Fluorescent Conjugated Polyfluorene with Pendant Lactopyranosyl Ligands for Studies of Ca2+-Mediated Carbohydrate-Carbohydrate Interaction

A well-defined fluorescent conjugated polyfluorene with pendant lactopyranosyl ligands was easily prepared through Cu(I)-catalyzed azide/alkyne "click" ligation and Suzuki coupling polymerization. As a fluorescent multivalent model system of glycoconjugates, the polymer was first used for studies of metal ion-mediated carbohydrate-carbohydrate interaction based on fluorescence spectroscopy. A significant fluorescence quenching of the lactosyl-bearing polyfluorene was observed upon addition of calcium ion, which is attributed to the polymer aggregation derived from Ca2+-mediated complex formation. Dynamic light scattering can also prove Ca2+-induced aggregation of the polymer based on determination of the corresponding hydrodynamic diameters. The calcium-mediated lactose-lactose interaction was reversible when treated with EDTA. In control studies, Ca2+-induced fluorescence quenching can not be observed for cellobiosyl- or galactosyl-functionalized polymer analogues, which show that specific sugar structures are critical for carbohydrate-metal complex formation.