ABSTRACT: The interactions between functionalized noble-metal particles in an aqueous solution are central to applications relying on controlled equilibrium association. Herein, we obtain the potentials of mean force (PMF) for pair-interactions between functionalized gold nanoparticles (AuNPs) in physiological saline. These results are based upon >1000 ns experiments in silico of all-atom model systems under equilibrium and non-equilibrium conditions. Four types of functionalization are built by coating each globular Au144 cluster with 60 thiolate groups: GS-AuNP (glutathionate), PhS-AuNP (thiophenol), CyS-AuNP (cysteinyl), and p-APhS-AuNP (para-amino-thiophenol), which are, respectively, negatively charged, hydrophobic (neutral-nonpolar), hydrophilic (neutral-polar), and positively charged at neutral pH. The results confirm the behavior expected of neutral (hydrophilic or hydrophobic) particles in a dilute aqueous environment, however the PMF curves demonstrate that the charged AuNPs interact with one another in a unique way-mediated by H2O molecules and an electrolyte (Na(+), Cl(-))-in a physiological environment. In the case of two GS-AuNPs, the excess, neutralizing Na(+) ions form a mobile (or 'dynamic') cloud of enhanced concentration between the like-charged GS-AuNPs, inducing a moderate attraction (?25 kT) between them. Furthermore, to a lesser degree, for a pair of p-APhS-AuNPs, the excess, neutralizing Cl(-) ions (less mobile than Na(+)) also form a cloud of higher concentration between the two like-charged p-APhS-AuNPs, inducing weaker yet significant attractions (?12 kT). On combining one GS- with one p-APhS-AuNP, the direct, attractive Coulombic force is completely screened out while the solvation effects give rise to moderate repulsion between the two unlike-charged AuNPs.
