Eyes on the Prize: Tracking Electron Transfer in G-Rich Duplex and Quadruplex DNA Using Enantiopure Ruthenium Polypyridyl Infrared Redox Probes

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22310%2F25%3A43932257" target="_blank" >RIV/60461373:22310/25:43932257 - isvavai.cz</a>

Výsledek na webu

<a href="https://pubs.acs.org/doi/10.1021/jacs.5c05736" target="_blank" >https://pubs.acs.org/doi/10.1021/jacs.5c05736</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/jacs.5c05736" target="_blank" >10.1021/jacs.5c05736</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Eyes on the Prize: Tracking Electron Transfer in G-Rich Duplex and Quadruplex DNA Using Enantiopure Ruthenium Polypyridyl Infrared Redox Probes

Popis výsledku v původním jazyce

Photosensitized damage by the mechanism of direct 1e- transfer from a nucleobase to the metal complex is a complementary approach to type I and type II methods of photodynamic therapy. In this ultrafast spectroscopic study we report the ability of a nitrile infrared redox probe to report on the photo-oxidation of guanine-rich DNA, comprising persistent runs of guanine, by the dppz-10-CN containing complex [Ru(TAP)2(dppz-10-CN)]2+ (1 2+), dppz-10-CN = 10-cyano-dipyrido[3,2-a:2 &apos;,3 &apos;-c]phenazine and TAP = 1,4,5,8-tetraazaphenanthrene. Our study reveals the ability of the enantiomers of 1 2+ to photo-oxidize guanine in double-stranded and quadruplex DNA. Transient visible absorption reveals a high yield of the formation of the photoreduced metal complex due to photo-oxidation of guanine in the quadruplex-bound 1 2+ systems, and that this is greater for the Lambda enantiomer. Spectro-electrochemical and computational studies indicate the role of the dppz-10-CN as the preferred site of reduction, while time-resolved electronic absorption (TrA) spectroscopy highlights the impact of the enantiomers on the yield of photo-oxidation in the DNA systems. Notably, time-resolved infrared (TRIR) spectroscopy allows comprehensive tracking of the photo-oxidation dynamics by monitoring four key components, namely: (1) the transient band of the Ru/TAP-based lowest 3MLCT excited state, (2) bleach bands associated with DNA bases in close proximity to the excited state &quot;site effect&quot;, (3) the guanine radical cation band at ca. 1700 cm-1 and (4) the amplification of the red-shifted nitrile stretching vibration of the transient dppz-reduced complex. Together, these results allow detailed profiling of photoinduced electron transfer in DNA-bound ruthenium(II) polypyridyl complex systems and highlight the potential of such redox probes. Overall, this study presents an important insight regarding the nature of charge transfer in a Hoogsteen-bound guanine quadruplex compared to Watson-Crick GC base pairings.

Název v anglickém jazyce

Eyes on the Prize: Tracking Electron Transfer in G-Rich Duplex and Quadruplex DNA Using Enantiopure Ruthenium Polypyridyl Infrared Redox Probes

Popis výsledku anglicky

Photosensitized damage by the mechanism of direct 1e- transfer from a nucleobase to the metal complex is a complementary approach to type I and type II methods of photodynamic therapy. In this ultrafast spectroscopic study we report the ability of a nitrile infrared redox probe to report on the photo-oxidation of guanine-rich DNA, comprising persistent runs of guanine, by the dppz-10-CN containing complex [Ru(TAP)2(dppz-10-CN)]2+ (1 2+), dppz-10-CN = 10-cyano-dipyrido[3,2-a:2 &apos;,3 &apos;-c]phenazine and TAP = 1,4,5,8-tetraazaphenanthrene. Our study reveals the ability of the enantiomers of 1 2+ to photo-oxidize guanine in double-stranded and quadruplex DNA. Transient visible absorption reveals a high yield of the formation of the photoreduced metal complex due to photo-oxidation of guanine in the quadruplex-bound 1 2+ systems, and that this is greater for the Lambda enantiomer. Spectro-electrochemical and computational studies indicate the role of the dppz-10-CN as the preferred site of reduction, while time-resolved electronic absorption (TrA) spectroscopy highlights the impact of the enantiomers on the yield of photo-oxidation in the DNA systems. Notably, time-resolved infrared (TRIR) spectroscopy allows comprehensive tracking of the photo-oxidation dynamics by monitoring four key components, namely: (1) the transient band of the Ru/TAP-based lowest 3MLCT excited state, (2) bleach bands associated with DNA bases in close proximity to the excited state &quot;site effect&quot;, (3) the guanine radical cation band at ca. 1700 cm-1 and (4) the amplification of the red-shifted nitrile stretching vibration of the transient dppz-reduced complex. Together, these results allow detailed profiling of photoinduced electron transfer in DNA-bound ruthenium(II) polypyridyl complex systems and highlight the potential of such redox probes. Overall, this study presents an important insight regarding the nature of charge transfer in a Hoogsteen-bound guanine quadruplex compared to Watson-Crick GC base pairings.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10405 - Electrochemistry (dry cells, batteries, fuel cells, corrosion metals, electrolysis)

Projekt

<a href="/cs/project/GN23-05760O" target="_blank" >GN23-05760O: Redoxní a fotochemické vlastnosti polypyridylových biosenzorů</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2025

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Journal of the American Chemical Society

ISSN

0002-7863

e-ISSN

1520-5126

Svazek periodika

147

Číslo periodika v rámci svazku

33

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

14

Strana od-do

29801-29814

Kód UT WoS článku

001547416300001

EID výsledku v databázi Scopus

2-s2.0-105013739384