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| Content Provider | World Health Organization (WHO)-Global Index Medicus |
|---|---|
| Author | Ashwood, Brennan Pollum, Marvin Crespo-hernández, Carlos E. |
| Description | Author Affiliation: Ashwood B ( Department of Chemistry and Center for Chemical Dynamics, Case Western Reserve University, Cleveland, Ohio, 44106, USA.); Pollum M ( Department of Chemistry and Center for Chemical Dynamics, Case Western Reserve University, Cleveland, Ohio, 44106, USA.); Crespo-Hernández CE ( Department of Chemistry and Center for Chemical Dynamics, Case Western Reserve University, Cleveland, Ohio, 44106, USA. cxc302@case.edu.) |
| Abstract | In 2014, two unnatural nucleosides, d5SICS and dNaM, were shown to selectively base pair and replicate with high fidelity in a modified strain of E. coli, thus effectively expanding its genetic alphabet from four to six letters. More recently, a significant reduction in cell proliferation was reported in cells cultured with d5SICS, and putatively with dNaM, upon exposure to brief periods of near-visible radiation. The photosensitizing properties of the lowest-energy excited triplet state of both d5SICS and dNaM were implicated in their cytotoxicity. Importantly, however, the excited-state mechanisms by which near-visible excitation populates the triplet states of d5SICS and dNaM are currently unknown. In this study, steady-state and time-resolved spectroscopies are combined with quantum-chemical calculations in order to reveal the excited-state relaxation mechanisms leading to efficient population of the triplet states in these unnatural nucleosides in solution. It is shown that excitation of d5SICS or dNaM with near-visible light leads overwhelmingly to ultrafast population of their triplet states on the femtosecond time scale. The results presented in this work lend strong support to the proposal that photoexcitation of these unnatural nucleosides can accelerate oxidatively generated damage to DNA and other biomolecules within the cellular environment. |
| ISSN | 09476539 |
| e-ISSN | 15213765 |
| Journal | Chemistry - A European Journal |
| Issue Number | 46 |
| Volume Number | 22 |
| Language | English |
| Publisher | Wiley-VCH;ChemPubSoc Europe |
| Publisher Date | 2016-11-07 |
| Publisher Place | Germany |
| Access Restriction | Open |
| Subject Keyword | Chemistry |
| Content Type | Text |
| Resource Type | Article |
| Subject | Organic Chemistry Catalysis |
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