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Title: Photophysics of 2{prime}-deoxyuridine (dU) nucleosides covalently substituted with either 1-pyrenyl or 1-pyrenoyl. Observation of pyrene-to-nucleoside charge-transfer emission in 5-(1-pyrenyl)-dU

Abstract

This paper reports syntheses electronic absorbance and emission spectra, and emission kinetics results for two types of pyrene-substituted uridine nucleosides as part of an ongoing study which is examining the photophysical and photochemical behaviors of these same nucleosides embedded in DNA oligomers and duplexes with varying base-sequence composition. The two labels are 1-pyrenyl itself and 1-carboxypyrenyl (1-pyrenoyl) which are each joined direcrly to the 5-position of 2`-deoxyuridine (dCT). These direct attachments significantly restrict the range of conformations available to the pyrene label when it is attached to a DNA oligomer or duplex. {pi},{pi}{sup *} emission is absent for 5-(1-pyrenyl)-dU, 1, in methanol (MeOH) but present in tetrahydrofuran (THF). The steady-state emission spectrum of 1 in MeOH shows that emission from the few long-lived {pi},{pi}{sup *} states is dominated at all wavelengths by the 0.9-ns lived CT emission. In contrast, only {pi},{pi}{sup *} emission is observed for 5-(1-pyrenoyl)-dU, 2, in both MeOH and THF with emission quantum yields of 0.002 and 0.028, respectively. The spectral and emission kinetics data for nucleosides 1 and 2 support the conclusions that each has multiple conformers in solution and that the relative orientation of the pyrene and uridine {pi}-systems plays a crucial role in determiningmore » the rates of both ET quenching of pyrene{sup *} and charge-recombination in the photoproduct. 98 refs., 2 figs., 3 tabs.« less

Authors:
; ;  [1]; ; ;  [2]
  1. Georgia State Univ., Atlanta, GA (United States)
  2. Washington State Univ., Pullman, WA (United States)
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
115677
Resource Type:
Journal Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 117; Journal Issue: 36; Other Information: PBD: 13 Sep 1995
Country of Publication:
United States
Language:
English
Subject:
40 CHEMISTRY; NUCLEOSIDES; PHOTOCHEMICAL REACTIONS; SYNTHESIS; ABSORPTION SPECTRA; EMISSION SPECTRA; ULTRAVIOLET SPECTRA; URIDINE; CHARGE TRANSPORT; BIOCHEMISTRY; PYRENE; KINETICS

Citation Formats

Netzel, T L, Zhao, M, Nafisi, K, Headrick, J, Sigman, M S, and Eaton, B E. Photophysics of 2{prime}-deoxyuridine (dU) nucleosides covalently substituted with either 1-pyrenyl or 1-pyrenoyl. Observation of pyrene-to-nucleoside charge-transfer emission in 5-(1-pyrenyl)-dU. United States: N. p., 1995. Web. doi:10.1021/ja00141a002.
Netzel, T L, Zhao, M, Nafisi, K, Headrick, J, Sigman, M S, & Eaton, B E. Photophysics of 2{prime}-deoxyuridine (dU) nucleosides covalently substituted with either 1-pyrenyl or 1-pyrenoyl. Observation of pyrene-to-nucleoside charge-transfer emission in 5-(1-pyrenyl)-dU. United States. https://doi.org/10.1021/ja00141a002
Netzel, T L, Zhao, M, Nafisi, K, Headrick, J, Sigman, M S, and Eaton, B E. Wed . "Photophysics of 2{prime}-deoxyuridine (dU) nucleosides covalently substituted with either 1-pyrenyl or 1-pyrenoyl. Observation of pyrene-to-nucleoside charge-transfer emission in 5-(1-pyrenyl)-dU". United States. https://doi.org/10.1021/ja00141a002.
@article{osti_115677,
title = {Photophysics of 2{prime}-deoxyuridine (dU) nucleosides covalently substituted with either 1-pyrenyl or 1-pyrenoyl. Observation of pyrene-to-nucleoside charge-transfer emission in 5-(1-pyrenyl)-dU},
author = {Netzel, T L and Zhao, M and Nafisi, K and Headrick, J and Sigman, M S and Eaton, B E},
abstractNote = {This paper reports syntheses electronic absorbance and emission spectra, and emission kinetics results for two types of pyrene-substituted uridine nucleosides as part of an ongoing study which is examining the photophysical and photochemical behaviors of these same nucleosides embedded in DNA oligomers and duplexes with varying base-sequence composition. The two labels are 1-pyrenyl itself and 1-carboxypyrenyl (1-pyrenoyl) which are each joined direcrly to the 5-position of 2`-deoxyuridine (dCT). These direct attachments significantly restrict the range of conformations available to the pyrene label when it is attached to a DNA oligomer or duplex. {pi},{pi}{sup *} emission is absent for 5-(1-pyrenyl)-dU, 1, in methanol (MeOH) but present in tetrahydrofuran (THF). The steady-state emission spectrum of 1 in MeOH shows that emission from the few long-lived {pi},{pi}{sup *} states is dominated at all wavelengths by the 0.9-ns lived CT emission. In contrast, only {pi},{pi}{sup *} emission is observed for 5-(1-pyrenoyl)-dU, 2, in both MeOH and THF with emission quantum yields of 0.002 and 0.028, respectively. The spectral and emission kinetics data for nucleosides 1 and 2 support the conclusions that each has multiple conformers in solution and that the relative orientation of the pyrene and uridine {pi}-systems plays a crucial role in determining the rates of both ET quenching of pyrene{sup *} and charge-recombination in the photoproduct. 98 refs., 2 figs., 3 tabs.},
doi = {10.1021/ja00141a002},
url = {https://www.osti.gov/biblio/115677}, journal = {Journal of the American Chemical Society},
number = 36,
volume = 117,
place = {United States},
year = {1995},
month = {9}
}