Rapid photothermal curing of PDMS on paper

A central challenge in the colloidal synthesis of metallic nanoparticles is the intrinsic heterogeneity of the resulting populations, which often leads to concerns regarding the reproducibility of structure-function relationships. While the impact of polydispersity on some properties, such as the localized surface plasmon resonance, can be extrapolated easily from our understanding of these phenomena, the influence on the underlying electronic structure - specifically the density of states and electronic environment at the Fermi level - remains poorly understood. In this work, we quantify the impact of synthetic variability on the electronic properties of dodecanethiolate-protected palladium nanoparticles (PdNPs) by comparing ostensibly identical syntheses performed by five different researchers. Using a combination of transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and multi-modal magnetic resonance techniques (NMR and EPR), we characterize the morphological, compositional, and electronic variance across batches. We apply a dual statistical framework comprising Welch's t-tests to detect measurable differences and Two One-Sided Tests (TOST) to evaluate chemical equivalence. Our results reveal that while t-tests frequently distinguish between batches based on morphological parameters (diameter, aspect ratio, and circularity), these variations largely fall within the bounds of chemical equivalence. Crucially, we find that the electronic structure, quantified by Pauli paramagnetic susceptibility and g-values, remains statistically equivalent across batches despite measurable synthetic variance. These findings suggest that current synthetic protocols for PdNPs provide sufficient reproducibility for properties driven by electronic structure, and outline a procedure for evaluating the degree and importance of synthetic variability with respect to other phenomena and synthetic targets.