Exciton Absorption and Luminescence in i-Motif DNA

Zakhar V. Reveguk, Evgeny V. Khoroshilov, Andrey V. Sharkov, Vladimir A. Pomogaev, Andrey A. Buglak, Alexander N. Tarnovsky, Alexei I. Kononov

Результат исследований: Научные публикации в периодических изданияхстатья

Выдержка

We have studied the excited-state dynamics for the i-motif form of cytosine chains (dC)10, using the ultrafast fluorescence up-conversion technique. We have also calculated vertical electronic transition energies and determined the nature of the corresponding excited states in a model tetramer i-motif structure. Quantum chemical calculations of the excitation spectrum of a tetramer i-motif structure predict a significant (0.3 eV) red shift of the lowest-energy transition in the i-motif form relative to its absorption maximum, which agrees with the experimental absorption spectrum. The lowest excitonic state in i-(dC)10 is responsible for a 2 ps red-shifted emission at 370 nm observed in the decay-associated spectra obtained on the femtosecond time-scale. This delocalized (excitonic) excited state is likely a precursor to a long-lived excimer state observed in previous studies. Another fast 310 fs component at 330 nm is assigned to a monomer-like locally excited state. Both emissive states form within less than the available time resolution of the instrument (100 fs). This work contributes to the understanding of excited-state dynamics of DNA within the first few picoseconds, which is the most interesting time range with respect to unraveling the photodamage mechanism, including the formation of the most dangerous DNA lesions such as cyclobutane pyrimidine dimers.
Язык оригиналаанглийский
Номер статьи15988
ЖурналScientific Reports
Том9
СостояниеОпубликовано - 5 ноя 2019

Отпечаток

deoxyribonucleic acid
excitons
luminescence
excitation
cyclobutane
pyrimidines
excimers
red shift
lesions
monomers
dimers
absorption spectra
fluorescence
energy
decay
electronics

Цитировать

Reveguk, Z. V., Khoroshilov, E. V., Sharkov, A. V., Pomogaev, V. A., Buglak, A. A., Tarnovsky, A. N., & Kononov, A. I. (2019). Exciton Absorption and Luminescence in i-Motif DNA. Scientific Reports, 9, [15988].
Reveguk, Zakhar V. ; Khoroshilov, Evgeny V. ; Sharkov, Andrey V. ; Pomogaev, Vladimir A. ; Buglak, Andrey A. ; Tarnovsky, Alexander N. ; Kononov, Alexei I. . / Exciton Absorption and Luminescence in i-Motif DNA. В: Scientific Reports. 2019 ; Том 9.
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title = "Exciton Absorption and Luminescence in i-Motif DNA",
abstract = "We have studied the excited-state dynamics for the i-motif form of cytosine chains (dC)10, using the ultrafast fluorescence up-conversion technique. We have also calculated vertical electronic transition energies and determined the nature of the corresponding excited states in a model tetramer i-motif structure. Quantum chemical calculations of the excitation spectrum of a tetramer i-motif structure predict a significant (0.3 eV) red shift of the lowest-energy transition in the i-motif form relative to its absorption maximum, which agrees with the experimental absorption spectrum. The lowest excitonic state in i-(dC)10 is responsible for a 2 ps red-shifted emission at 370 nm observed in the decay-associated spectra obtained on the femtosecond time-scale. This delocalized (excitonic) excited state is likely a precursor to a long-lived excimer state observed in previous studies. Another fast 310 fs component at 330 nm is assigned to a monomer-like locally excited state. Both emissive states form within less than the available time resolution of the instrument (100 fs). This work contributes to the understanding of excited-state dynamics of DNA within the first few picoseconds, which is the most interesting time range with respect to unraveling the photodamage mechanism, including the formation of the most dangerous DNA lesions such as cyclobutane pyrimidine dimers.",
keywords = "Biological fluorescence, Biological physics, Photochemistry, Physical chemistry",
author = "Reveguk, {Zakhar V.} and Khoroshilov, {Evgeny V.} and Sharkov, {Andrey V.} and Pomogaev, {Vladimir A.} and Buglak, {Andrey A.} and Tarnovsky, {Alexander N.} and Kononov, {Alexei I.}",
note = "Reveguk, Z.V., Khoroshilov, E.V., Sharkov, A.V. et al. Exciton Absorption and Luminescence in i-Motif DNA. Sci Rep 9, 15988 (2019) doi:10.1038/s41598-019-52242-1",
year = "2019",
month = "11",
day = "5",
language = "English",
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journal = "Scientific Reports",
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Reveguk, ZV, Khoroshilov, EV, Sharkov, AV, Pomogaev, VA, Buglak, AA, Tarnovsky, AN & Kononov, AI 2019, 'Exciton Absorption and Luminescence in i-Motif DNA', Scientific Reports, том. 9, 15988.

