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Rapid Commun."],"published-print":{"date-parts":[[2025,9]]},"abstract":"<jats:title>ABSTRACT<\/jats:title><jats:p>Well\u2010defined acid\u2010degradable amphiphilic block copolymers (ABPs) and their nanoassemblies labeled with acid\u2010labile groups have been developed for smart drug delivery, exhibiting controlled\/enhanced release of therapeutics in tumoral tissues and endo\/lysosomes. In general, controlled polymerization techniques, particularly atom transfer radical polymerization (ATRP) and ring opening polymerization (ROP) have been utilized to synthesize poly(ethylene glycol)\u2010based ABPs labeled with acetals and ketals. Despite comprehensive studies on their acid\u2010catalyzed hydrolysis rate with substituents attached to oxygen atoms, the stability of the groups under ATRP and tin\u2010catalyzed ROP conditions have been rarely studied. Herein, we report our investigation with benzaldehyde acetal (BzAc) as a typical acetal and cyclohexyl ketal (CyHK) as a typical ketal to understand the relationship of sensitivity to acid and stability to controlled polymerizations for acetals and ketals. Our results, along with model studies, show that BzAc is stable under ATRP, but partially stable under tin\u2010catalyzed ROP conditions, while CyHK turns to be unstable under both ATRP and ROP conditions. Our work could provide important design principles for the synthesis of well\u2010defined acid\u2010degradable ABPs with respect to acid\u2010catalyzed hydrolysis rates, thus eventually, the release rate of encapsulated drug molecules from their nanoassemblies in an acidic environment.<\/jats:p>","DOI":"10.1002\/marc.202500399","type":"journal-article","created":{"date-parts":[[2025,7,4]],"date-time":"2025-07-04T15:09:21Z","timestamp":1751641761000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["Stability of Acetals\/Ketals Under Controlled Radical and Ring Opening Polymerization"],"prefix":"10.1002","volume":"46","author":[{"given":"Brandon","family":"Andrade\u2010Gagnon","sequence":"first","affiliation":[{"name":"Department of Chemistry and Biochemistry Concordia University  Montreal Quebec Canada"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Sofia Nieves","family":"Casillas\u2010Popova","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Biochemistry Concordia University  Montreal Quebec Canada"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4220-308X","authenticated-orcid":false,"given":"Jung Kwon","family":"Oh","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Biochemistry Concordia University  Montreal Quebec Canada"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2025,7,4]]},"reference":[{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1038\/nmat3776"},{"key":"e_1_2_8_2_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jconrel.2007.03.023"},{"key":"e_1_2_8_2_3","doi-asserted-by":"publisher","DOI":"10.1039\/C0SM00534G"},{"key":"e_1_2_8_2_4","doi-asserted-by":"publisher","DOI":"10.1039\/c2cc32408c"},{"key":"e_1_2_8_2_5","doi-asserted-by":"publisher","DOI":"10.1039\/C8PY01808A"},{"key":"e_1_2_8_2_6","doi-asserted-by":"publisher","DOI":"10.1021\/acs.molpharmaceut.7b00284"},{"key":"e_1_2_8_2_7","doi-asserted-by":"publisher","DOI":"10.1002\/adma.200803276"},{"key":"e_1_2_8_2_8","doi-asserted-by":"publisher","DOI":"10.1039\/c3cs35469e"},{"key":"e_1_2_8_2_9","doi-asserted-by":"publisher","DOI":"10.1021\/ma201924h"},{"key":"e_1_2_8_2_10","doi-asserted-by":"publisher","DOI":"10.1021\/ma300094t"},{"key":"e_1_2_8_2_11","doi-asserted-by":"publisher","DOI":"10.1038\/nchem.2343"},{"key":"e_1_2_8_2_12","doi-asserted-by":"publisher","DOI":"10.1021\/acsnano.8b06104"},{"key":"e_1_2_8_2_13","doi-asserted-by":"publisher","DOI":"10.1039\/D0PY01408G"},{"key":"e_1_2_8_2_14","doi-asserted-by":"publisher","DOI":"10.1016\/j.progpolymsci.2023.101765"},{"key":"e_1_2_8_2_15","doi-asserted-by":"publisher","DOI":"10.1002\/wnan.1742"},{"key":"e_1_2_8_2_16","doi-asserted-by":"publisher","DOI":"10.1039\/D4PY00660G"},{"key":"e_1_2_8_3_1","doi-asserted-by":"publisher","DOI":"10.1039\/c2cc36589h"},{"key":"e_1_2_8_3_2","doi-asserted-by":"publisher","DOI":"10.1039\/C6PY01872F"},{"key":"e_1_2_8_3_3","doi-asserted-by":"publisher","DOI":"10.1002\/asia.201600452"},{"key":"e_1_2_8_3_4","doi-asserted-by":"publisher","DOI":"10.1016\/j.polymer.2021.124024"},{"key":"e_1_2_8_3_5","doi-asserted-by":"publisher","DOI":"10.1002\/marc.201800917"},{"key":"e_1_2_8_3_6","doi-asserted-by":"publisher","DOI":"10.1016\/j.ejps.2016.12.011"},{"key":"e_1_2_8_3_7","doi-asserted-by":"publisher","DOI":"10.1016\/j.jconrel.2020.09.044"},{"key":"e_1_2_8_4_1","first-page":"4373","volume":"49","author":"Tannock I. 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