Surface-Engineered Nanomaterials in Water: Understanding Critical Dynamics of Soft Organic Coatings and Relative Aggregation Density

Inorganic-organic nanocomposites, typically as an inorganic core with surface organic coating(s), have received interest as potential platform materials for sensor, catalyst, sorbent, and environmental applications, among others. Here, we describe the critical role of organic surface coatings with regard to the colloidal stability of engineered manganese oxide nanoparticles (MnxOy NPs). Specifically, we prepared libraries of monodisperse MnxOy NPs with a serial selection of surface coatings (stearic acid (SA), oleic acid (OA), poly(maleic anhydride-alt-1-octadecene) (PMAO), linear polyethyleneimine (LPEI), and multibranched polyethyleneimine (BPEI)), which were chosen based on comparable structure(s) and functional group(s). We systematically evaluated the role of surface organic coatings via critical coagulation concentrations (CCCs), which were compared with theoretical calculations (Schulze-Hardy rule). Through a newly developed light scattering protocol, we observed that the effective density of nanoclusters can exceed NPs' primary (bulk) density depending on the open space(s) within organic coatings. Interestingly, PMAO-coated NPs were more stable at the point of zero charge (PZC) than at neutral pH (pH 7), despite the loss of effective surface charge potential. CCC was 334 mM in NaCl and 1.5 mM in CaCl2 at pH 7, compared to CCC values of 807 mM in NaCl and 210 mM in CaCl2 at PZC. This increase in stability is due to polymer (re)configuration (at PZC), which was further confirmed with a quartz crystal microbalance-based technique to evaluate surface-based polymer dynamics. Taken together, this work quantifies the role of organic coating dynamics, including structure, grafting density, and configuration on the colloidal stability of organiccoated NPs.