A comparison of glycans and polyglycans using solid-state NMR and X-ray powder diffraction

Individual polyglycans and their corresponding monomers have been studied separately for several decades. Attention has focused primarily on the modifications of these polyglycans instead of the simple relationship between the polyglycans themselves and their corresponding monomers. Two polyglycans, chitin and chitosan, were examined along with their respective monomeric units, N-acetyl-d-glucosamine (GlcNAc) and (+)d-glucosamine (GlcN) using solid-state proton decoupling Magic Angle Turning (MAT) techniques and X-Ray Powder Diffraction (XRPD). A down-field shift in isotropic 13C chemical shifts was observed for both polymers in Cross Polarization/Magic Angle Spinning (CP/MAS) spectra. An explanation of misleading peak assignments in previous NMR studies for these polyglycans was determined by comparing sideband patterns of the polymers with their corresponding monomers generated in a 2D FIve π REplicated Magic Angle Turning (FIREMAT) experiment processed by Technique for Importing Greater Evolution Resolution (TIGER). Structural changes in the crystalline framework were supported by XRPD diffraction data.