Cyclic Polyethylene Glycol as Nanoparticle Surface Ligand

Cyclic polymers behave different than linear polymers due to the lack of end groups and smaller coil dimensions. Herein, we demonstrate that cyclic polyethylene glycol (PEG) can be used as an alternative of classical linear PEG ligands for gold nanoparticle (AuNP) stabilization. We observed that the brush height of cyclic PEG on AuNPs of diameter 4.4 and 13.2 nm increases identically as that of linear brushes with (Nσ^1/2)^0.7 (N, number of monomers in a chain and σ, grafting density) and that cyclic brushes are more stretched than their linear analogues when compared to their unperturbed dimensions. Such structural effect and the reduced footprint diameter in cyclic brushes with the entire chain in a concentrated polymer brush regime explains the distinct response of NPs to ionic strength and temperature, respectively, compared to linear analogues. These experiments are an important step in understanding the effect of polymer brush topology on colloidal properties.