In pursuit of this goal, we combined experimental and computational approaches to better understand how compounds bearing the catechol-motif modulate the fluorescence of (GT)6-SWCNT conjugates. Experimentally, we observed that optical modulation in these sensors is strongly influenced by certain electrochemical properties of catechols. Manipulating electron densities on the aryl motif of catechols sensitively alters fluorescence turn-on response, with higher electron densities correlating positively with stronger turn-on response. Reduction potentials also reflected this trend, where electron-rich catechol oxidized more easily and elicited stronger fluorescence turn-on responses. Interestingly however, no oxidative products were generated during the molecular recognition process, as implied by the correlation between optical response and reduction potential. This suggested that a transient perturbative phenomenon, rather than permanent charge transfer, is responsible for optical modulation observed in these sensors. To rationalize our experimental observations, we employed molecular dynamics (MD) simulations. These simulations provided insights into analyte-sensor interactions, which, when combined with experimental data, allowed us to identify key molecular parameters that collectively define a "perturbation cross section" for catechol-bearing ligands. Our work suggests that ligand binding and analyte electrochemical properties play a concerted role in modulating optical responses in ssDNA-SWCNT biosensors.