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Molecules 2016, 21(2), 216; doi:10.3390/molecules21020216

DNA Scaffolded Silver Clusters: A Critical Study

1
Department of Chemistry, Tougaloo College, 500 West County Line Road, Tougaloo, MS 39174, USA
2
Department of Chemistry, Columbia University, 3000 Broadway, New York, NY 10027, USA
*
Author to whom correspondence should be addressed.
Academic Editor: Ramon Eritja
Received: 28 December 2015 / Revised: 1 February 2016 / Accepted: 2 February 2016 / Published: 17 February 2016
(This article belongs to the Special Issue Frontiers in Nucleic Acid Chemistry)
View Full-Text   |   Download PDF [4301 KB, uploaded 17 February 2016]   |  

Abstract

Fluorescent silver nanoclusters (Ag-NCs) are in prominence as novel sensing materials due to their biocompatibility, photostability, and molecule-like optical properties. The present work is carried out on an array (17 sequences) of 16 bases long cytosine rich, single stranded DNA templates 5′-C3XiC3XiiC3XiiiC3Xiv-3′ where i, ii, iii, iv correspond to T/G/C deoxynucleobases (with default base A). Among all the oligonucleotides, a sequence C3AC3AC3TC3G (3T4G) has been identified, which grows three different near-infrared-emitting NC species with absorption/emission maxima at ~620/700 (species I), 730/800 (species II), and 830 (Species III) nm, respectively. The nature of the spectral profiles, along with relevant parameters namely absorption maximum (\(\lambda_{abs}^{max}\)), emission maximum (\(\lambda_{em}^{max}\)), anisotropy (r), lifetime (\(\tau\)), circular dichroism spectral data are used to understand the microenvironments of the fluorescent NC species I, II, and III. DNA:Ag stiochiometric, pH and solvent dependent studies proved that i-motif scaffolds with different folding topologies are associated with the growth of these three species and a certain concentration of silver and H+ favor the growth of species III. Size exclusion chromatographic measurements provided similar indications that a folded, more compact, classic i-motif template is associated with the formation of the longer NIR (~830 nm) absorbing species. This study provides a more definitive approach to design and obtain a targeted DNA templated Ag-NC with required emission properties for biophysical and cellular applications. View Full-Text
Keywords: i-motif; microenvironment; circular dichroism; fluorescence; size exclusion chromatography i-motif; microenvironment; circular dichroism; fluorescence; size exclusion chromatography
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Sengupta, B.; Corley, C.; Cobb, K.; Saracino, A.; Jockusch, S. DNA Scaffolded Silver Clusters: A Critical Study. Molecules 2016, 21, 216.

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