Molecular Weight-Independent "Polysoap" Nanostructure Characterized via In Situ Resonant Soft X-ray Scattering

Studying polymer micelle structure and loading dynamics under environmental conditions is critical for nanocarrier applications but challenging due to a lack of in situ nanoprobes. Here, the structure and loading of amphiphilic polyelectrolyte copolymer micelles, formed by 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and n-dodecyl acrylamide (DDAM), were investigated using a multimodal approach centered around in situ resonant soft X-ray scattering (RSoXS). We observe aqueous micelles formed from polymers of wide-ranging molecular weights and aqueous concentrations. Despite no measurable critical micelle concentration (CMC), structural analyses point toward multimeric structures for most molecular weights, with the lowest molecular weight micelles containing mixed coronas and forming loose micelle clusters that enhance hydrocarbon uptake. The sizes of the micelle substructures are independent of both the concentration and molecular weight. Combining these results with a measured molecular weight-invariant surface charge and zeta potential strengthens the link between the nanoparticle size and ionic charge in solution that governs the polysoap micelle structure. Such control would be critical for nanocarrier applications, such as drug delivery and water remediation.