Chloride Ligands on DNA-Stabilized Silver Nanoclusters
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DNA-stabilized silver nanoclusters (AgN-DNAs) are known to have one or two DNA oligomer ligands per nanocluster. Here, we present the first evidence that AgN-DNA species can possess additional chloride ligands that lead to increased stability in biologically relevant concentrations of chloride. Mass spectrometry of five chromatographically isolated near-infrared (NIR)-emissive AgN-DNA species with previously reported X-ray crystal structures determines their molecular formulas to be (DNA)2[Ag16Cl2]8+. Chloride ligands can be exchanged for bromides, which red-shift the optical spectra of these emitters. Density functional theory (DFT) calculations of the 6-electron nanocluster show that the two newly identified chloride ligands were previously assigned as low-occupancy silvers by X-ray crystallography. DFT also confirms the stability of chloride in the crystallographic structure, yields qualitative agreement between computed and measured UV-vis absorption spectra, and provides interpretation of the 35Cl-nuclear magnetic resonance spectrum of (DNA)2[Ag16Cl2]8+. A reanalysis of the X-ray crystal structure confirms that the two previously assigned low-occupancy silvers are, in fact, chlorides, yielding (DNA)2[Ag16Cl2]8+. Using the unusual stability of (DNA)2[Ag16Cl2]8+ in biologically relevant saline solutions as a possible indicator of other chloride-containing AgN-DNAs, we identified an additional AgN-DNA with a chloride ligand by high-throughput screening. Inclusion of chlorides on AgN-DNAs presents a promising new route to expand the diversity of AgN-DNA structure-property relationships and to imbue these emitters with favorable stability for biophotonics applications.
Originalsprog | Engelsk |
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Tidsskrift | Journal of the American Chemical Society |
Vol/bind | 145 |
Udgave nummer | 19 |
Sider (fra-til) | 10721−10729 |
Antal sider | 9 |
ISSN | 0002-7863 |
DOI | |
Status | Udgivet - 2023 |
Bibliografisk note
Funding Information:
This work was supported by NSF Biophotonics CBET-2025790. A.G.-R. acknowledges a Balsells Graduate Fellowship. The computational work was supported by the Academy of Finland and by the Excellence Funding from the JYU rector. The computations were made at the Finnish national supercomputing center CSC. The authors acknowledge Malak Rafik for assistance with screening for Ag-DNA stability in saline solutions. N
Publisher Copyright:
© 2023 The Authors. Published by American Chemical Society.
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