Cryogenic Absorption and Emission Spectroscopy of the Oxyluciferin Anion In Vacuo

Jeppe Langeland; Nanna Falk Christensen; Emil Vogt; Christina Kjær; Thomas Toft Lindkvist; Steen Brøndsted Nielsen; Henrik G. Kjaergaard

doi:10.1021/acs.jpclett.3c01206

Cryogenic Absorption and Emission Spectroscopy of the Oxyluciferin Anion In Vacuo

Jeppe Langeland, Nanna Falk Christensen, Emil Vogt, Christina Kjær, Thomas Toft Lindkvist, Steen Brøndsted Nielsen^*, Henrik G. Kjaergaard^*

^*Corresponding author for this work

Department of Physics and Astronomy

Research output: Contribution to journal/Conference contribution in journal/Contribution to newspaper › Journal article › Research › peer-review

Abstract

Bioluminescence from fireflies, click beetles, and railroad worms ranges in color from green-yellow to orange to red. The keto form of oxyluciferin is considered a key emitter species in the proposed mechanisms to account for color variation. To establish the intrinsic photophysics in the absence of a microenvironment, we present experimental and theoretical gas-phase absorption and emission spectra of the 5,5-dimethyloxyluciferin anion (keto form) at room and cryogenic temperatures as well as lifetime measurements based on fluorescence. The theoretical model includes all 75 vibrational modes. The spectral impact of the large number of excited states at elevated temperatures is captured by an effective state distribution. At low temperature, spectral congestion is greatly reduced, and the observed well-resolved vibrational features are assigned to multiple Franck-Condon progressions involving different vibrational modes. An in-plane ∼60 cm^-1 scissoring mode is found to be involved in the dominant progressions.

Original language	English
Journal	Journal of Physical Chemistry Letters
Volume	14
Issue	25
Pages (from-to)	5949-5954
Number of pages	6
ISSN	1948-7185
DOIs	https://doi.org/10.1021/acs.jpclett.3c01206
Publication status	Published - Jun 2023

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10.1021/acs.jpclett.3c01206

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@article{53f852e09f7a4405a80641cb3f20c662,

title = "Cryogenic Absorption and Emission Spectroscopy of the Oxyluciferin Anion In Vacuo",

abstract = "Bioluminescence from fireflies, click beetles, and railroad worms ranges in color from green-yellow to orange to red. The keto form of oxyluciferin is considered a key emitter species in the proposed mechanisms to account for color variation. To establish the intrinsic photophysics in the absence of a microenvironment, we present experimental and theoretical gas-phase absorption and emission spectra of the 5,5-dimethyloxyluciferin anion (keto form) at room and cryogenic temperatures as well as lifetime measurements based on fluorescence. The theoretical model includes all 75 vibrational modes. The spectral impact of the large number of excited states at elevated temperatures is captured by an effective state distribution. At low temperature, spectral congestion is greatly reduced, and the observed well-resolved vibrational features are assigned to multiple Franck-Condon progressions involving different vibrational modes. An in-plane ∼60 cm-1 scissoring mode is found to be involved in the dominant progressions.",

author = "Jeppe Langeland and Christensen, {Nanna Falk} and Emil Vogt and Christina Kj{\ae}r and Lindkvist, {Thomas Toft} and Nielsen, {Steen Br{\o}ndsted} and Kjaergaard, {Henrik G.}",

note = "Publisher Copyright: {\textcopyright} 2023 American Chemical Society.",

year = "2023",

month = jun,

doi = "10.1021/acs.jpclett.3c01206",

language = "English",

volume = "14",

pages = "5949--5954",

journal = "Journal of Physical Chemistry Letters",

issn = "1948-7185",

publisher = "American Chemical Society",

number = "25",

}

Cryogenic Absorption and Emission Spectroscopy of the Oxyluciferin Anion In Vacuo. / Langeland, Jeppe; Christensen, Nanna Falk; Vogt, Emil et al.
In: Journal of Physical Chemistry Letters, Vol. 14, No. 25, 06.2023, p. 5949-5954.

Research output: Contribution to journal/Conference contribution in journal/Contribution to newspaper › Journal article › Research › peer-review

TY - JOUR

T1 - Cryogenic Absorption and Emission Spectroscopy of the Oxyluciferin Anion In Vacuo

AU - Langeland, Jeppe

AU - Christensen, Nanna Falk

AU - Vogt, Emil

AU - Kjær, Christina

AU - Lindkvist, Thomas Toft

AU - Nielsen, Steen Brøndsted

AU - Kjaergaard, Henrik G.

PY - 2023/6

Y1 - 2023/6

N2 - Bioluminescence from fireflies, click beetles, and railroad worms ranges in color from green-yellow to orange to red. The keto form of oxyluciferin is considered a key emitter species in the proposed mechanisms to account for color variation. To establish the intrinsic photophysics in the absence of a microenvironment, we present experimental and theoretical gas-phase absorption and emission spectra of the 5,5-dimethyloxyluciferin anion (keto form) at room and cryogenic temperatures as well as lifetime measurements based on fluorescence. The theoretical model includes all 75 vibrational modes. The spectral impact of the large number of excited states at elevated temperatures is captured by an effective state distribution. At low temperature, spectral congestion is greatly reduced, and the observed well-resolved vibrational features are assigned to multiple Franck-Condon progressions involving different vibrational modes. An in-plane ∼60 cm-1 scissoring mode is found to be involved in the dominant progressions.

AB - Bioluminescence from fireflies, click beetles, and railroad worms ranges in color from green-yellow to orange to red. The keto form of oxyluciferin is considered a key emitter species in the proposed mechanisms to account for color variation. To establish the intrinsic photophysics in the absence of a microenvironment, we present experimental and theoretical gas-phase absorption and emission spectra of the 5,5-dimethyloxyluciferin anion (keto form) at room and cryogenic temperatures as well as lifetime measurements based on fluorescence. The theoretical model includes all 75 vibrational modes. The spectral impact of the large number of excited states at elevated temperatures is captured by an effective state distribution. At low temperature, spectral congestion is greatly reduced, and the observed well-resolved vibrational features are assigned to multiple Franck-Condon progressions involving different vibrational modes. An in-plane ∼60 cm-1 scissoring mode is found to be involved in the dominant progressions.

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U2 - 10.1021/acs.jpclett.3c01206

DO - 10.1021/acs.jpclett.3c01206

M3 - Journal article

C2 - 37345799

AN - SCOPUS:85164209000

SN - 1948-7185

VL - 14

SP - 5949

EP - 5954

JO - Journal of Physical Chemistry Letters

JF - Journal of Physical Chemistry Letters

IS - 25

ER -

Cryogenic Absorption and Emission Spectroscopy of the Oxyluciferin Anion In Vacuo

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