Photoselective DNA hairpin spin switches

Raanan Carmieli, Arun K. Thazhathveetil, Frederick D. Lewis, Michael R Wasielewski

Research output: Contribution to journalArticle

10 Citations (Scopus)

Abstract

DNA hairpins having both a tethered anthraquinone (Aq) end-capping group and a perylenediimide (PDI) base surrogate were synthesized, wherein Aq and PDI are each separated from a G-C base pair hole trap by A-T and I-C base pairs (G = guanine, A = adenine, T= thymine, C = cytosine, I = inosine). Selective photoexcitation of PDI at 532 nm generates a singlet radical ion pair (RP), 1(G+•-PDI-•), while selective photoexcitation of Aq at 355 nm generates the corresponding triplet RP, 3(G+•-Aq-•). Subsequent radical pair intersystem crossing within these spin-correlated RPs leads to mixed spin states that exhibit spin-polarized, time-resolved EPR spectra in which the singlet- and triplet-initiated RPs have opposite phases. These results demonstrate that a carefully designed DNA hairpin can serve as a photodriven molecular spin switch based on wavelength-selective formation of the singlet or triplet RP without significant competition from undesired energy transfer processes.

Original languageEnglish
Pages (from-to)10970-10973
Number of pages4
JournalJournal of the American Chemical Society
Volume135
Issue number30
DOIs
Publication statusPublished - Jul 31 2013

Fingerprint

Anthraquinones
DNA
Photoexcitation
Switches
Ions
Base Pairing
Hole traps
Inosine
Energy transfer
Thymine
Paramagnetic resonance
Cytosine
Energy Transfer
Guanine
Adenine
Wavelength
perylenediimide

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Photoselective DNA hairpin spin switches. / Carmieli, Raanan; Thazhathveetil, Arun K.; Lewis, Frederick D.; Wasielewski, Michael R.

In: Journal of the American Chemical Society, Vol. 135, No. 30, 31.07.2013, p. 10970-10973.

Research output: Contribution to journalArticle

Carmieli, R, Thazhathveetil, AK, Lewis, FD & Wasielewski, MR 2013, 'Photoselective DNA hairpin spin switches', Journal of the American Chemical Society, vol. 135, no. 30, pp. 10970-10973. https://doi.org/10.1021/ja4055405
Carmieli, Raanan ; Thazhathveetil, Arun K. ; Lewis, Frederick D. ; Wasielewski, Michael R. / Photoselective DNA hairpin spin switches. In: Journal of the American Chemical Society. 2013 ; Vol. 135, No. 30. pp. 10970-10973.
@article{098e9cf156d4474f82b20cbd10cfcce9,
title = "Photoselective DNA hairpin spin switches",
abstract = "DNA hairpins having both a tethered anthraquinone (Aq) end-capping group and a perylenediimide (PDI) base surrogate were synthesized, wherein Aq and PDI are each separated from a G-C base pair hole trap by A-T and I-C base pairs (G = guanine, A = adenine, T= thymine, C = cytosine, I = inosine). Selective photoexcitation of PDI at 532 nm generates a singlet radical ion pair (RP), 1(G+•-PDI-•), while selective photoexcitation of Aq at 355 nm generates the corresponding triplet RP, 3(G+•-Aq-•). Subsequent radical pair intersystem crossing within these spin-correlated RPs leads to mixed spin states that exhibit spin-polarized, time-resolved EPR spectra in which the singlet- and triplet-initiated RPs have opposite phases. These results demonstrate that a carefully designed DNA hairpin can serve as a photodriven molecular spin switch based on wavelength-selective formation of the singlet or triplet RP without significant competition from undesired energy transfer processes.",
author = "Raanan Carmieli and Thazhathveetil, {Arun K.} and Lewis, {Frederick D.} and Wasielewski, {Michael R}",
year = "2013",
month = "7",
day = "31",
doi = "10.1021/ja4055405",
language = "English",
volume = "135",
pages = "10970--10973",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "30",

}

TY - JOUR

T1 - Photoselective DNA hairpin spin switches

AU - Carmieli, Raanan

AU - Thazhathveetil, Arun K.

AU - Lewis, Frederick D.

AU - Wasielewski, Michael R

PY - 2013/7/31

Y1 - 2013/7/31

N2 - DNA hairpins having both a tethered anthraquinone (Aq) end-capping group and a perylenediimide (PDI) base surrogate were synthesized, wherein Aq and PDI are each separated from a G-C base pair hole trap by A-T and I-C base pairs (G = guanine, A = adenine, T= thymine, C = cytosine, I = inosine). Selective photoexcitation of PDI at 532 nm generates a singlet radical ion pair (RP), 1(G+•-PDI-•), while selective photoexcitation of Aq at 355 nm generates the corresponding triplet RP, 3(G+•-Aq-•). Subsequent radical pair intersystem crossing within these spin-correlated RPs leads to mixed spin states that exhibit spin-polarized, time-resolved EPR spectra in which the singlet- and triplet-initiated RPs have opposite phases. These results demonstrate that a carefully designed DNA hairpin can serve as a photodriven molecular spin switch based on wavelength-selective formation of the singlet or triplet RP without significant competition from undesired energy transfer processes.

AB - DNA hairpins having both a tethered anthraquinone (Aq) end-capping group and a perylenediimide (PDI) base surrogate were synthesized, wherein Aq and PDI are each separated from a G-C base pair hole trap by A-T and I-C base pairs (G = guanine, A = adenine, T= thymine, C = cytosine, I = inosine). Selective photoexcitation of PDI at 532 nm generates a singlet radical ion pair (RP), 1(G+•-PDI-•), while selective photoexcitation of Aq at 355 nm generates the corresponding triplet RP, 3(G+•-Aq-•). Subsequent radical pair intersystem crossing within these spin-correlated RPs leads to mixed spin states that exhibit spin-polarized, time-resolved EPR spectra in which the singlet- and triplet-initiated RPs have opposite phases. These results demonstrate that a carefully designed DNA hairpin can serve as a photodriven molecular spin switch based on wavelength-selective formation of the singlet or triplet RP without significant competition from undesired energy transfer processes.

UR - http://www.scopus.com/inward/record.url?scp=84881080218&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84881080218&partnerID=8YFLogxK

U2 - 10.1021/ja4055405

DO - 10.1021/ja4055405

M3 - Article

C2 - 23855976

AN - SCOPUS:84881080218

VL - 135

SP - 10970

EP - 10973

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 30

ER -