Unlike conventional antimicrobials, the study of bacterial resistance to silver nanoparticles (AgNPs) remains in its infancy and the mechanism(s) through which it evolves are limited and inconclusive. The central question remains whether bacterial resistance is driven by the AgNPs, released Ag(I) ions or a combination of these and other factors. Here, we show a specific resistance in an Escherichia coli K-12 MG1655 strain to subinhibitory concentrations of AgNPs, and not Ag(I) ions, as indicated by a statistically significant greater-than-twofold increase in the minimum inhibitory concentration occurring after eight repeated passages that was maintained after the AgNPs were removed and reintroduced. Whole-population genome sequencing identified a cusS mutation associated with the heritable resistance that possibly increased silver ion efflux. Finally, we rule out the effect of particle aggregation on resistance and suggest that the mechanism of resistance may be enhanced or mediated by flagellum-based motility.

We introduce the concept of domain building blocks (DBBs) as an effective approach to increasing the diversity and complexity of metal–organic frameworks (MOFs). DBBs are defined as distinct structural or compositional regions within a MOF material. Using the DBB approach, we illustrate how an immense number of multivariate MOF materials can be prepared from a small collection of molecular building blocks comprising the distinct domains. The multivariate nature of the MOFs is determined by the sequence of DBBs within the MOF. We then apply this approach to the construction of a rich library of UiO-67 stratified MOF (sMOF) particles consisting of multiple concentric DBBs. We discuss and highlight the negative consequences of linker exchange reactions on the compositional integrity of DBBs in the UiO-67 sMOFs and propose and demonstrate mitigation strategies. We also demonstrate that individual strata can be specifically postsynthetically addressed and manipulated. Finally, we demonstrate the versatility of these synthetic strategies through the preparation of sMOF–nanoparticle composite materials.

Bimetallic nanocatalysts have the potential to surmount current limitations in industrial catalysis if their electronic and optical properties can be effectively controlled. However, improving the performance of bimetallic photocatalysts requires a functional understanding of how the intricacies of their morphology and composition dictate every element of their optical response. In this work, we examine Au and Pt-decorated Au nanorods on a single-particle level to ascertain how Pt influences the plasmon resonance of the bimetallic nanostructure. We correlated scattering, photoluminescence, and pure absorption of individual nanostructures separately to expose the impact of Pt on each component. We found that the scattering and absorption spectra of uncoated Au nanorods followed expected trends in peak intensity and shape and were accurately reproduced by finite difference time domain simulations. In contrast, the scattering and absorption spectra of single Pt-decorated Au nanorods exhibited red-shifted, broad features and large deviations in line shape from particle to particle. Simulations using an idealized geometry confirmed that Pt damps the plasmon resonance of individual Au nanorods and that spectral changes after Pt deposition were a consequence of coupling between Au and Pt in the hybrid nanostructure. Simulations also revealed that the Au nanorod acts as an antenna and enhances absorption in the Pt islands. Furthermore, comparing photoluminescence spectra from Au and Pt-decorated Au nanorods illustrated that emission was significantly reduced in the presence of Pt. The reduction in photoluminescence intensity indicates that Pt lowers the number of hot carriers in the Au nanorod available for radiative recombination through either direct production of hot carriers in Pt following enhanced absorption or charge transfer from Au to Pt. Overall, these results confirm that the Pt island morphology and distribution on the nanorod surface contribute to the optical response of individual hybrid nanostructures and that the damping observed in ensemble measurements originates not only from structural heterogeneity but also because of significant damping in single nanostructures.

We report the use of gold nanoparticle surface chemistry as a tool for site-selective noble metal deposition onto colloidal gold nanoparticle substrates. Specifically, we demonstrate that partial passivation of the gold nanoparticle surface using thiolated ligands can induce a transition from linear palladium island deposition to growth of palladium selectively at plasmonic hotspots on the edges or vertices of the underlying particle substrate. Further, we demonstrate the broader applicability of this approach with respect to substrate morphology (e.g., prismatic and rod-shaped nanoparticles), secondary metal (e.g., palladium, gold, and platinum), and surface ligand (e.g., surfactant molecules and n-alkanethiols). Taken together, these results demonstrate the important role of metal-ligand surface chemistry and ligand packing density on the resulting modes of multimetallic nanoparticle growth, and in particular, the ability to direct that growth to particle regions of impact such as plasmonic hotspots.

Silver monolayer‐protected clusters (MPCs) are an important new class of small metal nanoparticles with discrete sizes and unique properties that are eminently tunable; however, a fundamental understanding of the mechanisms of MPC formation is still lacking. Here, the basic mechanism by which silver‐glutathione MPCs form is established by using real‐time in situ optical measurements and ex situ solution‐phase analyses to track MPC populations in the reaction mixture. These measurements identify that MPCs grow systematically, increasing in size sequentially as they transform from one known species to another, in contrast to existing models. In the new sequential growth model of MPC formation, the relative stability of each species in the series results in thermodynamic preferences for certain species as well as kinetic barriers to transformations between stable sizes. This model is shown to correctly predict the outcome of silver MPC synthetic reactions. Simple analytic expressions and simulations of rate equations are used to further validate the model and study its nature. The sequential growth model provides insights into how reactions may be directed, based on the interplay between relative MPC stabilities and reaction kinetics, providing tools for the synthesis of particular MPCs in high yield.