Nanotextured superhydrophobic electrodes enable detection of attomolar-scale DNA concentration within a droplet by non-faradaic impedance spectroscopy

Label-free, rapid detection of biomolecules in microliter volumes of highly diluted solutions (sub-femtomolar) is of essential importance for numerous applications in medical diagnostics, food safety, and chem-bio sensing for homeland security. At ultra-low concentrations, regardless of the sensitivity of the detection approach, the sensor response time is limited by physical diffusion of molecules towards the sensor surface. We have developed a fast, low cost, non-faradaic impedance sensing method for detection of synthetic DNA molecules in DI water at attomolar levels by beating the diffusion limit through evaporation of a micro-liter droplet of DNA on a nanotextured superhydrophobic electrode array. Continuous monitoring of the impedance of individual droplets as a function of evaporation time is exploited to dramatically improve the sensitivity and robustness of detection. Formation of the nanostructures on the electrode surface not only increases the surface hydrophobicity, but also allows robust pinning of the droplet contact area to the sensor surface. These two features are critical for performing highly stable impedance measurements as the droplet evaporates. Using this scheme, the detection limit of conventional non-faradaic methods is improved by five orders of magnitude. The proposed platform represents a step-forward towards realization of ultra-sensitive lab-on-chip biomolecule detectors for real time point-of-care application. Further works are however needed to ultimately realize the full potential of the proposed approach to appraise biological samples in complex buffer solutions rather than in DI water.