A Segregated, Partially Oxidized, and Compact Ag10 Cluster within an Encapsulating DNA Host

• Published in: Journal of the American Chemical Society 2016-03, Vol.138 (10), p.3469-3477
• Main Authors: Petty, Jeffrey T, Sergev, Orlin O, Ganguly, Mainak, Rankine, Ian J, Chevrier, Daniel M, Zhang, Peng
• Format: Article
• Language: English
• Subjects: DNA - chemistry; Oxidation-Reduction; Silver - chemistry; X-Ray Absorption Spectroscopy
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/jacs.5b13124

Silver clusters develop within DNA strands and become optical chromophores with diverse electronic spectra and wide-ranging emission intensities. These studies consider a specific cluster that absorbs at 400 nm, has low emission, and exclusively develops with single-stranded oligonucleotides. It is also a chameleon-like chromophore that can be transformed into different highly emissive fluorophores. We describe four characteristics of this species and conclude that it is highly oxidized yet also metallic. One, the cluster size was determined via electrospray ionization mass spectrometry. A common silver mass is measured with different oligonucleotides and thereby supports a Ag10 cluster. Two, the cluster charge was determined by mass spectrometry and Ag L3-edge X-ray absorption near-edge structure spectroscopy. Respectively, the conjugate mass and the integrated white-line intensity support a partially oxidized cluster with a +6 and +6.5 charge, respectively. Three, the cluster chirality was gauged by circular dichroism spectroscopy. This chirality changes with the length and sequence of its DNA hosts, and these studies identified a dispersed binding site with ∼20 nucleobases. Four, the structure of this complex was investigated via Ag K-edge extended X-ray absorption fine structure spectroscopy. A multishell fitting analysis identified three unique scattering environments with corresponding bond lengths, coordination numbers, and Debye–Waller factors for each. Collectively, these findings support the following conclusion: a Ag10 +6 cluster develops within a 20-nucleobase DNA binding site, and this complex segregates into a compact, metal-like silver core that weakly links to an encapsulating silver–DNA shell. We consider different models that account for silver–silver coordination within the core.