{"doi":"10.1002/chem.202000247","title":"One Way Traffic: Base‐to‐Backbone Hole Transfer in Nucleoside Phosphorodithioate","abstract":"Abstract The directionality of the hole‐transfer processes between DNA backbone and base was investigated by using phosphorodithioate [P(S − )=S] components. ESR spectroscopy in homogeneous frozen aqueous solutions and pulse radiolysis in aqueous solution at ambient temperature confirmed initial formation 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 the μs timescale. In parallel, ESR spectroscopy, pulse radiolysis, and density functional theory (DFT) calculations confirmed P‐2S . formation in an 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 σ 2 ‐σ* 1 ‐bonded dimer anion radical [‐P‐2S 2S‐P‐] − [Δ G (150 K, DFT)=−7.2 kcal mol −1 ]. However, [‐P‐2S 2S‐P‐] − formation was not observed by pulse radiolysis [Δ G ° (298 K, DFT)=−1.4 kcal mol −1 ]. Neither P‐2S . nor [‐P‐2S 2S‐P‐] − oxidized guanine base; only base‐to‐backbone hole transfer occurs in phosphorodithioate.","journal":"Chemistry - A European Journal","year":2020,"id":111621,"datarank":0.0,"base_score":0.0,"endowment":0.0,"self_citation_contribution":0.0,"citation_network_contribution":0.0,"self_endowment_contribution":0.0,"citer_contribution":0.0,"corpus_percentile":null,"corpus_rank":null,"citation_count":4,"citer_count":0,"citers_with_citation_signal":0,"citers_with_endowment":0,"datacite_reuse_total":0,"is_dataset":false,"is_dataset_confidence":0.9504,"is_data_producer":false,"deposit_databanks":null,"is_oa":true,"file_count":0,"downloads":0,"has_version_chain":false,"published_date":"2020-01-01","fair_score":null,"fair_percentile":null,"algorithm_id":"datarank_citation_only_1hop_v6","ranking_scope":"data_only","authors":[{"id":529881,"name":"Samuel Ward","orcid":null,"position":1,"is_corresponding":false},{"id":529882,"name":"Dipra Debnath","orcid":null,"position":2,"is_corresponding":false},{"id":529883,"name":"Taisiya Jacobs","orcid":null,"position":3,"is_corresponding":false},{"id":529088,"name":"Alexander D. Stark","orcid":"0000-0002-6830-2713","position":4,"is_corresponding":false},{"id":430285,"name":"Dariusz Korczyñski","orcid":"0000-0002-4201-3198","position":5,"is_corresponding":false},{"id":529089,"name":"Anil Kumar","orcid":"0000-0002-9979-7798","position":6,"is_corresponding":false},{"id":529090,"name":"Michael D. Sevilla","orcid":"0000-0001-8799-5458","position":7,"is_corresponding":false},{"id":529091,"name":"Sergey A. Denisov","orcid":"0000-0001-7881-1979","position":8,"is_corresponding":false},{"id":529092,"name":"Viacheslav Shcherbakov","orcid":"0000-0003-3628-1804","position":9,"is_corresponding":false},{"id":529093,"name":"Pascal Pernot","orcid":"0000-0001-8586-6222","position":10,"is_corresponding":false},{"id":529094,"name":"Mehran Mostafavi","orcid":"0000-0002-4510-8272","position":11,"is_corresponding":false},{"id":430290,"name":"Roman Dembiński","orcid":"0000-0002-2608-9694","position":12,"is_corresponding":false},{"id":529095,"name":"Amitava Adhikary","orcid":"0000-0001-9024-9579","position":13,"is_corresponding":false},{"id":430283,"name":"Renata Kaczmarek","orcid":"0000-0002-3869-1068","position":0,"is_corresponding":true}],"reference_count":50,"raw_metadata":null,"created_at":"2026-07-18T23:13:05.597252Z","pmid":"32059063","pmcid":null,"fwci":null,"citation_percentile":null,"influential_citations":0,"oa_status":null,"license":null,"views":0,"total_file_size_bytes":0,"version_count":0,"fair_f":null,"fair_a":null,"fair_i":null,"fair_r":null,"fair_zscore":null,"fair_rationale":null,"fair_model":null,"fair_agent_version":null,"fair_fulltext_source":null,"fair_has_llm":null,"fair_computed_at":null,"clinical_trials":[],"software_tools":[],"db_accessions":[],"linked_datasets":[],"topics":[]}