Electrochemical biosensors are being developed for detecting specific sequences of nucleic acids using DNA modified gold surfaces[1]. A single crystal gold bead electrode was used to study the arrangement on DNA on different gold surfaces[2]. The gold surface was prepared with a mercaptoundecanol (MUDOL) self-assembled monolayer (SAM). Using a specific desorption potential of -0.850 V/SCE, the MUDOL was reductively desorbed from the Au(111) facet. The defects in the SAM were passivated with a shorter alkylthiol, mercaptohexanol. Thiol modified DNA which is also labeled with a fluorophore was allowed to populate the 111 facet specifically. This was studied using fluorescence microscopy coupled with electrochemical control. A fluorescence image of the gold bead (Figure a) showed that only the 111 facets were modified. The density of the DNA modification was also evaluated using the reorientation of DNA based on the electrode charge density. At positive potentials the DNA was positioned close to the electrode and the fluorescence was quenched. At negative potentials the DNA was repelled and the fluorescence increased. This change in fluorescence is indicative of the density of DNA on the surface. The same approach will be used to assemble DNA modified Quantum Dots (QDs) onto the Au(111) facets. A complementary ssDNA was attached to a glutathione capped quantum dot vis a his-tag peptide. The QD labelled ssDNA was allowed to hybridize with the ssDNA on the gold electrode. Figure (b) is the cartoon depiction of such a layer. Recent research results will be described on the characterization of QD labelled DNA SAMs. The QDs due to their broad absorption and narrow emission spectrum also offer the advantage of building more complicated multiplexed systems in future.

(1) Hsieh, K.; Ferguson, B. S.; Eisenstein, M.; Plaxco, K. W.; Soh, H. T. Integrated Electrochemical Microsystems for Genetic Detection of Pathogens at the Point of Care. Acc. Chem. Res. 2015, 48, 911–920.

(2) Yu, Z. L.; Casanova-Moreno, J.; Guryanov, I.; Maran, F.; Bizzotto, D. Influence of Surface Structure on Single or Mixed Component Self-Assembled Monolayers via in Situ Spectroelectrochemical Fluorescence Imaging of the Complete Stereographic Triangle on a Single Crystal Au Bead Electrode. J. Am. Chem. Soc 2015, 137, 276–288.