{
  "abstract": "Methylthio substituents are compact models for larger sulfur-linked quinone conjugates, yet their fidelity for calculated one-electron reduction-energy shifts is uncertain. We audited a historical survey of 38 methylthio attachment sites in 26 quinones; four source-energy outputs remain unreconciled, leaving 34 archive-corroborated site shifts across 25 parents. In a historical matched comparison of ten SMe and N-acetylcysteine methyl ester-derived (AcCysOMe) conjugate models, the original median absolute mismatch was 0.175900 eV. An explicitly retrospective, source-corroborated eightsite subset retained a median mismatch of 0.162917 eV, above the prespecified 0.05 eV screening tolerance, with category agreement of 1/3 among decisive SMe cases. Four separately conformercorrected case studies included opposite-sign shifts for benz[a]anthracene-3,4-dione and its 7-methyl analogue. An alternative-functional PBE0-D4 fixed-geometry analysis retained both numerical sign differences, although the 7-methyl analogue's AcCysOMe shift (−0.037065 eV) was near zero under the original category rule. Retrospective spin-population checks indicated predominantly quinonecentered radical-anion states. Thus, sulfur-fragment truncation can materially alter a computed site-",
  "abstract_shown": true,
  "affiliations": [
    "Stanford Online High School, 415 Broadway, Redwood City, California, 94063"
  ],
  "article_type": null,
  "arxiv": null,
  "author_total": 1,
  "authors": [
    {
      "affs": [
        0
      ],
      "name": "Aris Tsai",
      "orcid": "0009-0004-8641-7647"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/aw1tjvv54a2ck.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15010764/v1",
  "fulltext_url": null,
  "id": "aw1tjvv54a2ck",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010764/v1",
  "language": null,
  "licence": "CC-BY",
  "licence_label": "CC BY",
  "licence_source": "journal",
  "licence_url": "https://creativecommons.org/licenses/by/4.0/",
  "metadata_licence": null,
  "native_subjects": [
    [
      "openalex",
      "3107|Advanced Chemical Physics Studies"
    ]
  ],
  "openalex": "W7223112924",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15010764/v1",
  "pmcid": null,
  "pmid": null,
  "published": "2026-10-21",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/aw1tjvv54a2ck.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:24Z",
      "native_id": "10.26434/chemrxiv.15010764",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010764/v1"
    }
  ],
  "subjects": [
    {
      "field": "physics",
      "origin": "openalex:3107|Advanced Chemical Physics Studies",
      "subfield": "amo"
    }
  ],
  "title": "Chemical Representation Dependence of Quinone Reduction Energetics: Site-Specific Limits of Methylthio Surrogates for Cysteine-Derived Conjugates",
  "title_text": "Chemical Representation Dependence of Quinone Reduction Energetics: Site-Specific Limits of Methylthio Surrogates for Cysteine-Derived Conjugates",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:24Z",
  "url": "https://research.draconitic.com/paper/aw1tjvv54a2ck",
  "venue": "ChemRxiv",
  "versions": []
}