A Multipronged Bioengineering, Spectroscopic and Theoretical Approach in Unravelling the Excited-State Dynamics of the Archetype Mycosporine Amino Acid

Michael Hymas; Sopida Wongwas; Simin Roshan; Abigail L Whittock; Christophe Corre; Reza Omidyan; Vasilios G Stavros

doi:10.1021/acs.jpclett.4c01254

A Multipronged Bioengineering, Spectroscopic and Theoretical Approach in Unravelling the Excited-State Dynamics of the Archetype Mycosporine Amino Acid

Michael Hymas, Sopida Wongwas, Simin Roshan, Abigail L Whittock, Christophe Corre^*, Reza Omidyan^*, Vasilios G Stavros^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

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Abstract

Mycosporine glycine (MyG) was produced by the fermentation of a purposely engineered bacterial strain and isolated from this sustainable source. The ultrafast spectroscopy of MyG was then investigated in its native, zwitterionic form (MyGzwitter), via femtosecond transient electronic absorption spectroscopy. Complementary nonadiabatic (NAD) simulations suggest that, upon photoexcitation to the lowest excited singlet state (S1), MyGzwitter undergoes efficient nonradiative decay to repopulate the electronic ground state (S0). We propose an initial ultrafast ring-twisting mechanism toward an S1/S0 conical intersection, followed by internal conversion to S0 and subsequent vibrational cooling. This study illuminates the workings of the archetype mycosporine, providing photoprotection, in the UV-B range, to organisms such as corals, macroalgae, and cyanobacteria. This study also contributes to our growing understanding of the photoprotection mechanisms of life.

Original language	English
Pages (from-to)	7424-7429
Number of pages	6
Journal	Journal of Physical Chemistry Letters
Volume	15
Issue number	29
Early online date	12 Jul 2024
DOIs	https://doi.org/10.1021/acs.jpclett.4c01254
Publication status	Published - 25 Jul 2024

Bibliographical note

Acknowledgments
S.W. and C.C. wish to thank Matthew P. Harwood (University of Warwick) for his assistance with the plasmid design. M.H. was supported by NERC CENTA2 (Grant No. NE/S007350/1). The Research Council of the University of Isfahan is kindly appreciated for financial support. The use of the computing facility cluster GMPCS of the LUMAT Federation (No. FR LUMAT2764) is acknowledged. V.G.S. thanks the Royal Society for a Royal Society Industry Fellowship. A.L.W. thanks the University of Warwick and Lubrizol for funding a Ph.D. studentship through the Centre for Doctoral Training in Analytical Science. R.O. thanks the support of Royal Society International Exchange (No. IES\R2\232279).

Keywords

Glycine/chemistry
Bioengineering
Ultraviolet Rays
Cyclohexanols

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10.1021/acs.jpclett.4c01254Licence: Creative Commons: Attribution (CC BY)

HymasM2024AMultiprongedFinal published version, 2.45 MBLicence: Creative Commons: Attribution (CC BY)

Exploiting Microbial Photoprotection: Insights from Theoretical approaches
Stavros, V.
The Royal Society
1/11/23 → 31/01/25
Project: Research Councils

Cite this

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title = "A Multipronged Bioengineering, Spectroscopic and Theoretical Approach in Unravelling the Excited-State Dynamics of the Archetype Mycosporine Amino Acid",

abstract = "Mycosporine glycine (MyG) was produced by the fermentation of a purposely engineered bacterial strain and isolated from this sustainable source. The ultrafast spectroscopy of MyG was then investigated in its native, zwitterionic form (MyGzwitter), via femtosecond transient electronic absorption spectroscopy. Complementary nonadiabatic (NAD) simulations suggest that, upon photoexcitation to the lowest excited singlet state (S1), MyGzwitter undergoes efficient nonradiative decay to repopulate the electronic ground state (S0). We propose an initial ultrafast ring-twisting mechanism toward an S1/S0 conical intersection, followed by internal conversion to S0 and subsequent vibrational cooling. This study illuminates the workings of the archetype mycosporine, providing photoprotection, in the UV-B range, to organisms such as corals, macroalgae, and cyanobacteria. This study also contributes to our growing understanding of the photoprotection mechanisms of life.",

