Electron paramagnetic resonance spectroscopy as a novel approach to measure macromolecule–surface interactions and activities of extracellular enzymes

The dynamics of high molecular weight organic matter in marine systems are influenced by molecular conformation, interactions with surfaces and susceptibility to enzymatic hydrolysis, parameters that are difficult to observe experimentally. Here we use electron paramagnetic resonance spectroscopy (EPR) and spin-labeled (SL-) polysaccharides to monitor the sorption of SL-polysaccharides to natural sediment surfaces and to montmorillonite and to observe decreases in polysaccharide size due to enzymatic hydrolysis. SL-pullulan, SL-xylan and SL-maltoheptaose all sorbed rapidly to muddy sediments but not to sandy sediments. SL-pullulan and SL-maltoheptaose also both sorbed to montmorillonite; however, SL-pullulan reached substantially greater final surface loadings than did SL-maltoheptaose. Using EPR has the advantages of being rapid (spectra can be acquired in 100 seconds), non-destructive and functional in complex media, including sediment slurries, muddy water or other optically opaque samples, permitting investigation of the interactions between biomacromolecules, extracellular enzymes and mineral surfaces in aquatic environments.