Distance Dependence of Single-Molecule Energy Transfer to Graphene Measured with DNA Origami Nanopositioners

Abstract

Despite the thorough investigation of graphene since 2004, altering its surface chemistry and reproducible functionalization remain challenging. This hinders fabrication of more complex hybrid materials with controlled architectures, and as a consequence the development of sensitive and reliable sensors and biological assays. In this contribution, we introduce DNA origami structures as nanopositioners for placing single dye molecules at controlled distances from graphene. The measurements of fluorescence intensity and lifetime of single emitters carried out for distances ranging from 3 to 58 nm confirmed the d −4 dependence of the excitation energy transfer to graphene. Moreover, we determined the characteristic distance for 50% efficiency of the energy transfer from single dyes to graphene to be 17.7 nm. Using pyrene molecules as a glue to immobilize DNA origami nanostructures of various shape on graphene opens new possibilities to develop graphene-based biophysics and biosensing.

Graphene Energy Transfer for Single‐Molecule Biophysics, Biosensing, and Super‐Resolution Microscopy

“…[ 1–5 ] While only 2.3% of visible light is absorbed, graphene constitutes an efficient acceptor for nonradiative energy transfer for fluorescent dyes in the near‐field in analogy to FRET. [ 6–10 ] Accordingly, excited state energy is nonradiatively transferred to graphene with a d −4 scaling law and a wavelength independent characteristic length scale of ≈18 nm with 50% energy transfer efficiency. [ 6,8,9 ] The fluorescence quenching property has been used for graphene characterization [ 10–12 ] and for biosensors based on graphene‐related materials such as graphene oxide or reduced graphene oxide [ 13–16 ] but only recently its potential for applications in the life science including super‐resolution microscopy has been realized.…”

DNA Origami-Enabled Biosensors

“…Tinnefeld's group changed the traditional FRET pairs by introducing grapheme with unique electronic, optical, and mechanical properties as quencher. They used rectangular, disc, and pillar-shaped DNA origami structures as nanopositioner for arranging single dye molecules at defined distance from graphene [82]. In virtue of this system, they investigated the regularity of single molecule energy transferring from single dyes to grapheme with the distance ranging from 3 to 58 nm.…”

Recent advances in fluorescence sensors based on DNA–MOF hybrids

“…Lipid, peptide and DNA are all attractive surface ligands for MOFs . Among these, due to DNA designable sequence and precise base‐pairing properties, DNA has been a superstar molecule in the field of nanomaterials …”