keywords = "Glycine/chemistry, Bioengineering, Ultraviolet Rays, Cyclohexanols",

author = "Michael Hymas and Sopida Wongwas and Simin Roshan and Whittock, {Abigail L} and Christophe Corre and Reza Omidyan and Stavros, {Vasilios G}",

note = "Acknowledgments S.W. and C.C. wish to thank Matthew P. Harwood (University of Warwick) for his assistance with the plasmid design. M.H. was supported by NERC CENTA2 (Grant No. NE/S007350/1). The Research Council of the University of Isfahan is kindly appreciated for financial support. The use of the computing facility cluster GMPCS of the LUMAT Federation (No. FR LUMAT2764) is acknowledged. V.G.S. thanks the Royal Society for a Royal Society Industry Fellowship. A.L.W. thanks the University of Warwick and Lubrizol for funding a Ph.D. studentship through the Centre for Doctoral Training in Analytical Science. R.O. thanks the support of Royal Society International Exchange (No. IES\R2\232279).",

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AU - Wongwas, Sopida

AU - Roshan, Simin

AU - Whittock, Abigail L

AU - Corre, Christophe

AU - Omidyan, Reza

AU - Stavros, Vasilios G

N1 - Acknowledgments S.W. and C.C. wish to thank Matthew P. Harwood (University of Warwick) for his assistance with the plasmid design. M.H. was supported by NERC CENTA2 (Grant No. NE/S007350/1). The Research Council of the University of Isfahan is kindly appreciated for financial support. The use of the computing facility cluster GMPCS of the LUMAT Federation (No. FR LUMAT2764) is acknowledged. V.G.S. thanks the Royal Society for a Royal Society Industry Fellowship. A.L.W. thanks the University of Warwick and Lubrizol for funding a Ph.D. studentship through the Centre for Doctoral Training in Analytical Science. R.O. thanks the support of Royal Society International Exchange (No. IES\R2\232279).

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N2 - Mycosporine glycine (MyG) was produced by the fermentation of a purposely engineered bacterial strain and isolated from this sustainable source. The ultrafast spectroscopy of MyG was then investigated in its native, zwitterionic form (MyGzwitter), via femtosecond transient electronic absorption spectroscopy. Complementary nonadiabatic (NAD) simulations suggest that, upon photoexcitation to the lowest excited singlet state (S1), MyGzwitter undergoes efficient nonradiative decay to repopulate the electronic ground state (S0). We propose an initial ultrafast ring-twisting mechanism toward an S1/S0 conical intersection, followed by internal conversion to S0 and subsequent vibrational cooling. This study illuminates the workings of the archetype mycosporine, providing photoprotection, in the UV-B range, to organisms such as corals, macroalgae, and cyanobacteria. This study also contributes to our growing understanding of the photoprotection mechanisms of life.

AB - Mycosporine glycine (MyG) was produced by the fermentation of a purposely engineered bacterial strain and isolated from this sustainable source. The ultrafast spectroscopy of MyG was then investigated in its native, zwitterionic form (MyGzwitter), via femtosecond transient electronic absorption spectroscopy. Complementary nonadiabatic (NAD) simulations suggest that, upon photoexcitation to the lowest excited singlet state (S1), MyGzwitter undergoes efficient nonradiative decay to repopulate the electronic ground state (S0). We propose an initial ultrafast ring-twisting mechanism toward an S1/S0 conical intersection, followed by internal conversion to S0 and subsequent vibrational cooling. This study illuminates the workings of the archetype mycosporine, providing photoprotection, in the UV-B range, to organisms such as corals, macroalgae, and cyanobacteria. This study also contributes to our growing understanding of the photoprotection mechanisms of life.

KW - Glycine/chemistry

KW - Bioengineering

KW - Ultraviolet Rays

KW - Cyclohexanols

U2 - 10.1021/acs.jpclett.4c01254

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SN - 1948-7185

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EP - 7429

JO - Journal of Physical Chemistry Letters

JF - Journal of Physical Chemistry Letters

IS - 29

ER -

A Multipronged Bioengineering, Spectroscopic and Theoretical Approach in Unravelling the Excited-State Dynamics of the Archetype Mycosporine Amino Acid

Abstract

Bibliographical note

Keywords

Access to Document

Projects

Exploiting Microbial Photoprotection: Insights from Theoretical approaches

Cite this