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Here, we demonstrate that interaction design provides an alternative mechanism for structural selection under fixed confinement. Using functionalized star polymers, whose effective interactions arise from the competition between corona-mediated entropic repulsion and sticky-end-induced enthalpic attraction, we achieve temperature-controlled structural transitions from a disordered liquid to a zigzag structure and ultimately to a double helix at a constant cylindrical diameter. Combining theoretical analysis, umbrella sampling simulations, and free-energy calculations, we reveal that these transitions originate from temperature-dependent effective interactions, which stabilize the zigzag and double-helix structures in distinct temperature regimes. Furthermore, the zigzag-to-double-helix transition proceeds through a finite free-energy barrier associated with the formation of a complete helical turn. These findings establish entropy\u2013enthalpy competition as a mechanism for controlling confined self-assembly and provide a general strategy for programming soft-matter assembly through interaction design.<\/jats:p>","DOI":"10.1063\/5.0355487","type":"journal-article","created":{"date-parts":[[2026,10,22]],"date-time":"2026-10-22T10:50:25Z","timestamp":1792666225000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":0,"title":["Entropy\u2013enthalpy competition controls self-assembly of functionalized star polymers under cylindrical confinement"],"prefix":"10.1063","volume":"165","author":[{"given":"Yuting","family":"Zhang","sequence":"first","affiliation":[{"name":"School of Physics and Electronics, Hunan University , Changsha 410082,","place":["China"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yihang","family":"Sun","sequence":"additional","affiliation":[{"name":"School of Physics and Electronics, Hunan University , Changsha 410082,","place":["China"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3207-1105","authenticated-orcid":false,"given":"Guolong","family":"Zhu","sequence":"additional","affiliation":[{"name":"School of Physics and Electronics, Hunan University , Changsha 410082,","place":["China"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"317","published-online":{"date-parts":[[2026,10,22]]},"reference":[{"key":"2026102206502214500_c1","doi-asserted-by":"publisher","first-page":"54539","DOI":"10.1039\/c6ra10430d","article-title":"Hierarchical hybrid nanostructures: Controlled assembly of polymer-encapsulated gold nanoparticles via a rayleigh-instability-driven transformation under cylindrical confinement","volume":"6","year":"2016","journal-title":"RSC Adv."},{"key":"2026102206502214500_c2","doi-asserted-by":"publisher","first-page":"486","DOI":"10.1021\/mz5002146","article-title":"Assembly of polymer-tethered gold nanoparticles under cylindrical confinement","volume":"3","year":"2014","journal-title":"ACS Macro Lett."},{"key":"2026102206502214500_c3","doi-asserted-by":"publisher","first-page":"613","DOI":"10.1146\/annurev.physchem.55.091602.094319","article-title":"Biomimetic nanoscale reactors and networks","volume":"55","year":"2004","journal-title":"Annu. 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