Assembling PNIPAM-Capped Gold Nanoparticles in Aqueous Solutions.

Employing small-angle X-ray scattering (SAXS), we explore the conditions under which assembly of gold nanoparticles (AuNPs) grafted with the thermosensitive polymer poly(N-isopropylacrylamide) (PNIPAM) emerges. We find that short-range order assembly emerges by combining the addition of electrolytes or polyelectrolytes with raising the temperature of the suspensions above the lower-critical solution temperature (LCST) of PNIPAM. Our results show that the longer the PNIPAM chain is, the better organization in the assembled clusters. Interestingly, without added electrolytes, there is no evidence of AuNPs assembly as a function of temperature, although untethered PNIPAM is known to undergo a coil-to-globule transition above its LCST. This study demonstrates another approach to assembling potential thermosensitive nanostructures for devices by leveraging the unique properties of PNIPAM.

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

HYPOTHESIS: Introducing charged terminal groups to polymers that graft nanoparticles enable Coulombic control over their assembly by tuning the pH and salinity of their aqueous suspensions. EXPERIMENTS: Gold nanoparticles (AuNPs) are grafted with poly (ethylene glycol) (PEG) terminated with (charge-neutral), (negatively charged) or groups (positively charged), and characterized with dynamic light scattering, ζ-potential, and thermal gravimetric analysis. Liquid surface X-ray reflectivity (XR) and grazing incidence small-angle X-ray scattering (GISAXS) are used to determine the density profile and in-plane structure of the AuNPs assembly at the aqueous surface. FINDINGS: Assembly of PEG-AuNPs at the liquid/vapor interface is tunable by adjusting pH or salinity for COOH but less for terminals. The distinct assembly behaviors are attributed to the overall charge of PEG-AuNPs as well as PEG conformation. COOH-PEG corona is more compact than those of the other terminal groups, leading to a crystalline structure with a smaller superlattice. 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. [1] The closeness to overall charge neutrality, and hydrogen bonding in play, brought by -PEG, drive -PEG-AuNPs to assembly and crystallinity without additives to the suspensions.