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Record W4410338629 · doi:10.26434/chemrxiv-2025-241v9

Mechanistic and Kinetic Insights into Nucleobase Oxidation: Detection of Radical Intermediates in Thymine Oxidation Using SH2′ Radical Trapping

2025· preprint· en· W4410338629 on OpenAlexafffund
Peter J. H. Williams, Andrew R. Rickard, Victor Chechik

Bibliographic record

VenueChemRxiv · 2025
Typepreprint
Languageen
FieldBiochemistry, Genetics and Molecular Biology
TopicDNA and Nucleic Acid Chemistry
Canadian institutionsUniversity of Victoria
FundersEngineering and Physical Sciences Research CouncilLaidlaw Foundation
KeywordsNucleobaseThyminePhotochemistryChemistryKinetic energyRadical ionTrappingHydroxyl radicalKineticsRadicalIonDNAOrganic chemistryBiochemistryBiology

Abstract

fetched live from OpenAlex

Short-lived radical intermediates, such as reactive oxygen species (ROS), play a crucial role in oxidative stress, aging, and carcinogenesis. However, understanding of these processes is impeded by limitations of existing radical characterisation techniques. Previous investigations demonstrated that the recently-developed SH2′ radical trapping technique could be used to probe biochemical oxidation mechanisms. In this study, SH2′ radical trapping and mass spectrometry (MS) techniques were used to investigate ●OH-initiated degradation of thymine, relevant to oxidative damage of DNA. Numerous substrate-derived radical intermediates were trapped and characterised, aiding elucidation of, and offering validation to, proposed mechanisms. Isotope exchange and chromatographic separations helped to distinguish between isomeric structures. Observation of thymine dimer radicals and products suggests that this methodology can be useful for studying radical cross-linking of nucleobases. Overall, SH¬2′ radical trapping was demonstrated to be a powerful technique for investigating oxidation pathways in biological systems.

Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.

How this classification was reachedexpand

Full frame machine prediction

Teacher imitation

Not calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.

metaresearch head score (Codex)0.001
metaresearch head score (Gemma)0.000
Version: metacan-v3-hybrid-931329e0061cValidation status: machine_predicted_unvalidated
Candidate categoriesnone
Consensus categoriesnone
DomainCandidate signal: none · Consensus signal: none
Study designCandidate signal: Bench or experimental · Consensus signal: Bench or experimental
GenreCandidate signal: Empirical · Consensus signal: Empirical
Teacher disagreement score0.002
Threshold uncertainty score0.007

Distilled classifier scores by category (both heads)

CategoryCodexGemma
Metaresearch0.0010.000
Meta-epidemiology (narrow)0.0010.000
Meta-epidemiology (broad)0.0000.000
Bibliometrics0.0000.000
Science and technology studies0.0000.000
Scholarly communication0.0000.001
Open science0.0000.000
Research integrity0.0010.001
Insufficient payload (model declined to judge)0.0020.001

Machine scores (provisional)

The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.

Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.

Opus teacher head0.010
GPT teacher head0.246
Teacher spread0.237 · how far apart the two teachers sit on this one work
Validation statusscore_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from it

Classification

machine, unvalidated

Machine predicted; a candidate call from one source (direct Gemma or distilled Codex), not a consensus.

The models applied no category: nothing in the taxonomy fit this work.
Study designBench or experimental
Domainnot available
GenreEmpirical

How this classification was reached, model by model and score by score, is at the end of the page under "How this classification was reached".

Quick stats

Citations0
Published2025
Admission routes2
Has abstractyes

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