Heavy-Atom-Substituted Nucleobases in Photodynamic Applications: Substitution of Sulfur with Selenium in 6-Thioguanine Induces a Remarkable Increase in the Rate of Triplet Decay in 6-Selenoguanine

Journal of the American Chemical Society
Kieran M FarrellCarlos E Crespo-Hernández

Abstract

Sulfur substitution of carbonyl oxygen atoms of DNA/RNA nucleobases promotes ultrafast intersystem crossing and near-unity triplet yields that are being used for photodynamic therapy and structural-biology applications. Replacement of sulfur with selenium or tellurium should significantly red-shift the absorption spectra of the nucleobases without sacrificing the high triplet yields. Consequently, selenium/tellurium-substituted nucleobases are thought to facilitate treatment of deeper tissue carcinomas relative to the sulfur-substituted analogues, but their photodynamics are yet unexplored. In this contribution, the photochemical relaxation mechanism of 6-selenoguanine is elucidated and compared to that of the 6-thioguanine prodrug. Selenium substitution leads to a remarkable enhancement of the intersystem crossing lifetime both to and from the triplet manifold, resulting in an efficiently populated, yet short-lived triplet state. Surprisingly, the rate of triplet decay in 6-selenoguanine increases by 835-fold compared to that in 6-thioguanine. This appears to be an extreme manifestation of the classical heavy-atom effect in organic photochemistry, which challenges conventional wisdom.

References

Jan 15, 1973·Biochemical Pharmacology·A F RossR E Parks
Apr 16, 1998·Journal of Photochemistry and Photobiology. B, Biology·A FavreP Laugâa
Apr 15, 2004·Chemical Reviews·Carlos E Crespo-HernándezBern Kohler
Mar 29, 2007·Journal of the American Chemical Society·Jozef SalonZhen Huang
Nov 18, 2008·Annual Review of Physical Chemistry·Chris T MiddletonBern Kohler
Jul 10, 2010·Chemical Communications : Chem Comm·Christian Reichardt, Carlos E Crespo-Hernández
Mar 10, 2011·The Journal of Physical Chemistry. B·Christian ReichardtCarlos E Crespo-Hernández
May 26, 2011·British Journal of Cancer·S W PridgeonA V Boddy
Oct 20, 2011·The Journal of Dermatological Treatment·Emilios GemenetzidisGiuseppe Trigiante
Nov 3, 2011·Photochemical & Photobiological Sciences : Official Journal of the European Photochemistry Association and the European Society for Photobiology·Olivier ReelfsAntony R Young
Jul 19, 2013·Organic Letters·Jozef SalonZhen Huang
Nov 30, 2013·Physical Chemistry Chemical Physics : PCCP·Ignacio FaustinoModesto Orozco
Dec 17, 2014·Journal of the American Chemical Society·Marvin PollumCarlos E Crespo-Hernández
Oct 7, 2015·Physical Chemistry Chemical Physics : PCCP·M PollumC E Crespo-Hernández
Aug 20, 2016·Physical Chemistry Chemical Physics : PCCP·Ashley A BecksteadBern Kohler
Mar 8, 2017·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Brennan AshwoodCarlos E Crespo-Hernández
Mar 14, 2018·ChemMedChem·Marvin PollumCarlos E Crespo-Hernández
Jul 7, 2018·Photochemistry and Photobiology·Brennan AshwoodCarlos E Crespo-Hernández

❮ Previous
Next ❯

Citations

May 23, 2020·Physical Chemistry Chemical Physics : PCCP·Qin PengGanglong Cui
Jul 16, 2020·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Kelechi O UleanyaCaroline E H Dessent
Feb 15, 2020·Chemical Science·Gabrielle C Hoover, Dwight S Seferos
Feb 16, 2021·Journal of the American Chemical Society·Luis A Ortiz-RodríguezCarlos E Crespo-Hernández
Mar 3, 2021·Physical Chemistry Chemical Physics : PCCP·Danillo ValverdeAntonio Carlos Borin
May 25, 2021·Physical Chemistry Chemical Physics : PCCP·Yun-Hua ZhuGanglong Cui
May 1, 2019·Journal of Chemical Theory and Computation·Sebastian MaiLeticia González
Oct 3, 2019·Journal of the American Chemical Society·Van-Nghia NguyenJuyoung Yoon
Dec 16, 2021·Physical Chemistry Chemical Physics : PCCP·Peipei JinJinquan Chen

❮ Previous
Next ❯

Related Concepts

Trending Feeds

COVID-19

Coronaviruses encompass a large family of viruses that cause the common cold as well as more serious diseases, such as the ongoing outbreak of coronavirus disease 2019 (COVID-19; formally known as 2019-nCoV). Coronaviruses can spread from animals to humans; symptoms include fever, cough, shortness of breath, and breathing difficulties; in more severe cases, infection can lead to death. This feed covers recent research on COVID-19.

Blastomycosis

Blastomycosis fungal infections spread through inhaling Blastomyces dermatitidis spores. Discover the latest research on blastomycosis fungal infections here.

Nuclear Pore Complex in ALS/FTD

Alterations in nucleocytoplasmic transport, controlled by the nuclear pore complex, may be involved in the pathomechanism underlying multiple neurodegenerative diseases including Amyotrophic Lateral Sclerosis and Frontotemporal Dementia. Here is the latest research on the nuclear pore complex in ALS and FTD.

Applications of Molecular Barcoding

The concept of molecular barcoding is that each original DNA or RNA molecule is attached to a unique sequence barcode. Sequence reads having different barcodes represent different original molecules, while sequence reads having the same barcode are results of PCR duplication from one original molecule. Discover the latest research on molecular barcoding here.

Chronic Fatigue Syndrome

Chronic fatigue syndrome is a disease characterized by unexplained disabling fatigue; the pathology of which is incompletely understood. Discover the latest research on chronic fatigue syndrome here.

Evolution of Pluripotency

Pluripotency refers to the ability of a cell to develop into three primary germ cell layers of the embryo. This feed focuses on the mechanisms that underlie the evolution of pluripotency. Here is the latest research.

Position Effect Variegation

Position Effect Variagation occurs when a gene is inactivated due to its positioning near heterochromatic regions within a chromosome. Discover the latest research on Position Effect Variagation here.

STING Receptor Agonists

Stimulator of IFN genes (STING) are a group of transmembrane proteins that are involved in the induction of type I interferon that is important in the innate immune response. The stimulation of STING has been an active area of research in the treatment of cancer and infectious diseases. Here is the latest research on STING receptor agonists.

Microbicide

Microbicides are products that can be applied to vaginal or rectal mucosal surfaces with the goal of preventing, or at least significantly reducing, the transmission of sexually transmitted infections. Here is the latest research on microbicides.

Related Papers

Journal of the American Chemical Society
Marvin PollumCarlos E Crespo-Hernández
Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry
Leandro Henrique Zucolotto CoccaLeonardo De Boni
© 2022 Meta ULC. All rights reserved