Adsorption Behavior of Extracellular Polymeric Substances on Graphene Materials Explored by Fluorescence Spectroscopy...

Adsorption isotherms of extracellular polymeric substances (EPS) on graphene oxide (GO) and reduced GO (rGO) were studied using fluorescence excitation-emission matrix-parallel factor analysis (EEM-PARAFAC) and two-dimensional correlation spectroscopy (2D-COS) combined with Fourier transform infrared spectroscopy (FTIR). Chemical reduction of GO resulted in a greater extent of carbon adsorption with a higher degree of isotherm nonlinearity, suggesting that heterogeneous adsorption sites were additionally created by GO reduction. Two protein-like and two humic-like components were identified from EPS by EEM-PARAFAC. Adsorption of protein-like components was greater than that of humic-like components, and the preferential adsorption was more pronounced for GO versus rGO. Adsorption of protein-like components was more governed by site-limiting mechanisms than humic-like components as shown by the higher isotherm nonlinearity. 2D-COS provided further information on the adsorption of secondary protein structures. Adsorption of the EPS structures related to amide I and aromatic C-C bands was greater for rGO versus GO. Protein structures of EPS were more favorable for adsorption in the order of α-helix → amide II → β-sheet structures with increasing site limitation. Our results revealed successful applicability of EEM-PARAFAC and 2D-COS in examining the adsorption behavior of heterogeneous biological materials on graphene materials.