دورية أكاديمية
One Way Traffic: Base‐to‐backbone Hole Transfer in Nucleoside Phosphorodithioates
| العنوان: | One Way Traffic: Base‐to‐backbone Hole Transfer in Nucleoside Phosphorodithioates |
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| المؤلفون: | Kaczmarek, Renata, Ward, Samuel, Debnath, Dipra, Jacobs, Taisiya, Stark, Alexander, Korczyński, Dariusz, Kumar, Anil, Sevilla, Michael, Denisov, Sergey, Shcherbakov, Viacheslav, Pernot, Pascal, Mostafavi, Mehran, Dembinski, Roman, Adhikary, Amitava |
| المساهمون: | Department of Bioorganic Chemistry Centre of Molecular and Macromolecular Studies Polish Academy of Sciences, Polska Akademia Nauk = Polish Academy of Sciences = Académie polonaise des sciences (PAN), Oakland University, Institut de Chimie Physique (ICP), Institut de Chimie - CNRS Chimie (INC-CNRS)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS) |
| المصدر: | ISSN: 0947-6539. |
| بيانات النشر: | HAL CCSD Wiley-VCH Verlag |
| سنة النشر: | 2020 |
| مصطلحات موضوعية: | Phosphorodithioate, backbone-to-base hole transfer, base-to-backbone hole transfer, guanine cation radical, thiyl radicals, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry |
| الوصف: | International audience ; Directionality of the hole transfer processes between DNA-backbone and -base was investigated using phosphorodithioate [P(S−)=S] components. ESR spectroscopy in homogeneous frozen aqueous solutions, pulse radiolysis in aqueous solution at ambient temperature confirmed initialformation of G•+-P(S−)=S. The ionization potential of G-P(S−)=S was calculated to be slightly lower than that of guanine in 5’-dGMP. Subsequent thermally-activated hole transfer from G•+ to P(S−)=S led to dithiyl radical (P-2S•) formation on μs timescale. In parallel, ESR spectroscopy andpulse radiolysis, and density functional theory (DFT) calculations confirmed P-2S• formation in abasic phosphorodithioate model compound. ESR investigations at low temperatures and higher G-P(S−)=S concentrations showed a bimolecular conversion of P-2S• to the σ2-σ*1-bonded dimeranion radical [-P-2S∸2S-P-]− [ΔG (150 K, DFT) = −7.2 kcal/mol]. However, [-P-2S∸2S-P-]−formation was not observed by pulse radiolysis [ΔG° (298 K, DFT) = −1.4 kcal/mol]. Neither P-2S• nor [-P-2S∸2S-P-]− oxidized guanine base; base-to-backbone hole transfer occurs in phosphorodithioate. |
| نوع الوثيقة: | article in journal/newspaper |
| اللغة: | English |
| العلاقة: | hal-02563589; https://hal.science/hal-02563589Test; https://hal.science/hal-02563589/documentTest; https://hal.science/hal-02563589/file/Kaczmarek2021.pdfTest |
| DOI: | 10.1002/chem.202000247 |
| الإتاحة: | https://doi.org/10.1002/chem.202000247Test https://hal.science/hal-02563589Test https://hal.science/hal-02563589/documentTest https://hal.science/hal-02563589/file/Kaczmarek2021.pdfTest |
| حقوق: | info:eu-repo/semantics/OpenAccess |
| رقم الانضمام: | edsbas.422E729 |
| قاعدة البيانات: | BASE |
| DOI: | 10.1002/chem.202000247 |
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