Dual-Color Nanoscale Assemblies of Structurally Stable, Few-Atom Silver Clusters, As Reported by Fluorescence Resonance Energy Transfer

• Published in: ACS nano 2013-11, Vol.7 (11), p.9798-9807
• Main Authors: Schultz, Danielle, Copp, Stacy M, Markešević, Nemanja, Gardner, Kira, Oemrawsingh, Sumant S. R, Bouwmeester, Dirk, Gwinn, Elisabeth
• Format: Article
• Language: English
• Subjects: Assemblies; Base Sequence; Clamps; Clusters; Coloring Agents - chemistry; Deoxyribonucleic acid; DNA - chemistry; Fluorescence; Fluorescence Resonance Energy Transfer; Fretting; Metal Nanoparticles - chemistry; Molecular Sequence Data; Nanostructure; Nanotechnology - methods; Normal Distribution; Oligonucleotides - chemistry; Rhodamines - chemistry; Silver; Silver - chemistry; Spectra; Spectrometry, Fluorescence; Temperature
• ISSN: 1936-0851; 1936-086X
• DOI: 10.1021/nn4033097

We develop approaches to hold fluorescent silver clusters composed of only 10–20 atoms in nanoscale proximity, while retaining the individual structure of each cluster. This is accomplished using DNA clamp assemblies that incorporate a 10 atom silver cluster and a 15 or 16 atom silver cluster. Thermally modulated fluorescence resonance energy transfer (FRET) verifies assembly formation. Comparison to Förster theory, using measured spectral overlaps, indicates that the DNA clamps hold clusters within roughly 5 to 6 nm separations, in the range of the finest resolutions achievable on DNA scaffolds. The absence of spectral shifts in dual-cluster FRET pairs, relative to the individual clusters, shows that select few-atom silver clusters of different sizes are sufficiently stable to retain structural integrity within a single nanoscale DNA construct. The spectral stability of the cluster persists in a FRET pair with an organic dye molecule, in contrast to the blue-shifted emission of the dye.