Effect of Charged Block Length Mismatch on Double Diblock Polyelectrolyte Complex Micelle Cores

Stevens, Kaden C.; Marras, Alexander E.; Campagna, Trinity R.; Ting, Jeffrey M.; Tirrell, Matthew V.

doi:10.1021/acs.macromol.3c00555

Effect of Charged Block Length Mismatch on Double Diblock Polyelectrolyte Complex Micelle Cores

Journal Article · Thu Jul 06 00:00:00 EDT 2023 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.3c00555· OSTI ID:2470039

^[1]; ^[2]; Campagna, Trinity R. ^[1]; ^[3]; ^[1]

The University of Chicago, IL (United States)
The University of Texas, Austin, TX (United States)
Nanite Inc., Boston, MA (United States)

Polyelectrolyte complex micelles are hydrophilic nanoparticles that self-assemble in aqueous environments due to associative microphase separation between oppositely charged blocky polyelectrolytes. In this work, we employ a suite of physical characterization tools to examine the effect of charged block length mismatch on the equilibrium structure of double diblock polyelectrolyte complex micelles (D-PCMs) by mixing a diverse library of peptide and synthetic charged-neutral block polyelectrolytes with a wide range of charged block lengths (25–200 units) and chemistries. Early work on D-PCMs suggested that this class of micelles can only be formed from blocky polyelectrolytes with identical charged block lengths, a phenomenon referred to as chain length recognition. Here, we use salt annealing to create PCMs at equilibrium, which shows that chain length recognition, a longstanding hurdle to repeatable self-assembly from mismatched polyelectrolytes, can be overcome. Interestingly, D-PCM structure–property relationships display a range of values that vary systematically with the charged block lengths and chemical identity of constituent polyelectrolyte pairings and cannot be described by generalizable scaling laws. We discuss the interdependent growth behavior of the radius, ionic pair aggregation number, and density in the micelle core for three chemically distinct diblock pairings and suggest a potential physical mechanism that leads to this unique behavior. By comparing the results of these D-PCMs to the scaling laws recently developed for single diblock polyelectrolyte complex micelles (S-PCMs: diblock + homopolymer), we observe that D-PCM design schemes reduce the size and aggregation number and restrict their growth to a function of charged block length relative to S-PCMs. Understanding these favorable attributes enables more predictive use of a wider array of charged molecular building blocks to anticipate and control macroscopic properties of micelles spanning countless storage and delivery applications.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); National Science Foundation (NSF); US Department of Commerce

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 2470039

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 14 Vol. 56; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Effect of Charged Block Length Mismatch on Double Diblock Polyelectrolyte Complex Micelle Cores

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