Spatiotemporal Formation and Growth Kinetics of Polyelectrolyte Complex Micelles with Millisecond Resolution

Wu, Hao; Ting, Jeffrey M.; Yu, Boyuan; Jackson, Nicholas E.; Meng, Siqi; de Pablo, Juan J.; Tirrell, Matthew V.

doi:10.1021/acsmacrolett.0c00543

Spatiotemporal Formation and Growth Kinetics of Polyelectrolyte Complex Micelles with Millisecond Resolution

Journal Article · Sun Nov 01 23:00:00 EST 2020 · ACS Macro Letters

DOI:https://doi.org/10.1021/acsmacrolett.0c00543· OSTI ID:1840607

^[1]; ^[2]; ^[1]; ^[3]; ^[1]; ^[3]; Tirrell, Matthew V. ^[3]

Univ. of Chicago, IL (United States)
Univ. of Chicago, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States); 3 M Company, Saint Paul, MN (United States)
Univ. of Chicago, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States)

We have directly observed the in situ self-assembly kinetics of polyelectrolyte complex (PEC) micelles by synchrotron time-resolved small-angle X-ray scattering, equipped with a stopped-flow device that provides millisecond temporal resolution. A synthesized neutral-charged diblock polycation and homopolyanion that we have previously investigated as a model charge-matched, core-shell micelle system were selected for this work. The initial micellization of the oppositely charged polyelectrolytes was completed within the dead time of mixing of 100 ms, followed by micelle growth and equilibration up to several seconds. By combining the structural evolution of the radius of gyration (R-g) with complementary molecular dynamics simulations, we show how the self-assemblies evolve incrementally in size over time through a two-step kinetic process: first, oppositely charged polyelectrolyte chains pair to form nascent aggregates that immediately assemble into spherical micelles, and second, these PEC micelles grow into larger micellar entities. Furthermore, this work has determined one possible kinetic pathway for the initial formation of PEC micelles, which provides useful physical insights for increasing fundamental understanding self-assembly dynamics, driven by polyelectrolyte complexation that occurs on ultrafast time scales.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: National Institute of Standards and Technology (NIST); Center for Hierarchical Materials Design (CHiMaD); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1840607

Journal Information:: ACS Macro Letters, Journal Name: ACS Macro Letters Journal Issue: 11 Vol. 9; ISSN 2161-1653

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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