文摘
We introduce herein the use of atomic-force electrochemical microscopy (AFM-SECM) to simultaneouslyprobe locally the conformation and motional dynamics of nanometer-sized single-stranded (ss) and double-stranded (ds) DNA oligonucleotides end-tethered to electrode surfaces. The ss-DNA system studied hereconsists of a low-density monolayer of (dT)20 oligonucleotides, 5'-thiol end-tethered onto a flat gold surfacevia a C6 alkyl linker and bearing at their free 3'-end a redox ferrocene label. It is shown that, as a result ofthe flexibility of the relatively long C6 linker, hinge motion, rather than elastic deformation of the DNAchain, is the major component of the dynamics of both the (dT)20 strand and its post-hybridized (dT-dA)20duplex. DNA chain elasticity is nevertheless sufficiently contributing to the overall dynamics to result in ~4times slower dynamics for (dT-dA)20 than for (dT)20. Taking advantage of this dissimilar dynamical behaviorof ss- and ds-DNA, it is demonstrated that hybridization can be easily locally detected at the scale of ~200molecules by AFM-SECM.