Electronic interactions in helical stacked arrays of the modified DNA base pyrrolocytosine

Prakash P. Neelakandan; Martin McCullagh; George C Schatz; Frederick D Lewis

doi:10.1021/jp302385c

Electronic interactions in helical stacked arrays of the modified DNA base pyrrolocytosine

Prakash P. Neelakandan, Martin McCullagh, George C Schatz, Frederick D Lewis^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

7 Scopus citations

Abstract

The thermal stability and ultraviolet and circular dichroism spectra of nine synthetic DNA hairpins possessing one or more ^PC-G base pairs (^PC = pyrrolocytosine) have been investigated. One group of hairpins possess 1-5 sequential ^PC-G base pairs while another group possess two ^PC-G base pairs separated by 1-3 A-T base pairs. The first group displays a nearly linear dependence of UV and exciton-coupled circular dichroism (EC-CD) band intensity upon the number of neighboring chromophores, whereas the second group shows weak EC-CD only at the shortest distances between non-neighboring chromophores. This result stands in marked contrast to the exciton coupling seen between stilbene chromophores separated by as many as a dozen base pairs. The weak exciton coupling between non-neighboring ^PC chromophores, like that of the natural nucelobases, is attributed to their relatively weak electronic transition dipoles.

Original language	English (US)
Pages (from-to)	5199-5204
Number of pages	6
Journal	Journal of Physical Chemistry B
Volume	116
Issue number	17
DOIs	https://doi.org/10.1021/jp302385c
State	Published - May 3 2012

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Surfaces, Coatings and Films
Materials Chemistry

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title = "Electronic interactions in helical stacked arrays of the modified DNA base pyrrolocytosine",

abstract = "The thermal stability and ultraviolet and circular dichroism spectra of nine synthetic DNA hairpins possessing one or more PC-G base pairs (PC = pyrrolocytosine) have been investigated. One group of hairpins possess 1-5 sequential PC-G base pairs while another group possess two PC-G base pairs separated by 1-3 A-T base pairs. The first group displays a nearly linear dependence of UV and exciton-coupled circular dichroism (EC-CD) band intensity upon the number of neighboring chromophores, whereas the second group shows weak EC-CD only at the shortest distances between non-neighboring chromophores. This result stands in marked contrast to the exciton coupling seen between stilbene chromophores separated by as many as a dozen base pairs. The weak exciton coupling between non-neighboring PC chromophores, like that of the natural nucelobases, is attributed to their relatively weak electronic transition dipoles.",

author = "Neelakandan, {Prakash P.} and Martin McCullagh and Schatz, {George C} and Lewis, {Frederick D}",

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T1 - Electronic interactions in helical stacked arrays of the modified DNA base pyrrolocytosine

AU - Neelakandan, Prakash P.

AU - McCullagh, Martin

AU - Schatz, George C

AU - Lewis, Frederick D

PY - 2012/5/3

Y1 - 2012/5/3

N2 - The thermal stability and ultraviolet and circular dichroism spectra of nine synthetic DNA hairpins possessing one or more PC-G base pairs (PC = pyrrolocytosine) have been investigated. One group of hairpins possess 1-5 sequential PC-G base pairs while another group possess two PC-G base pairs separated by 1-3 A-T base pairs. The first group displays a nearly linear dependence of UV and exciton-coupled circular dichroism (EC-CD) band intensity upon the number of neighboring chromophores, whereas the second group shows weak EC-CD only at the shortest distances between non-neighboring chromophores. This result stands in marked contrast to the exciton coupling seen between stilbene chromophores separated by as many as a dozen base pairs. The weak exciton coupling between non-neighboring PC chromophores, like that of the natural nucelobases, is attributed to their relatively weak electronic transition dipoles.

AB - The thermal stability and ultraviolet and circular dichroism spectra of nine synthetic DNA hairpins possessing one or more PC-G base pairs (PC = pyrrolocytosine) have been investigated. One group of hairpins possess 1-5 sequential PC-G base pairs while another group possess two PC-G base pairs separated by 1-3 A-T base pairs. The first group displays a nearly linear dependence of UV and exciton-coupled circular dichroism (EC-CD) band intensity upon the number of neighboring chromophores, whereas the second group shows weak EC-CD only at the shortest distances between non-neighboring chromophores. This result stands in marked contrast to the exciton coupling seen between stilbene chromophores separated by as many as a dozen base pairs. The weak exciton coupling between non-neighboring PC chromophores, like that of the natural nucelobases, is attributed to their relatively weak electronic transition dipoles.

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Electronic interactions in helical stacked arrays of the modified DNA base pyrrolocytosine

Abstract

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