Fluorescent excimers and exciplexes of the purine base derivative 8-phenylethynyl-guanine in DNA hairpins

Kristen E. Brown, Arunoday P.N. Singh, Yi Lin Wu, Lin Ma, Ashutosh K. Mishra, Brian T. Phelan, Ryan M. Young, Frederick D. Lewis, Michael R Wasielewski

Research output: Contribution to journalArticle

Abstract

The ground- and excited-state electronic interactions between the nucleobase analog 8-(4′-phenylethynyl)deoxyguanosine, EG, with natural nucleobases and 7-deazaguanine, as well as between adjacent EG base analogs, have been characterized using a combination of steady-state spectroscopy and time-resolved fluorescence, absorption, and stimulated Raman spectroscopies. The properties of the nucleoside EG-H2 are only weakly perturbed upon incorporation into synthetic DNA hairpins in which thymine, cytosine or adenine are the bases flanking EG. Incorporation of the nucleoside to be adjacent to guanine or deazaguanine results in the formation of short-lived (40-80 ps) exciplexes, the charge transfer character of which increases as the oxidation potential of the donor decreases. Hairpins possessing two or three adjacent EG base analogs display exciton-coupled circular dichroism in the ground state and form long-lived fluorescent excited states upon electronic excitation. Incorporation of EG into the helical scaffold of the DNA hairpins places it adjacent to its neighboring nucleobases or a second EG, thus providing the close proximity required for the formation of exciplex or excimer intermediates upon geometric relaxation of the short-lived EG excited state. The three time-resolved spectroscopic methods employed permit both the characterization of the several intermediates and the kinetics of their formation and decay.

Original languageEnglish
Pages (from-to)217-232
Number of pages16
JournalFaraday Discussions
Volume207
DOIs
Publication statusPublished - Jan 1 2018

Fingerprint

purines
guanines
Guanine
excimers
Excited states
deoxyribonucleic acid
Derivatives
Nucleosides
Ground state
nucleosides
DNA
analogs
excitation
Deoxyguanosine
Thymine
Cytosine
Adenine
Scaffolds
ground state
thymine

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Fluorescent excimers and exciplexes of the purine base derivative 8-phenylethynyl-guanine in DNA hairpins. / Brown, Kristen E.; Singh, Arunoday P.N.; Wu, Yi Lin; Ma, Lin; Mishra, Ashutosh K.; Phelan, Brian T.; Young, Ryan M.; Lewis, Frederick D.; Wasielewski, Michael R.

In: Faraday Discussions, Vol. 207, 01.01.2018, p. 217-232.

Research output: Contribution to journalArticle

Brown, KE, Singh, APN, Wu, YL, Ma, L, Mishra, AK, Phelan, BT, Young, RM, Lewis, FD & Wasielewski, MR 2018, 'Fluorescent excimers and exciplexes of the purine base derivative 8-phenylethynyl-guanine in DNA hairpins', Faraday Discussions, vol. 207, pp. 217-232. https://doi.org/10.1039/c7fd00186j
Brown, Kristen E. ; Singh, Arunoday P.N. ; Wu, Yi Lin ; Ma, Lin ; Mishra, Ashutosh K. ; Phelan, Brian T. ; Young, Ryan M. ; Lewis, Frederick D. ; Wasielewski, Michael R. / Fluorescent excimers and exciplexes of the purine base derivative 8-phenylethynyl-guanine in DNA hairpins. In: Faraday Discussions. 2018 ; Vol. 207. pp. 217-232.
@article{73633b9be0904404810dfdef01d839af,
title = "Fluorescent excimers and exciplexes of the purine base derivative 8-phenylethynyl-guanine in DNA hairpins",
abstract = "The ground- and excited-state electronic interactions between the nucleobase analog 8-(4′-phenylethynyl)deoxyguanosine, EG, with natural nucleobases and 7-deazaguanine, as well as between adjacent EG base analogs, have been characterized using a combination of steady-state spectroscopy and time-resolved fluorescence, absorption, and stimulated Raman spectroscopies. The properties of the nucleoside EG-H2 are only weakly perturbed upon incorporation into synthetic DNA hairpins in which thymine, cytosine or adenine are the bases flanking EG. Incorporation of the nucleoside to be adjacent to guanine or deazaguanine results in the formation of short-lived (40-80 ps) exciplexes, the charge transfer character of which increases as the oxidation potential of the donor decreases. Hairpins possessing two or three adjacent EG base analogs display exciton-coupled circular dichroism in the ground state and form long-lived fluorescent excited states upon electronic excitation. Incorporation of EG into the helical scaffold of the DNA hairpins places it adjacent to its neighboring nucleobases or a second EG, thus providing the close proximity required for the formation of exciplex or excimer intermediates upon geometric relaxation of the short-lived EG excited state. The three time-resolved spectroscopic methods employed permit both the characterization of the several intermediates and the kinetics of their formation and decay.",
author = "Brown, {Kristen E.} and Singh, {Arunoday P.N.} and Wu, {Yi Lin} and Lin Ma and Mishra, {Ashutosh K.} and Phelan, {Brian T.} and Young, {Ryan M.} and Lewis, {Frederick D.} and Wasielewski, {Michael R}",
year = "2018",
month = "1",
day = "1",
doi = "10.1039/c7fd00186j",
language = "English",
volume = "207",
pages = "217--232",
journal = "Faraday Discussions",
issn = "1364-5498",
publisher = "Royal Society of Chemistry",

