Formation and Structure of Fluorescent Silver Nanoclusters at Interfacial Binding Sites Facilitating Oligomerization of DNA Hairpins

Fluorescent, DNA‐stabilized silver nanoclusters (DNA‐AgNCs) are applied in a range of applications within nanoscience and nanotechnology. However, their diverse optical properties, mechanism of formation, and aspects of their composition remain unexplored, making the rational design of nanocluster p...

Full description

Saved in:
Bibliographic Details
Published in:Angewandte Chemie 2020-09, Vol.132 (37), p.16225-16231
Main Authors: Geczy, Reka, Christensen, Niels Johan, Rasmussen, Kim K., Kálomista, Ildikó, Tiwari, Manish K., Shah, Pratik, Yang, Seong Wook, Bjerrum, Morten J., Thulstrup, Peter W.
Format: Article
Language:English
Subjects:
Binding sites
Chemistry
Deoxyribonucleic acid
DNA
DNA nanotechnology
DNA probes
DNA structures
Electrophoresis
Fluorescence
Gel electrophoresis
Gene sequencing
Inductively coupled plasma mass spectrometry
Mass spectrometry
Mass spectroscopy
Nanoclusters
Nanotechnology
Nucleotide sequence
Oligomerization
Optical properties
self-assembly
silver
Small angle X ray scattering
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:Fluorescent, DNA‐stabilized silver nanoclusters (DNA‐AgNCs) are applied in a range of applications within nanoscience and nanotechnology. However, their diverse optical properties, mechanism of formation, and aspects of their composition remain unexplored, making the rational design of nanocluster probes challenging. Herein, a synthetic procedure is described for obtaining a high yield of emissive DNA‐AgNCs with a C‐loop hairpin DNA sequence, with subsequent purification by size‐exclusion chromatography (SEC). Through a combination of optical spectroscopy, gel electrophoresis, inductively coupled plasma mass spectrometry (ICP‐MS), and small‐angle X‐ray scattering (SAXS) in conjunction with the systematic study of various DNA sequences, the low‐resolution structure and mechanism of the formation of AgNCs were investigated. Data indicate that fluorescent DNA‐AgNCs self‐assemble by a head‐to‐head binding of two DNA hairpins, bridged by a silver nanocluster, resulting in the modelling of a dimeric structure harboring an Ag12 cluster. Emissive silver nanoclusters formed with cytosine‐loop hairpin DNA sequences self‐assemble as highly emissive dimers exhibiting a head‐to‐head interaction interface. These dimeric species only form emissive dimers when synthesis is initiated from DNA in the monomeric hairpin conformation. The orange emissive AgNCs were found to be composed of 12 Ag per dimer with the dimerization mediated by the nanocluster.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.202005102