Exciton Absorption and Luminescence in i-Motif DNA. / Reveguk, Zakhar V. ; Khoroshilov, Evgeny V.; Sharkov, Andrey V.; Pomogaev, Vladimir A.; Buglak, Andrey A. ; Tarnovsky, Alexander N.; Kononov, Alexei I. .

В: Scientific Reports, Том 9, 15988, 05.11.2019.

Результат исследований: Научные публикации в периодических изданияхстатья

TY - JOUR

T1 - Exciton Absorption and Luminescence in i-Motif DNA

AU - Reveguk, Zakhar V.

AU - Khoroshilov, Evgeny V.

AU - Sharkov, Andrey V.

AU - Pomogaev, Vladimir A.

AU - Buglak, Andrey A.

AU - Tarnovsky, Alexander N.

AU - Kononov, Alexei I.

N1 - Reveguk, Z.V., Khoroshilov, E.V., Sharkov, A.V. et al. Exciton Absorption and Luminescence in i-Motif DNA. Sci Rep 9, 15988 (2019) doi:10.1038/s41598-019-52242-1

PY - 2019/11/5

Y1 - 2019/11/5

N2 - We have studied the excited-state dynamics for the i-motif form of cytosine chains (dC)10, using the ultrafast fluorescence up-conversion technique. We have also calculated vertical electronic transition energies and determined the nature of the corresponding excited states in a model tetramer i-motif structure. Quantum chemical calculations of the excitation spectrum of a tetramer i-motif structure predict a significant (0.3 eV) red shift of the lowest-energy transition in the i-motif form relative to its absorption maximum, which agrees with the experimental absorption spectrum. The lowest excitonic state in i-(dC)10 is responsible for a 2 ps red-shifted emission at 370 nm observed in the decay-associated spectra obtained on the femtosecond time-scale. This delocalized (excitonic) excited state is likely a precursor to a long-lived excimer state observed in previous studies. Another fast 310 fs component at 330 nm is assigned to a monomer-like locally excited state. Both emissive states form within less than the available time resolution of the instrument (100 fs). This work contributes to the understanding of excited-state dynamics of DNA within the first few picoseconds, which is the most interesting time range with respect to unraveling the photodamage mechanism, including the formation of the most dangerous DNA lesions such as cyclobutane pyrimidine dimers.

AB - We have studied the excited-state dynamics for the i-motif form of cytosine chains (dC)10, using the ultrafast fluorescence up-conversion technique. We have also calculated vertical electronic transition energies and determined the nature of the corresponding excited states in a model tetramer i-motif structure. Quantum chemical calculations of the excitation spectrum of a tetramer i-motif structure predict a significant (0.3 eV) red shift of the lowest-energy transition in the i-motif form relative to its absorption maximum, which agrees with the experimental absorption spectrum. The lowest excitonic state in i-(dC)10 is responsible for a 2 ps red-shifted emission at 370 nm observed in the decay-associated spectra obtained on the femtosecond time-scale. This delocalized (excitonic) excited state is likely a precursor to a long-lived excimer state observed in previous studies. Another fast 310 fs component at 330 nm is assigned to a monomer-like locally excited state. Both emissive states form within less than the available time resolution of the instrument (100 fs). This work contributes to the understanding of excited-state dynamics of DNA within the first few picoseconds, which is the most interesting time range with respect to unraveling the photodamage mechanism, including the formation of the most dangerous DNA lesions such as cyclobutane pyrimidine dimers.

KW - Biological fluorescence

KW - Biological physics

KW - Photochemistry

KW - Physical chemistry

UR - https://www.nature.com/articles/s41598-019-52242-1

M3 - Article

VL - 9

JO - Scientific Reports

JF - Scientific Reports

SN - 2045-2322

M1 - 15988

ER -

Reveguk ZV, Khoroshilov EV, Sharkov AV, Pomogaev VA, Buglak AA, Tarnovsky AN и соавт. Exciton Absorption and Luminescence in i-Motif DNA. Scientific Reports. 2019 Нояб. 5;9. 15988.