High-Resolution Tracking of Multiple Distributions in Metallic Nanostructures: Advanced Analysis Was Carried Out with...

Multifunctional metallic nanostructures are essential in the architecture of modern technology. However, their characterization remains challenging due to their hybrid nature. In this study, we present a novel photoreduction-based protocol for augmenting the inherent properties of imidazolium-containing ionic polymers (IIP)s through orthogonal functionalization with gold nanoparticles (Au NPs) to produce IIP_Au NPs, as well as novel and advanced characterization via three-dimensional correlation thermal field-flow fractionation (3DCoThFFF). Coordination chemistry is applied to anchor Au³⁺ onto the nitrogen atom of the imidazolium rings, for subsequent photoreduction to Au NPs using UV irradiation. Thermal field-flow fractionation (ThFFF) and the localized surface plasmon resonance (LSPR) of Au NPs are both dependent on size, shape, and composition, thus synergistically co-opted herein to develop mutual correlation for the advanced analysis of 3D spectral data. With 3DCoThFFF, multiple sizes, shapes, compositions, and their respective distributions are synchronously correlated using time-resolved LSPR, as derived from multiple two-dimensional UV-vis spectra per unit ThFFF retention time. As such, higher resolutions and sensitivities are observed relative to those of regular ThFFF and batch UV-vis. In addition, 3DCoThFFF is shown to be highly suitable for monitoring and evaluating the thermostability and dynamics of the metallic nanostructures through the sequential correlation of UV-vis spectra measured under incremental ThFFF temperature gradients. Comparable sizes are measured for IIP and IIP_Au NPs. However, distinct elution profiles and UV-vis absorbances are recorded, thereby reaffirming the versatility of ThFFF as a robust tool for validating the successful functionalization of IIP with Au to produce IIP_Au NPs.