Force Spectroscopy of Metal-Crown Ether Multivalency: Effect of Local Environments on Energy Landscape and Sensing Kinetics

Sandwich complexation involving alkali or alkaline-earth metals, multivalency, and effects associated with local environments is widely encountered in biological and synthetic systems yet the mechanic properties remain unexplored. Herein, AFM (atomic force microscopy)-based single-molecule force spectroscopy is employed to investigate a classical model of M(n+)[15C5]2, a metal cation hosted jointly by two 15-crown-5 moieties immobilized on both the substrate and the AFM tip. Factors reportedly promoting the recognition performance are examined. The rupture force required to break apart M(n+)[15C5]2 is found to be in the order of tens of pico-Newton, e.g., f(β)=31 pN for K(+)[15C5]2. The presence of a second functional group, carboxylate, confers K(+)[15C5]2 with a longer lifetime (from 13 to 16 ms), faster association (from 0.4 to 1.3×10(6) M(-1) s(-1)), and slower dissociation (from 77 to 62 s(-1)). The effect of local environments is significant on association yet less critical on dissociation pathways.