{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,5]],"date-time":"2026-10-05T20:32:01Z","timestamp":1791232321770,"version":"4.1.0"},"reference-count":67,"publisher":"Wiley","issue":"14","license":[{"start":{"date-parts":[[2026,2,5]],"date-time":"2026-02-05T00:00:00Z","timestamp":1770249600000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"},{"start":{"date-parts":[[2026,2,5]],"date-time":"2026-02-05T00:00:00Z","timestamp":1770249600000},"content-version":"tdm","delay-in-days":0,"URL":"http:\/\/doi.wiley.com\/10.1002\/tdm_license_1.1"}],"content-domain":{"domain":["advanced.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Advanced Materials"],"published-print":{"date-parts":[[2026,3]]},"abstract":"<jats:title>ABSTRACT<\/jats:title>\n                  <jats:p>\n                    Designing and fabricating recyclable polymers combining closed\u2010loop depolymerizability with high mechanical performance remains a major challenge in sustainable materials. To reach both high recyclability without compromising the mechanical properties, precise controlling of the crystallization behaviors emerges as a crucial strategy. Here, we demonstrate unexpected crystallization behavior in a depolymerizable polythioester (PTE), PaGMTE, and report the first crystal structure of this kind. Derived from organocatalytic ring\u2010opening polymerization of\n                    <jats:italic>\u03b1<\/jats:italic>\n                    \u2010gem\u2010dimethyl\u2010\n                    <jats:italic>\u03b2<\/jats:italic>\n                    \u2010thiolactone, PaGMTE exhibits exceptionally slow quiescent crystallization, which stands in sharp contrast to its polyester analog polypivalolactone that crystallizes rapidly. However, large\u2010amplitude rapid stretching (strain ~600%, strain rate \u2265 10 s\n                    <jats:sup>\u22121<\/jats:sup>\n                    ), where the Deborah number based on the Rouse time of entanglement strand exceeds 1, triggers its crystallization, accelerating the crystallization rate by &gt; 200,000 fold and achieving ~40% crystallinity within 1 s. This approach yields highly oriented fibers with outstanding mechanical properties (Young's modulus of 0.80 GPa, tensile strength of 120 MPa, breaking strain of 70%), high transparency, and the potential as a waveguide. We unveil PaGMTE's orthorhombic crystal structure (space group\n                    <jats:italic>P<\/jats:italic>\n                    2\n                    <jats:sub>1<\/jats:sub>\n                    2\n                    <jats:sub>1<\/jats:sub>\n                    2\n                    <jats:sub>1<\/jats:sub>\n                    ,\n                    <jats:italic>a<\/jats:italic>\n                    = 1.075 nm,\n                    <jats:italic>b<\/jats:italic>\n                    = 0.622 nm,\n                    <jats:italic>c<\/jats:italic>\n                    = 3.618 nm) with antiparallel\u2010packed homochiral 8\n                    <jats:sub>3<\/jats:sub>\n                    helices. The slow quiescent crystallization shall arise from entropic barriers associated with conformational adjustments toward the helix. Our findings highlight sulfur substitution's profound impact on polymer properties and prove that significantly enhancing the crystallization process holds promise for making PTE a high\u2010value\u2010added recyclable material.\n                  <\/jats:p>","DOI":"10.1002\/adma.202521662","type":"journal-article","created":{"date-parts":[[2026,2,5]],"date-time":"2026-02-05T13:11:00Z","timestamp":1770297060000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":3,"title":["A Recyclable Polythioester With\n                    <i>\u03b1<\/i>\n                    \u2010Gem\u2010Dimethyl Substitution: Instantaneous Crystallization Triggered by Large and Rapid Stretching"],"prefix":"10.1002","volume":"38","author":[{"ORCID":"https:\/\/orcid.org\/0009-0006-9043-1761","authenticated-orcid":false,"given":"Chun\u2010Yan","family":"Lyu","sequence":"first","affiliation":[{"name":"Beijing National Laboratory for Molecular Sciences Center for Soft Matter Science and Engineering Key Laboratory of Polymer Chemistry and Physics of Ministry of Education College of Chemistry and Molecular Engineering Peking University  Beijing People's Republic of China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Wei","family":"Xia","sequence":"additional","affiliation":[{"name":"Beijing National Laboratory for Molecular Sciences Center for Soft Matter Science and Engineering Key Laboratory of Polymer Chemistry and Physics of Ministry of Education College of Chemistry and Molecular Engineering Peking University  Beijing People's Republic of China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Tianyi","family":"Ma","sequence":"additional","affiliation":[{"name":"Beijing National Laboratory for Molecular Sciences CAS Key Laboratory of Engineering Plastics Institute of Chemistry Chinese Academy of Sciences  Beijing People's Republic of China"},{"name":"University of Chinese Academy of Sciences  Beijing People's Republic of China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Chaoqun","family":"Weng","sequence":"additional","affiliation":[{"name":"Beijing National Laboratory for Molecular Sciences Center for Soft Matter Science and Engineering Key Laboratory of Polymer Chemistry and Physics of Ministry of Education College of Chemistry and Molecular Engineering Peking University  Beijing People's Republic of China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ming\u2010He","family":"Sun","sequence":"additional","affiliation":[{"name":"Beijing National Laboratory for Molecular Sciences Center for Soft Matter Science and Engineering Key Laboratory of Polymer Chemistry and Physics of Ministry of Education College of Chemistry and Molecular Engineering Peking University  Beijing People's Republic of China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Bai\u2010Yu","family":"Wu","sequence":"additional","affiliation":[{"name":"Beijing National Laboratory for Molecular Sciences Center for Soft Matter Science and Engineering Key Laboratory of Polymer Chemistry and Physics of Ministry of Education College of Chemistry and Molecular Engineering Peking University  Beijing People's Republic of China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xiaoyan","family":"Tang","sequence":"additional","affiliation":[{"name":"Beijing National Laboratory for Molecular Sciences Center for Soft Matter Science and Engineering Key Laboratory of Polymer Chemistry and Physics of Ministry of Education College of Chemistry and Molecular Engineering Peking University  Beijing People's Republic of China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Guoming","family":"Liu","sequence":"additional","affiliation":[{"name":"Beijing National Laboratory for Molecular Sciences CAS Key Laboratory of Engineering Plastics Institute of Chemistry Chinese Academy of Sciences  Beijing People's Republic of China"},{"name":"University of Chinese Academy of Sciences  Beijing People's Republic of China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2180-3091","authenticated-orcid":false,"given":"Hua","family":"Lu","sequence":"additional","affiliation":[{"name":"Beijing National Laboratory for Molecular Sciences Center for Soft Matter Science and Engineering Key Laboratory of Polymer Chemistry and Physics of Ministry of Education College of Chemistry and Molecular Engineering Peking University  Beijing People's Republic of China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Er\u2010Qiang","family":"Chen","sequence":"additional","affiliation":[{"name":"Beijing National Laboratory for Molecular Sciences Center for Soft Matter Science and Engineering Key Laboratory of Polymer Chemistry and Physics of Ministry of Education College of Chemistry and Molecular Engineering Peking University  Beijing People's Republic of 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