Hybridization and self‐assembly behaviors of surface‐immobilized DNA in close proximity: A single‐molecule perspective

Solid surfaces that are immobilized with DNA molecules underlie an array of biotechnological devices. These surfaces may also mediate the self‐assembly of hierarchical DNA nanostructures. However, a number of fundamental questions concerning the structure–function relationship of these biointerfaces remain, including how these DNA probe molecules organize on the surface and how the spatial organization influences molecular recognition kinetics and interfacial affinity of these DNA molecules at the regime where crowding interactions are important (1–10 nm). This mini‐review covers recent advances in understanding this structure–function relationship by spatially resolving surface hybridization events at the single‐molecule level. Counterintuitive cooperative effects in surface hybridization are discussed and as is how modeling these cooperative effects can be used to predict the hybridization kinetics of a prototypical DNA sensor. Future opportunities in using mechanistic understanding to improve the performance and reliability of DNA sensors and form hierarchical supramolecular structures are also discussed.