The Oxidation of Cobalt Nanoparticles into Kirkendall-Hollowed CoO and Co₃O₄: The Diffusion Mechanisms and Atomic Structural Transformations

We report on the atomic structural changes and diffusion processes during the chemical transformation of ε-Co nanoparticles (NPs) through oxidation in air into hollow CoO NPs and then Co₃O₄ NPs. Through XAS, XRD, TEM, and DFT calculations, the mechanisms of the transformation from ε-Co to CoO to Co₃O₄ are investigated. Our DFT calculations and experimental results suggest that a two-step diffusion process is responsible for the Kirkendall hollowing of ε-Co into CoO NPs. The first step is O in-diffusion by an indirect exchange mechanism through interstitial O and vacancies of type I Co sites of the ε-Co phase. This indirect exchange mechanism of O has a lower energy barrier than a vacancy-mediated diffusion of O through type I sites. When the CoO phase is established, the Co then diffuses outward faster than the O diffuses inward, resulting in a hollow NP. The lattice orientations during the transformation show preferential orderings after the single-crystalline ε-Co NPs are transformed to polycrystalline CoO and Co₃O₄ NPs. Our Co₃O₄ NPs possess a high ratio of {110} surface planes, which are known to have favorable catalytic activity. The Co₃O₄ NPs can be redispersed in an organic solvent by adding surfactants, thus rendering a method to create solution-processable colloidal, monodisperse Co₃O₄ NPs

Electrolyte-Mediated Assembly of Charged Nanoparticles

Solutions at high salt concentrations are used to crystallize or segregate charged colloids, including proteins and polyelectrolytes via a complex mechanism referred to as “salting-out”. Here, we combine small-angle X-ray scattering (SAXS), molecular dynamics (MD) simulations, and liquid-state theory to show that salting-out is a long-range interaction, which is controlled by electrolyte concentration and colloid charge density. As a model system, we analyze Au nanoparticles coated with noncomplementary DNA designed to prevent interparticle assembly via Watson–Crick hybridization. SAXS shows that these highly charged nanoparticles undergo “gas” to face-centered cubic (FCC) to “glass-like” transitions with increasing NaCl or CaCl₂ concentration. MD simulations reveal that the crystallization is concomitant with interparticle interactions changing from purely repulsive to a “long-range potential well” condition. Liquid-state theory explains this attraction as a sum of cohesive and depletion forces that originate from the interelectrolyte ion and electrolyte–ion–nanoparticle positional correlations. Our work provides fundamental insights <i>into the effect of ionic correlations</i> in the salting-out mechanism and suggests new routes for the crystallization of colloids and proteins using concentrated salts

Defining the Structure of a Protein–Spherical Nucleic Acid Conjugate and Its Counterionic Cloud

Protein–spherical nucleic acid conjugates (Pro-SNAs) are an emerging class of bioconjugates that have properties defined by their protein cores and dense shell of oligonucleotides. They have been used as building blocks in DNA-driven crystal engineering strategies and show promise as agents that can cross cell membranes and affect both protein and DNA-mediated processes inside cells. However, ionic environments surrounding proteins can influence their activity and conformational stability, and functionalizing proteins with DNA substantively changes the surrounding ionic environment in a nonuniform manner. Techniques typically used to determine protein structure fail to capture such irregular ionic distributions. Here, we determine the counterion radial distribution profile surrounding Pro-SNAs dispersed in RbCl with 1 nm resolution through <i>in situ</i> anomalous small-angle X-ray scattering (ASAXS) and classical density functional theory (DFT). SAXS analysis also reveals the radial extension of the DNA and the linker used to covalently attach the DNA to the protein surface. At the experimental salt concentration of 50 mM RbCl, Rb⁺ cations compensate ∼90% of the negative charge due to the DNA and linker. Above 75 mM, DFT calculations predict overcompensation of the DNA charge by Rb⁺. This study suggests a method for exploring Pro-SNA structure and function in different environments through predictions of ionic cloud densities as a function of salt concentration, DNA grafting density, and length. Overall, our study demonstrates that solution X-ray scattering combined with DFT can discern counterionic distribution and submolecular features of highly charged, complex nanoparticle constructs such as Pro-SNAs and related nucleic acid conjugate materials