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A DNA-Encapsulated and Fluorescent Ag106+ Cluster with a Distinct Metal-Like Core

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† Department of Chemistry, Furman University, Greenville, South Carolina 29613, United States
‡ Department of Chemistry, Dalhousie University, Halifax, NS, Canada B3H 4R2
*E-mail: [email protected]. Phone: 864-294-2689.
Cite this: J. Phys. Chem. C 2017, 121, 27, 14936–14945
Publication Date (Web):June 23, 2017
https://doi.org/10.1021/acs.jpcc.7b04506
Copyright © 2017 American Chemical Society
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    Abstract

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    Silver cluster–DNA complexes are optical chromophores, and pairs of these conjugates can be toggled from fluorescently dim to bright states using DNA hybridization. This paper highlights spectral and structural differences for a specific cluster pair. We have previously characterized a cluster with low emission and violet absorption that forms a compact structure with single-stranded oligonucleotides. We now consider its counterpart with blue absorption and strong green emission. This cluster develops with a single-stranded/duplex DNA construct and is favored by low silver concentrations with ≲8 Ag+:DNA, an oxygen atmosphere, and neutral pH. The resulting cluster displays key signatures of a molecular metal with well-defined absorption/emission bands at 490/550 nm, and with a fluorescence quantum yield of 15% and lifetime of 2.4 ns. The molecular cluster conjugates with the larger DNA host because it chromatographically elutes with the DNA and it exhibits circular dichroism. The silver cluster is identified as Ag106+ using two modes of mass spectrometry and elemental analysis. Our key finding is that it adopts a low-dimensional shape, as determined from a Ag K-edge extended X-ray absorption fine structure analysis. The Ag0 in this oxidized cluster segregates from the Ag+ via a sparse number of metal-like bonds and a denser network of silver–DNA bonds. This structure contrasts with the compact, octahedral-like shape of the violet counterpart to the blue cluster, which is also a Ag106+ species. We consider that the blue- and violet-absorbing clusters may be isomers with shapes that are controlled by the secondary structures of their DNA templates.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jpcc.7b04506.

    • Figures describing absorption spectra of the cluster with four stem-loop hairpins, absorption spectra of S1-Hp and S2-Hp complexes with the blue cluster, absorption spectra of the S1-Hp with varying amounts of Ag+, absorption spectra of S1-Hp/cluster complexes with and without oxygen, absorption spectra of the S1-Hp/cluster complex at different pH values, emission spectra of the S1-Hp/cluster complex, fluorescence lifetime measurements, reversed phase chromatograms of the S1-Hp/cluster samples, circular dichroism spectra of the S1-Hp and S2-Hp complexes, mass spectra of S1-Hp with and without Ag+, mass spectra of the −5, −6, −7, and −8 charge states of the S1-Hp/cluster complex, mass spectra that show how the intensity distributions shift with the numbers of hydrogens, positive ion mode mass spectra of the S1-Hp/cluster complex, mass spectra at different pH values, mass spectra of S1-Hp/Ag+ complexes at pH 7 and 9, Ag K-edge k-space of S1-Hp and S2-Hp Ag10 blue clusters and FT-EXAFS of the Ag10 S2-Hp cluster with a simulated three-shell fit, and Ag K-edge FT-EXAFS and XANES spectra for Ag10 blue clusters and Ag10 violet clusters (PDF)

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    Cited By

    This article is cited by 26 publications.

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    20. Stacy M. Copp, Anna Gonzàlez-Rosell. Large-scale investigation of the effects of nucleobase sequence on fluorescence excitation and Stokes shifts of DNA-stabilized silver clusters. Nanoscale 2021, 13 (8) , 4602-4613. https://doi.org/10.1039/D0NR08300C
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