}

TY - JOUR

T1 - Fluorescent excimers and exciplexes of the purine base derivative 8-phenylethynyl-guanine in DNA hairpins

AU - Brown, Kristen E.

AU - Singh, Arunoday P.N.

AU - Wu, Yi Lin

AU - Ma, Lin

AU - Mishra, Ashutosh K.

AU - Phelan, Brian T.

AU - Young, Ryan M.

AU - Lewis, Frederick D.

AU - Wasielewski, Michael R

PY - 2018/1/1

Y1 - 2018/1/1

N2 - The ground- and excited-state electronic interactions between the nucleobase analog 8-(4′-phenylethynyl)deoxyguanosine, EG, with natural nucleobases and 7-deazaguanine, as well as between adjacent EG base analogs, have been characterized using a combination of steady-state spectroscopy and time-resolved fluorescence, absorption, and stimulated Raman spectroscopies. The properties of the nucleoside EG-H2 are only weakly perturbed upon incorporation into synthetic DNA hairpins in which thymine, cytosine or adenine are the bases flanking EG. Incorporation of the nucleoside to be adjacent to guanine or deazaguanine results in the formation of short-lived (40-80 ps) exciplexes, the charge transfer character of which increases as the oxidation potential of the donor decreases. Hairpins possessing two or three adjacent EG base analogs display exciton-coupled circular dichroism in the ground state and form long-lived fluorescent excited states upon electronic excitation. Incorporation of EG into the helical scaffold of the DNA hairpins places it adjacent to its neighboring nucleobases or a second EG, thus providing the close proximity required for the formation of exciplex or excimer intermediates upon geometric relaxation of the short-lived EG excited state. The three time-resolved spectroscopic methods employed permit both the characterization of the several intermediates and the kinetics of their formation and decay.

AB - The ground- and excited-state electronic interactions between the nucleobase analog 8-(4′-phenylethynyl)deoxyguanosine, EG, with natural nucleobases and 7-deazaguanine, as well as between adjacent EG base analogs, have been characterized using a combination of steady-state spectroscopy and time-resolved fluorescence, absorption, and stimulated Raman spectroscopies. The properties of the nucleoside EG-H2 are only weakly perturbed upon incorporation into synthetic DNA hairpins in which thymine, cytosine or adenine are the bases flanking EG. Incorporation of the nucleoside to be adjacent to guanine or deazaguanine results in the formation of short-lived (40-80 ps) exciplexes, the charge transfer character of which increases as the oxidation potential of the donor decreases. Hairpins possessing two or three adjacent EG base analogs display exciton-coupled circular dichroism in the ground state and form long-lived fluorescent excited states upon electronic excitation. Incorporation of EG into the helical scaffold of the DNA hairpins places it adjacent to its neighboring nucleobases or a second EG, thus providing the close proximity required for the formation of exciplex or excimer intermediates upon geometric relaxation of the short-lived EG excited state. The three time-resolved spectroscopic methods employed permit both the characterization of the several intermediates and the kinetics of their formation and decay.

UR - http://www.scopus.com/inward/record.url?scp=85045514578&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85045514578&partnerID=8YFLogxK

U2 - 10.1039/c7fd00186j

DO - 10.1039/c7fd00186j

M3 - Article

C2 - 29362748

AN - SCOPUS:85045514578

VL - 207

SP - 217

EP - 232

JO - Faraday Discussions

JF - Faraday Discussions

SN - 1364-5498

ER -