Nanoparticle Probes for Quantifying Supramolecular Determinants of Biosurface Affinity

Interactions between macromolecular systems and biosurfaces are complicated by the complexity of these multivalent interactions and challenges in quantifying affinities. In this study, a library of gold nanoparticles (AuNPs) with different functional head groups as multivalent probes to quantify biosurface affinity, using hair as a model targeted substrate, is used. The adhesion of the AuNPs is quantified by inductively coupled plasma mass spectrometry. Using this method it is demonstrated that multiple supramolecular forces affect affinity. As expected, electrostatic interaction is a strong driving force for adhesion of the nanoparticle tags onto hair in aqueous solution, evidenced by a much higher level of gold adsorption for cationic AuNPs compared to anionic or neutral AuNPs. Functionalized cationic AuNPs are synthesized with systematically varied terminal groups and are screened for deposition onto hair. AuNP adhesion onto hair in water generally decreases as a function of increasing hydrophobicity; however, electron‐rich aromatic rings provide significantly enhanced attachment. Although the intact, healthy hair cuticle is considered negatively charged and hydrophobic, the findings indicate that hydrophobic interactions are not as critical to deposition of AuNPs onto hair as the electrostatic component from the presence and accessibility of the cationic moieties, which are the greatest drivers for deposition onto hair.