Poly(N-Heterocyclic Carbene)-Capped Alloy and Core-Shell AuAg Bimetallic Nanoparticles.

N-Heterocyclic carbene (NHC)-stabilized metal nanoparticles (NPs) have recently attracted considerable attention. While most efforts in the field have been devoted to the development of NHC-tethered monometallic NPs and enhancing their stabilities under various conditions, their bimetallic counterparts are rare in the literature. Herein, we demonstrate that the covalent immobilization of Au and Ag atoms on polymerized NHCs is a powerful method to access bimetallic AuAg NPs. In addition, we show that while AuAg alloy NPs are often obtained via this method, the use of bimetallic polymeric substrates with lower Ag content, relative to Au, results in the formation of core-shell NPs with Au core and Ag shell. Application of these nanomaterials for oxygen reduction reaction is demonstrated with all materials exhibiting electrocatalytic activity. This work demonstrates for the first time that while bimetallic poly(NHC-metal)s are viable substrates to access NHC-stabilized bimetallic NPs, careful adjustment of metal content in the polymeric substrates can finetune the microstructure of the resulting NPs, i.e. alloy vs. core-shell.

Insight into the nature of carbon-metal bonding for N-heterocyclic carbenes in gold/silver complexes and nanoparticles using DFT-correlated Raman spectroscopy: strong evidence for π-backbonding.

N-Heterocyclic carbenes (NHCs) have emerged as promising ligands for stabilizing metallic complexes, nanoclusters, nanoparticles (NPs) and surfaces. The carbon-metal bond between NHCs and metal atoms plays a crucial role in determining the resulting material's stability, reactivity, function, and electronic properties. Using Raman spectroscopy coupled with density functional theory calculations, we investigate the nature of carbon-metal bonding in NHC-silver and NHC-gold complexes as well as their corresponding NPs. While low wavenumbers are inaccessible to standard infrared spectroscopy, Raman detection reveals previously unreported NHC-Au/Ag bond-stretching vibrations between 154-196 cm-1. The computationally efficient r2SCAN-3c method allows an excellent correlation between experimental and predicted Raman spectra which helps calibrate an accurate description of NHC-metal bonding. While π-backbonding should stabilize the NHC-metal bond, conflicting reports for the presence and absence of π-backbonding are seen in the literature. This debate led us to further investigate experimental and theoretical results to ultimately confirm and quantify the presence of π-backbonding in these systems. Experimentally, an observed decrease in the NHC's CN stretching due to the population of the π* orbital is a good indication for the presence of π-backbonding. Using energy decomposition analysis - natural orbitals for chemical valence (EDA-NOCV), our calculations concur and quantify π-backbonding in these NHC-bound complexes and NPs. Surprisingly, we observe that NPs are less stabilized by π-backbonding compared to their respective complexes-a result that partially explains the weaker NHC-NP bond. The protocol described herein will help optimize metal-carbon bonding in NHC-stabilized metal complexes, nanoparticles and surfaces.

Size-tunable fluorescent dendrimersomes via aggregation-induced emission.

Tetraphenylethylene-functionalized amphiphilic Janus dendrimers of up to third generation are synthesized. Their self-assembly has been studied under kinetic and thermodynamic control. By varying the dendrimer generation number and the self-assembly condition, fluorescent dendrimersomes of tunable size (∼60-200 nm) and quantum yield (5.7-17.4%) are obtained in aqueous medium.

Perylene diimide-tagged N-heterocyclic carbene-stabilized gold nanoparticles: How much ligand desorbs from surface in presence of thiols?

N-Heterocyclic carbenes (NHCs) have recently emerged as viable alternatives to commonly used thiols to stabilize a variety of metal surfaces and nanoparticles. In this context, thanks to their biocompatibility and novel optical properties, NHC-stabilized gold nanoparticles (AuNPs) have been extensively studied. It has been shown that such materials exhibit improved stabilities in acidic and basic solutions, high temperatures, electrolyte solutions, cell culture media, and to some extent to nucleophilic thiols. Despite intense efforts, instability of NHC-functionalized AuNPs to thiols has been an ongoing challenge. In order to circumvent this problem, quantification of NHC desorption from nanoparticle surface by the invading thiols would constitute a necessary first step. To do this, we have first developed water-soluble azide decorated NHC-stabilized "clickable" AuNPs. Optically active perylene diimide (PDI)-tagged AuNP hybrids are then obtained by means of Cu-catalyzed alkyne-azide cycloaddition between these AuNPs and an alkyne-decorated PDI derivative. Investigation of photophysical properties of these AuNP/PDI hybrids revealed that the fluorescence of PDI molecules is effectively quenched by AuNPs in aqueous solution. The extent of NHC desorption from AuNP surface in presence of glutathione (4 mM), as a biologically relevant thiol, is then quantified by means of fluorescence emission restoration of PDI molecules upon detachment from AuNP surfaces. Our results demonstrate that while ∼20% of surface NHCs are displaced by glutathione within the first 24 h of their exposure to the thiol, ligand desorption reaches ∼45% after one week. We believe that these findings will provide more insight on true stability of NHC-stabilized materials.

Degradable Spirocyclic Polyacetal-Based Core-Amphiphilic Assemblies for Encapsulation and Release of Hydrophobic Cargo.

Polymeric nanomaterials that degrade in acidic environments have gained considerable attention in nanomedicine for intracellular drug delivery and cancer therapy. Among various acid-degradable linkages, spirocyclic acetals have rarely been used to fabricate such vehicles. In addition to acid sensitivity, they benefit from conformational rigidity that is otherwise not attainable by their non-spirocyclic analogs. Herein, amphiphilic spirocyclic polyacetals are synthesized by Cu-catalyzed alkyne-azide "click" polymerization. Unlike conventional block copolymers, which often form core-shell structures, these polymers self-assemble to form core amphiphilic assemblies capable of encapsulating Nile red as a hydrophobic model drug. In vitro experiments show that while release from these materials can occur at neutral pH with preservation of their integrity, acidic pH accelerates efficient cargo release and leads to the complete degradation of assemblies. Moreover, cellular assays reveal that these materials are fully cytocompatible, interact with the plasma membrane, and can be internalized by cells, rendering them as potential candidates for cancer therapy and/or drug delivery.