), for this purpose. We prove that the hydrophilic EHEC and MEHEC samples are homogenously swelled in DO/HO-based radical solutions, a necessity to ensure uniform DNP enhancement throughout the material. And we illustrate how the high sensitivity enhancements obtained can be used to perform selective, J-coupling-based C1 to C2 transfer experiments to measure the fraction of substituted C2 positions in these cellulose ethers. Moreover, with further refinement, the methodology outlined in this work holds promise for elucidating C3-specific substitution patterns.