Amphiphilic Bottlebrush Block Copolymers: Analysis of Aqueous Self-Assembly by Small-Angle Neutron Scattering and Surface Tension Measurements

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dc.citation.firstpage465en_US
dc.citation.journalTitleMacromoleculesen_US
dc.citation.lastpage476en_US
dc.citation.volumeNumber52en_US
dc.contributor.authorAlaboalirat, Mohammeden_US
dc.contributor.authorQi, Luqingen_US
dc.contributor.authorArrington, Kyle J.en_US
dc.contributor.authorQian, Shuoen_US
dc.contributor.authorKeum, Jong K.en_US
dc.contributor.authorMei, Haoen_US
dc.contributor.authorLittrell, Kenneth C.en_US
dc.contributor.authorSumpter, Bobby G.en_US
dc.contributor.authorCarrillo, Jan-Michael Y.en_US
dc.contributor.authorVerduzco, Rafaelen_US
dc.contributor.authorMatson, John B.en_US
dc.date.accessioned2019-08-16T16:07:50Zen_US
dc.date.available2019-08-16T16:07:50Zen_US
dc.date.issued2019en_US
dc.description.abstractA systematic series of 16 amphiphilic bottlebrush block copolymers (BCPs) containing polystyrene and poly(N-acryloylmorpholine) (PACMO) side chains were prepared by a combination of atom-transfer radical polymerization (ATRP), photoiniferter polymerization, and ring-opening metathesis polymerization (ROMP). The grafting-through method used to prepare the polymers enabled a high degree of control over backbone and side-chain molar masses for each block. Surface tension measurements on the self-assembled amphiphilic bottlebrush BCPs in water revealed an ultralow critical micelle concentration (cmc), 1–2 orders of magnitude lower than linear BCP analogues on a molar basis, even for micelles with >90% PACMO content. Combined with coarse-grained molecular dynamics simulations, fitting of small-angle neutron scattering traces (SANS) allowed us to evaluate solution conformations for individual bottlebrush BCPs and micellar nanostructures for self-assembled macromolecules. Bottlebrush BCPs showed an increase in anisotropy with increasing PACMO content in toluene-d8, which is a good solvent for both blocks, reflecting an extended conformation for the PACMO block. SANS traces of bottlebrush BCPs assembled into micelles in D2O, a selective solvent for PACMO, were fitted to a core–shell–shell model, suggesting the presence of a partially hydrated inner shell. Results showed an average micelle diameter of 40 nm with combined shell diameters ranging from 16 to 18 nm. A general trend of increased stability of micelles (i.e., resistance to precipitation) was observed with increases in PACMO content. These results demonstrate the stability of bottlebrush polymer micelles, which self-assemble to form spherical micelles with ultralow (<70 nmol/L) cmc’s across a broad range of compositions.en_US
dc.identifier.citationAlaboalirat, Mohammed, Qi, Luqing, Arrington, Kyle J., et al.. "Amphiphilic Bottlebrush Block Copolymers: Analysis of Aqueous Self-Assembly by Small-Angle Neutron Scattering and Surface Tension Measurements." <i>Macromolecules,</i> 52, (2019) American Chemical Society: 465-476. https://doi.org/10.1021/acs.macromol.8b02366.en_US
dc.identifier.doihttps://doi.org/10.1021/acs.macromol.8b02366en_US
dc.identifier.urihttps://hdl.handle.net/1911/106262en_US
dc.language.isoengen_US
dc.publisherAmerican Chemical Societyen_US
dc.rightsThis is an author's peer-reviewed final manuscript, as accepted by the publisher. The published article is copyrighted by the American Chemical Society.en_US
dc.titleAmphiphilic Bottlebrush Block Copolymers: Analysis of Aqueous Self-Assembly by Small-Angle Neutron Scattering and Surface Tension Measurementsen_US
dc.typeJournal articleen_US
dc.type.dcmiTexten_US
dc.type.publicationpost-printen_US
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