(497d) Why Do Surface and Solution Hybridization Differ?

Hybridization to DNA monolayers is widely encountered in diagnostic, clinical, and materials science applications. This talk will overview sources of kinetic and thermodynamic differences between hybridization within interfacial regions compared to hybridization in solution. By examining kinetic and thermodynamic data compiled from various studies, we consider how molecular characteristics, interfacial crowding, and solution conditions manifest in discrepancies from "ideal" solution behavior. Literature data show that surface kinetics often exhibit slower forward rates and, more dramatically, much faster off rates consistent with reduced thermodynamic stabilities when hybridization occurs on surfaces. Surface-specific sources of deviations from solution behavior include barriers to partitioning of strands from solution, interstrand associations between immobilized chains, as well as interactions with the nearby solid support. This talk will overview how these various contributions fit together based on perspective from primarily experimental studies.