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Here we demonstrate a method to control the RROP of 2-methylene-1,3,6-trioxocane (MTC) in terms of molar mass, dispersity, end-group control and kinetics using the reversible addition and fragmentation chain transfer polymerisation (RAFT) methodology. Fine-tuning the ratio between the reactants allows for a better understanding of the interplay of RAFT and RROP. With so optimised reaction conditions, a well-defined PMTC-macroinitiator was obtained and a chain extension with MTC and 2-methylene-1,3-dioxepane (MDO) was applied to form P(CKA-b-CKA) block copolymers. These were then formulated into fully biodegradable polymeric nanoparticles with tuneable degradation time. This work hence pushes the boundaries of RROP towards a whole expanded range of defined homopolymers and fully CKA-based block-copolymers as well as their completely biodegradable nanoparticles. This controlled RROP opens more areas of application for RROP-based polyesters.<\/jats:p>","DOI":"10.1038\/s42004-026-01997-6","type":"journal-article","created":{"date-parts":[[2026,4,9]],"date-time":"2026-04-09T11:07:24Z","timestamp":1775732844000},"update-policy":"https:\/\/doi.org\/10.1007\/springer_crossmark_policy","source":"Crossref","is-referenced-by-count":3,"title":["RAFT enables controlled radical ring-opening polymerisation of cyclic ketene acetals for degradable nanoparticles"],"prefix":"10.1038","volume":"9","author":[{"given":"Fabian","family":"Mehner","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0002-5278-4882","authenticated-orcid":false,"given":"Aniket R.","family":"Bukane","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Daniel J.","family":"Keddie","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Martin","family":"Geisler","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Albena","family":"Lederer","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Brigitte","family":"Voit","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8858-982X","authenticated-orcid":false,"given":"Jens","family":"Gaitzsch","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"297","published-online":{"date-parts":[[2026,4,9]]},"reference":[{"key":"1997_CR1","doi-asserted-by":"crossref","unstructured":"Koltzenburg, S., Maskos, M. & Nuyken, O. 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