{
  "abstract": "With an interest in sustainable polymers derived from nucleoside building blocks, d-thymidine and carbon disulfide (CS2) were used as synthetic precursors to construct a trans-fused, 6,5-membered bicyclic xanthate, 3',5'-cyclic N3-(3-butenyl)-d-thymidine trans xanthate, for ring-opening polymerization (ROP) to yield stereo- and regiochemically defined homopolymer analogs of nucleic acids bearing thiocarbonate backbones. Screenings for CS2 insertion and succeeding cyclization to form the targeted monomer revealed two additional d-thymidine-derived cyclic moieties, including a xanthate and trithiocarbonate of cis-fused configurations, isolated in low yields. Therefore, ROP experiments using alkoxy-based initiators and organobase catalysts at room temperature and supporting DFT calculations for enthalpies of ring opening were extended to all three potential monomers, with only the trans-fused bicyclic xanthate undergoing ROP. Structural characterization by MALDI-TOF mass spectrometry and NMR spectroscopy of polymers obtained from ROPs of 3',5'-cyclic N3-(3-butenyl)-d-thymidine trans xanthate conducted at or somewhat below ambient temperatures indicated the presence of linear and cyclic species having primarily dimeric 5',5'-trithiocarbonate-co-3',3'-thionocarbonate connectivities from an alternating C-S and C-O cleavage pathway. Other minor trithiocarbonate, xanthate, and thionocarbonate functionalities were proposed to arise from backbiting reactions and/or minor regiorandom cleavages. In contrast, ROPs conducted at reduced temperatures (≤ -20 or -40 °C depending on the organobase) achieved selective C-S cleavage to yield 3',5'-xanthate-connected polymers of N3-(3-butenyl)-d-thymidine with more structural similarity to native DNA. These fundamental advances extend the breadth of nucleoside-derived polymers, emphasizing the influence of sulfur incorporation during monomer synthesis and upon subsequent ROPs, with outcomes being temperature-mediated alternating vs. unidirectional backbone compositional and structural regioregularity.",
  "abstract_shown": true,
  "affiliations": [
    "Departments of Chemistry, Texas A&M University, College Station, Texas77843, United States.",
    "Materials Science & Engineering, Texas A&M University, College Station, Texas77843, United States."
  ],
  "article_type": "research article",
  "arxiv": null,
  "author_total": 6,
  "authors": [
    {
      "affs": [
        0
      ],
      "name": "Autumn M Andras"
    },
    {
      "affs": [
        0
      ],
      "name": "Nehal Fatima"
    },
    {
      "affs": [
        0
      ],
      "name": "Kai-Hua Mick Kuo"
    },
    {
      "affs": [
        0
      ],
      "name": "David K Tran"
    },
    {
      "affs": [
        0
      ],
      "name": "Donald J Darensbourg",
      "orcid": "0000-0001-9285-4895"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Karen L Wooley",
      "orcid": "0000-0003-4086-384X"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/53vkvybkz4rmn.bib",
  "cited_by": 0,
  "doi": "10.1021/jacs.6c15290",
  "fulltext_url": "https://europepmc.org/articles/PMC13693707",
  "id": "53vkvybkz4rmn",
  "issns": [
    "0002-7863",
    "1520-5126"
  ],
  "landing_url": "https://europepmc.org/article/MED/42913605",
  "language": "eng",
  "licence": "CC-BY",
  "licence_label": "CC BY",
  "licence_source": "article",
  "licence_url": "https://creativecommons.org/licenses/by/4.0/",
  "metadata_licence": null,
  "native_subjects": [
    [
      "openalex",
      "2502|biodegradable polymer synthesis and properties"
    ]
  ],
  "openalex": "W7220462126",
  "pdf_url": "https://europepmc.org/articles/PMC13693707?pdf=render",
  "pmcid": "PMC13693707",
  "pmid": "42913605",
  "published": "2026-10-01",
  "publisher": null,
  "ris": "https://research.draconitic.com/paper/53vkvybkz4rmn.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:20:14Z",
      "native_id": "MED:42913605",
      "source": "europepmc",
      "url": "https://europepmc.org/article/MED/42913605"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:2502|biodegradable polymer synthesis and properties",
      "subfield": "materials-polymers"
    }
  ],
  "title": "Investigation of Sulfur-related Influences on the Construction and Ring Opening of a Six-membered Cyclic Xanthate Derived from d-Thymidine and CS2.",
  "title_text": "Investigation of Sulfur-related Influences on the Construction and Ring Opening of a Six-membered Cyclic Xanthate Derived from d-Thymidine and CS2.",
  "type": "peer-reviewed",
  "updated_at": "2026-10-30T12:20:14Z",
  "url": "https://research.draconitic.com/paper/53vkvybkz4rmn",
  "venue": "Journal of the American Chemical Society",
  "versions": []
}