title: A Segregated, Partially Oxidized, and Compact Ag10 Cluster within an Encapsulating DNA Host.
abstract: 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.
authors.affiliation: Department of Chemistry, Furman University , Greenville, South Carolina 29613, United States.
authors.forename: Jeffrey T
authors.initials: JT
authors.lastname: Petty
authors.affiliation: Department of Chemistry, Furman University , Greenville, South Carolina 29613, United States.
authors.forename: Orlin O
authors.initials: OO
authors.lastname: Sergev
authors.affiliation: Department of Chemistry, Furman University , Greenville, South Carolina 29613, United States.
authors.forename: Mainak
authors.initials: M
authors.lastname: Ganguly
authors.affiliation: Department of Chemistry, Furman University , Greenville, South Carolina 29613, United States.
authors.forename: Ian J
authors.initials: IJ
authors.lastname: Rankine
authors.affiliation: Department of Chemistry, Dalhousie University , Halifax, Nova Scotia B3H 4R2, Canada.
authors.forename: Daniel M
authors.initials: DM
authors.lastname: Chevrier
authors.affiliation: Department of Chemistry, Dalhousie University , Halifax, Nova Scotia B3H 4R2, Canada.
authors.forename: Peng
authors.initials: P
authors.lastname: Zhang
mesh_terms: D004247:DNA / Q000737:chemistry*; D010084:Oxidation-Reduction; D012834:Silver / Q000737:chemistry*; D056928:X-Ray Absorption Spectroscopy
chemical_list: D012834:Silver; D004247:DNA