Photophysics of tzAdenine and tzGuanine fluorescent nucleobases embedded into DNA and RNA

Roiney Beal; Danillo Valverde; Paulo F.B. Gonçalvez; Antonio Carlos Borin

doi:10.1002/jcc.27194

Photophysics of ^tzAdenine and ^tzGuanine fluorescent nucleobases embedded into DNA and RNA

Roiney Beal, Danillo Valverde, Paulo F.B. Gonçalvez, Antonio Carlos Borin

Namur Institute of Structured Matter

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

Abstract

UV–VIS photoinduced events of ^tzA and ^tzG embedded into DNA and RNA are described by combining the Extended Multi-State Second-Order Perturbation Theory (XMS-CASPT2) and electrostatic embedding molecular mechanics methods (QM/MM). Our results point out that the S₁¹(ππ* L_a) state is the bright state in both environments. After the photoexcitation to the S₁¹(ππ* L_a) state, the electronic population evolves barrierless towards its minimum, from where the excess of energy can be dissipated by fluorescence. As the minimum energy crossing point structure between the ground and first bright states lies in a high-energy region, the direct internal conversion to the ground state is an unviable mechanism. Other spectroscopic properties (for instance, absorption and Stokes shifts) and comparisons with photochemical properties of canonical nucleobases are also provided.

Original language	English
Pages (from-to)	2246-2255
Number of pages	10
Journal	Journal of Computational Chemistry
Volume	44
Issue number	29
DOIs	https://doi.org/10.1002/jcc.27194
Publication status	Published - 5 Nov 2023

Keywords

DNA and RNA
modified nucleobases
molecular dynamics simulations
photophysics
QM/MM calculations

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10.1002/jcc.27194

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title = "Photophysics of tzAdenine and tzGuanine fluorescent nucleobases embedded into DNA and RNA",

abstract = "UV–VIS photoinduced events of tzA and tzG embedded into DNA and RNA are described by combining the Extended Multi-State Second-Order Perturbation Theory (XMS-CASPT2) and electrostatic embedding molecular mechanics methods (QM/MM). Our results point out that the S11(ππ* La) state is the bright state in both environments. After the photoexcitation to the S11(ππ* La) state, the electronic population evolves barrierless towards its minimum, from where the excess of energy can be dissipated by fluorescence. As the minimum energy crossing point structure between the ground and first bright states lies in a high-energy region, the direct internal conversion to the ground state is an unviable mechanism. Other spectroscopic properties (for instance, absorption and Stokes shifts) and comparisons with photochemical properties of canonical nucleobases are also provided.",

keywords = "DNA and RNA, modified nucleobases, molecular dynamics simulations, photophysics, QM/MM calculations",

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T1 - Photophysics of tzAdenine and tzGuanine fluorescent nucleobases embedded into DNA and RNA

AU - Beal, Roiney

AU - Valverde, Danillo

AU - Gonçalvez, Paulo F.B.

AU - Borin, Antonio Carlos

PY - 2023/11/5

Y1 - 2023/11/5

N2 - UV–VIS photoinduced events of tzA and tzG embedded into DNA and RNA are described by combining the Extended Multi-State Second-Order Perturbation Theory (XMS-CASPT2) and electrostatic embedding molecular mechanics methods (QM/MM). Our results point out that the S11(ππ* La) state is the bright state in both environments. After the photoexcitation to the S11(ππ* La) state, the electronic population evolves barrierless towards its minimum, from where the excess of energy can be dissipated by fluorescence. As the minimum energy crossing point structure between the ground and first bright states lies in a high-energy region, the direct internal conversion to the ground state is an unviable mechanism. Other spectroscopic properties (for instance, absorption and Stokes shifts) and comparisons with photochemical properties of canonical nucleobases are also provided.

AB - UV–VIS photoinduced events of tzA and tzG embedded into DNA and RNA are described by combining the Extended Multi-State Second-Order Perturbation Theory (XMS-CASPT2) and electrostatic embedding molecular mechanics methods (QM/MM). Our results point out that the S11(ππ* La) state is the bright state in both environments. After the photoexcitation to the S11(ππ* La) state, the electronic population evolves barrierless towards its minimum, from where the excess of energy can be dissipated by fluorescence. As the minimum energy crossing point structure between the ground and first bright states lies in a high-energy region, the direct internal conversion to the ground state is an unviable mechanism. Other spectroscopic properties (for instance, absorption and Stokes shifts) and comparisons with photochemical properties of canonical nucleobases are also provided.

KW - DNA and RNA

KW - modified nucleobases

KW - molecular dynamics simulations

KW - photophysics

KW - QM/MM calculations

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ER -

Photophysics of ^tzAdenine and ^tzGuanine fluorescent nucleobases embedded into DNA and RNA

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Keywords

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