{
  "abstract": "Sequence-defined abiotic polymers could extend the structural organization underlying biological function to new backbones and operating environments, but this requires rules connecting monomer structure to folding. Predictive control over folding is essential for translating molecular information into defined structure and, ultimately, function. Here, we show that side-chain structure reprograms the conformational landscape of isotactic oligourethanes. A systematic series of isotactic tetramers bearing structurally diverse substituents was examined by circular dichroism, two-dimensional nuclear magnetic resonance, and Fourier-transform infrared spectroscopy, supported by molecular dynamics simulations. Side chains that combine effective backbone shielding with steric compatibility favor persistent 2.614-helical states in competitive polar media, whereas less compatible substituents populate broader, dynamically interconverting helical ensembles. Notably, side-chain substitution can reverse the chiroptical bias of an invariant SSSS-configured backbone, reflecting a change in the preferred helical handedness. Experiments and simulations further reveal that helix persistence is associated with the interplay of reduced solvent exposure of the polar backbone, steric compatibility within the folded geometry, and recurrent intramolecular hydrogen bonding. The results establish side-chain selection as a means of directing oligourethane folding without changing backbone stereochemistry and identify complementary molecular criteria for developing scaffold-specific folding rules.",
  "abstract_shown": true,
  "affiliations": [
    "Institute of Advanced Materials, Faculty of Chemistry, Wroclaw University of Science and Technology, Wybrzeże Wyspiańskiego 27, Wrocław, Poland, 50-370",
    "Center for Advanced Technologies, Adam Mickiewicz University, Uniwersytetu Poznańskiego 10, Poznań, Poland, 61-614",
    "NanoBioMedical Center, Adam Mickiewicz University, Wszechnicy Piastowskiej 3, Poznań, Poland, 61-614"
  ],
  "article_type": null,
  "arxiv": null,
  "author_total": 8,
  "authors": [
    {
      "affs": [
        0,
        1
      ],
      "name": "Maksymilian Szatko",
      "orcid": "0009-0007-2688-8166"
    },
    {
      "affs": [
        1
      ],
      "name": "Joanna Kaźmierczak",
      "orcid": "0000-0003-0868-5844"
    },
    {
      "affs": [
        1
      ],
      "name": "Eduardo Castellanos",
      "orcid": "0000-0002-4429-0295"
    },
    {
      "affs": [
        2
      ],
      "name": "Rafał Konefał",
      "orcid": "0000-0003-4568-4891"
    },
    {
      "affs": [
        1
      ],
      "name": "Andreia Fortuna",
      "orcid": "0000-0001-9692-3245"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Kasper Witruk",
      "orcid": "0009-0006-5345-1245"
    },
    {
      "affs": [
        0
      ],
      "name": "Tadeusz Andruniów",
      "orcid": "0000-0002-2215-5287"
    },
    {
      "affs": [
        1
      ],
      "name": "Róża Szweda",
      "orcid": "0000-0003-2152-7656"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/29wkgnaktn354.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15010970/v1",
  "fulltext_url": null,
  "id": "29wkgnaktn354",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010970/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",
      "1605|Supramolecular Chemistry and Complexes"
    ]
  ],
  "openalex": "W7223401329",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15010970/v1",
  "pmcid": null,
  "pmid": null,
  "published": "2026-10-23",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/29wkgnaktn354.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:26Z",
      "native_id": "10.26434/chemrxiv.15010970",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010970/v1"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1605|Supramolecular Chemistry and Complexes",
      "subfield": "organic"
    }
  ],
  "title": "Side-Chain Structure Reprograms Helical Folding in Isotactic Oligourethanes",
  "title_text": "Side-Chain Structure Reprograms Helical Folding in Isotactic Oligourethanes",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:26Z",
  "url": "https://research.draconitic.com/paper/29wkgnaktn354",
  "venue": "ChemRxiv",
  "versions": []
}