Two-dimensional assembly of nanoparticles grafted with charged-end-group polymers

{\bf Hypothesis:} Introducing charged terminal groups to polymers that graft nanoparticles enables Coulombic control over their assembly by tuning pH and salinity of aqueous suspensions. {\bf Experiments:} Gold nanoparticles (AuNPs) are grafted with poly(ethylene glycol) (PEG) terminated with CH3 (charge neutral), COOH (negatively charged), or NH2 (positively charged) groups. The nanoparticles are characterized using dynamic light scattering, {\zeta}-potential, and thermal gravimetric analysis. Liquid surface X-ray reflectivity (XR) and grazing incidence small-angle X-ray scattering (GISAXS) techniques are employed to determine the density profile and in-plane structure of the AuNP assembly across and on the aqueous surface. {\bf Findings:} The assembly of PEG-AuNPs at the liquid/vapor interface can be tuned by adjusting pH or salinity, particularly for COOH terminals. However, the effect is less pronounced for NH2 terminals. These distinct assembly behaviors are attributed to the overall charge of PEG-AuNPs and the conformation of PEG. The COOH-PEG corona is the most compact, resulting in smaller superlattice constants. The net charge per particle depends not only on the PEG terminal groups but also on the cation sequestration of PEG and the intrinsic negative charge of the AuNP surface. NH2-PEG, due to its closeness to overall charge neutrality and the presence of hydrogen bonding, enables the assembly of NH2-PEG-AuNPs more readily.