1H NMR spectroscopy for profiling complex carbohydrate mixtures in non-fractionated beer

A plethora of biological and biotechnological processes involve the enzymatic remodelling of carbohydrates in complex mixtures whose compositions affect both the processes and products. In the current study, we employed high-resolution 1H NMR spectroscopy for the analysis of cereal-derived carbohydrate mixtures as exemplified on six beer samples of different styles. Structural assignments of more than 50 carbohydrate moieties were obtained using 1H1–1H2 groups as structural reporters. Spectroscopically resolved carbohydrates include more than ʹʹ20 differentʹʹ small carbohydrates with more than 38 isomeric forms in addition to cereal polysaccharide fragments with suspected organoleptic and prebiotic function. Structural motifs at the cleavage sites of starch, β-glucan and arabinoxylan fragments were identified, showing different extent and specificity of enzymatic polysaccharide cleavage during the production of different beer samples. Diffusion ordered spectroscopy supplied independent size information for the characterisation and identification of polysaccharide fragments, indicating the presence especially of high molecular weight arabinoxylan fragments in the final beer.