Hydrophilization of Magnetic Nanoparticles with Modified Alternating Copolymers. Part 2: Behavior in Solution

Aqueous solutions of iron oxide nanoparticles (NPs) stabilized by poly(maleic acid-alt-1-octadecene) (PMAcOD) modified with the 5000 Da poly(ethylene glycol) (PEG) or the short ethylene glycol (EG) tails were analyzed by small-angle X-ray scattering (SAXS). Advanced SAXS data analysis methods were employed to systematically characterize the structure and interactions between the NPs. Depending on the type of the grafted tail and the grafting density, all NPs can be separated into three groups. All the samples contain mixtures of individual nanoparticles, their dynamic clusters, and aggregates, and the fractions of these species are different in the different groups. The first group consists of NPs coated with PMAcOD modified with the long PEG tails with the maximal grafting density, and the content of dynamic clusters and aggregates in the samples of this group does not exceed 4%. The samples from the second group with less dense coatings demonstrate a larger amount (5-7%) of the aggregates and dynamic clusters. The samples from the third group, consisting of the NPs protected by EG-modified PMAcOD, contain mostly individual NPs and some amount of dumbbell dimers without noticeable aggregation. Importantly, the solution behavior of the NPs is independent of the iron oxide core size. Our results, therefore, provide means of predicting the stabilization and avoiding aggregation of NPs based on the type of protective shell.