We report on the effect of interpolymer complexes (IPCs) of poly(acrylic acid) (PAA) with poly(ethylene glycol) functionalized Au nanoparticles (PEG-AuNPs) as they assemble at the vapor-liquid interface, using surface sensitive synchrotron X-ray scattering techniques. Depending on the suspension pH, PAA functions both as a weak polyelectrolyte and a hydrogen bond donor, and these two roles affect the interfacial assembly of PEG-AuNPs differently. Above its isoelectric point, we find that PAA leads to the formation of a PEG-AuNPs monolayer at the interface with hexagonal structure. In the presence of high concentration of HCl (i.e., below the isoelectric point), at which PAA forms IPCs with PEG, the hexagonal structure at the interface appears to deteriorate, concurrent with aggregation in the bulk. Thus, while electrolytic behavior of PAA induces interfacial assembly, hydrogen bonding behavior, as PAA becomes neutral, favors the formation of 3D assemblies. For comparison, we also report on the formation of PEG-AuNPs monolayers (in the absence of PAA) with strong electrolytes such as HCl, H2SO4 and NaOH that lead to a high degree of crystallinity.
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This document is the unedited Author’s version of a Submitted Work that was subsequently accepted for publication in Langmuir, copyright © American Chemical Society after peer review. To access the final edited and published work see doi: 10.1021/acs.langmuir.8b03535.