DNA-stabilized silver clusters are remarkable for the selection of fluorescence color by the sequence of the stabilizing DNA oligomer. Yet despite a growing number of applications that exploit this property, no large-scale studies have probed origins of cluster color or whether certain colors occur more frequently than others. Here we employ a set of 684 randomly chosen 10-base oligomers to address these questions. Rather than a flat distribution, we find that specific color bands dominate. Cluster size data indicate that these “magic colors” originate from the existence of magic numbers for DNA-stabilized silver clusters, which differ from those of spheroidal gold clusters stabilized by small-molecule ligands. Elongated cluster structures, enforced by multiple base ligands along the DNA, can account for both magic number sizes and color variation around peak wavelength populations.

Metal ion interactions with DNA have far-reaching implications in biochemistry and DNA nanotechnology. Ag⁺ is uniquely interesting because it binds exclusively to the bases rather than the backbone of DNA, without the toxicity of Hg²⁺. In contrast to prior studies of Ag⁺ incorporation into double-stranded DNA, we remove the constraints of Watson-Crick pairing by focusing on homo-base DNA oligomers of the canonical bases. High resolution electro-spray ionization mass spectrometry reveals an unanticipated Ag⁺-mediated pairing of guanine homo-base strands, with higher stability than canonical guanine-cytosine pairing. By exploring unrestricted binding geometries, quantum chemical calculations find that Ag⁺ bridges between non-canonical sites on guanine bases. Circular dichroism spectroscopy shows that the Ag⁺-mediated structuring of guanine homobase strands persists to at least 90 °C under conditions for which canonical guanine-cytosine duplexes melt below 20 °C. These findings are promising for DNA nanotechnology and metal-ion based biomedical science.

We use tandem HPLC-mass spectrometry with in-line spectroscopy to identify silver atom numbers, N_Ag, of 10 to 21 in visible- to infrared-emitting Ag:DNA complexes stabilized by oligonucleotide monomers and dimers. Qualitatively different absorbance spectra from bare, same-N_Ag silver clusters point to silver-base interactions as the origin for the color of Ag:DNAs.

DNA-protected silver clusters (Ag_N-DNA) possess unique fluorescence properties that depend on the specific DNA template that stabilizes the cluster. They exhibit peak emission wavelengths that range across the visible and near-IR spectrum. This wide color palette, combined with low toxicity, high fluorescence quantum yields of some clusters, low synthesis costs, small cluster sizes and compatibility with DNA are enabling many applications that employ Ag_N-DNA. Here we review what is known about the underlying composition and structure of Ag_N-DNA, and how these relate to the optical properties of these fascinating, hybrid biomolecule-metal cluster nanomaterials. We place Ag_N-DNA in the general context of ligand-stabilized metal clusters and compare their properties to those of other noble metal clusters stabilized by small molecule ligands. The methods used to isolate pure Ag_N-DNA for analysis of composition and for studies of solution and single-emitter optical properties are discussed. We give a brief overview of structurally sensitive chiroptical studies, both theoretical and experimental, and review experiments on bringing silver clusters of distinct size and color into nanoscale DNA assemblies. Progress towards using DNA scaffolds to assemble multi-cluster arrays is also reviewed.