{"doi":"10.1021/acs.macromol.1c00635","title":"Strong Variation of Micelle–Unimer Coexistence as a Function of Core Chain Mobility","abstract":"Polymeric micelles coexist in solution with unassembled chains (unimers). We have investigated the influence of glass transition temperature (Tg) (i.e., chain mobility) of the micelle core-forming blocks on micelle–unimer coexistence. We synthesized a series of seven PEG-b-P(nBA-ran-tBA) amphiphilic block copolymers [PEG = poly(ethylene glycol), nBA = n-butyl acrylate, and tBA = tert-butyl acrylate] with similar molecular weights (12 kg/mol). Varying the nBA/tBA molar ratio enabled the broad modulation of core block Tg with no significant change in core hydrophobicity or micelle size. NMR diffusometry revealed increasing unimer populations from 0 to 54% of total polymer concentration upon decreasing core block Tg from 25 to −46 °C. Additionally, unimer population at fixed polymer composition (and thus core Tg) increased with temperature. This study demonstrates the strong influence of core-forming block mobility on polymer self-assembly, providing information toward designing drug delivery systems and suggesting the need for a new dynamical theory.","journal":"Macromolecules","year":2021,"id":194913,"datarank":0.0,"base_score":0.0,"endowment":0.0,"self_citation_contribution":0.0,"citation_network_contribution":0.0,"self_endowment_contribution":0.0,"citer_contribution":0.0,"corpus_percentile":null,"corpus_rank":null,"citation_count":9,"citer_count":0,"citers_with_citation_signal":0,"citers_with_endowment":0,"datacite_reuse_total":0,"is_dataset":false,"is_dataset_confidence":0.9567,"is_data_producer":false,"deposit_databanks":null,"is_oa":true,"file_count":0,"downloads":0,"has_version_chain":false,"published_date":"2021-01-01","fair_score":null,"fair_percentile":null,"algorithm_id":"datarank_citation_only_1hop_v6","ranking_scope":"data_only","authors":[{"id":765486,"name":"Xiuli Li","orcid":"0000-0001-6203-4546","position":1,"is_corresponding":false},{"id":382985,"name":"Jeffrey C. Foster","orcid":"0000-0002-9097-8680","position":2,"is_corresponding":false},{"id":766129,"name":"Veera Venkata Shravan Uppala","orcid":null,"position":3,"is_corresponding":false},{"id":766130,"name":"Candace E. Wall","orcid":null,"position":4,"is_corresponding":false},{"id":765487,"name":"Alan R. Esker","orcid":"0000-0003-1440-5933","position":5,"is_corresponding":false},{"id":329686,"name":"Louis A. Madsen","orcid":"0000-0003-4588-5183","position":6,"is_corresponding":false},{"id":304541,"name":"John B. Matson","orcid":"0000-0001-7984-5396","position":7,"is_corresponding":false},{"id":333501,"name":"Ryan J. Carrazzone","orcid":"0000-0003-4629-086X","position":0,"is_corresponding":true}],"reference_count":56,"raw_metadata":null,"created_at":"2026-07-18T23:50:03.719152Z","pmid":"36910585","pmcid":null,"fwci":null,"citation_percentile":null,"influential_citations":0,"oa_status":null,"license":null,"views":0,"total_file_size_bytes":0,"version_count":0,"fair_f":null,"fair_a":null,"fair_i":null,"fair_r":null,"fair_zscore":null,"fair_rationale":null,"fair_model":null,"fair_agent_version":null,"fair_fulltext_source":null,"fair_has_llm":null,"fair_computed_at":null,"clinical_trials":[],"software_tools":[],"db_accessions":[],"linked_datasets":[],"topics":[]}