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Magic-number gold nanoclusters are atomically precise nanomaterials that have enabled unprecedented insight into structure-property relationships in nanoscience. Thiolates are the most common ligand, binding to the cluster via a staple motif in which only central gold atoms are in the metallic state. The lack of other strongly bound ligands for nanoclusters with different bonding modes has been a significant limitation in the field. Here, we report a previously unknown ligand for gold(0) nanoclusters-N-heterocyclic carbenes (NHCs)-which feature a robust metal-carbon single bond and impart high stability to the corresponding gold cluster. The addition of a single NHC to gold nanoclusters results in significantly improved stability and catalytic properties in the electrocatalytic reduction of CO2. By varying the conditions, nature and number of equivalents of the NHC, predominantly or exclusively monosubstituted NHC-functionalized clusters result. Clusters can also be obtained with up to five NHCs, as a mixture of species.

The Natural Sciences and Engineering Research Council of Canada (NSERC) and the Canada Foundation for Innovation (CFI) are thanked for financial support of this work in terms of operating and equipment grants to CMC and JHH. AJV and MRN thank the Ontario government for OGS fellowships. AJV thanks NSERC for a Vanier Scholarship and also the Walter C. Sumner foundation for additional scholarship support. Benzimidazolium hydrogen carbonate salts have been shown to act as N-heterocyclic carbene precursors which can remove oxide from copper oxide surfaces and functionalize the resulting metallic surfaces in a single step. Both the surfaces and the etching products are fully characterized by spectroscopic methods. Analysis of surfaces before and after NHC treatment by X-ray photoelectron spectroscopy demonstrates the complete removal of copper(II) oxide. Using 13C-labelling, we determine that the products of this transformation include a cyclic urea, a ring-opened formamide and a bis-carbene copper(I) complex. These results illustrate the potential of NHCs to functionalize a much broader class of metals, including those prone to oxide treatment, greatly facilitating the preparation of NHC-based films on metals other than gold. Postprint

Thiolate-protected Ag nanoparticles (NPs) exhibit interesting physical and chemical properties which may lead to various sensing, diagnostic, and therapeutic applications. Further, understanding structure–property relationships of Ag NPs is of great interest to optimize their application. Herein, we used TEM, UV–vis, and a series of synchrotron X-ray spectroscopy techniques to probe the local structure and chemical bonding properties of thiolate-stabilized Ag NPs. Compared with other Ag nanostructures prepared under slightly modified conditions, the Ag NPs were found to have pronounced structural changes, which led to immensely different optical properties. Notably, the NPs were also found to have similar surface structure to recently elucidated Ag nanoclusters prepared with different thiolates. These findings suggest that the NP structure and optical properties can be sensitively tailored by controlling the synthetic conditions. The multi-element, multi-core excitation approach (i.e., Ag K-, Ag L3-, and S K-edges) employed in the X-ray absorption spectroscopy measurements was also demonstrated as an effective tool to uncover the NP structure from both the metal core and the ligand shell perspectives.

Benzimidazolium hydrogen carbonate salts have been shown to act as N-heterocyclic carbene precursors which can remove oxide from copper oxide surfaces and functionalize the resulting metallic surfaces in a single step. Both the surfaces and the etching products are fully characterized by spectroscopic methods. Analysis of surfaces before and after NHC treatment by X-ray photoelectron spectroscopy demonstrates the complete removal of copper(II) oxide. Using 13C-labelling, we determine that the products of this transformation include a cyclic urea, a ring-opened formamide and a bis-carbene copper(I) complex. These results illustrate the potential of NHCs to functionalize a much broader class of metals, including those prone to oxide treatment, greatly facilitating the preparation of NHC-based films on metals other than gold.

The preparation and characterization of all-thiol-protected noble-metal nanoclusters represent significant advancements in the field of nanomaterials. One of the emerging trends in the study of silver nanoclusters in particular, is the generation of sulfide-type silver at their surfaces as a result of surface protection by thiols. Here, X-ray absorption spectroscopy (XAS) was used to identify the structure and composition of 2 nm tiopronin-protected silver nanoclusters arranged in one-dimensional chains. Silver K-edge XAS multipath refinements and wavelet-transformed XAS analysis found that the nanoclusters comprised small metal cores surrounded by thick sulfide-type shells. This further demonstrates that the sulfide-type shell is a prevalent surface structure throughout silver nanoclusters protected by thiols. In addition, the antibacterial activities of the nanoclusters were also examined; they were found to be active against both Gram-positive and Gram-negative bacteria, thereby shedding light on the e...

Silver nanoparticles (AgNPs) have gained much attention in biomedical research because of their antibacterial properties. However, they have also exhibited cytotoxicity toward certain mammalian cells. In order to improve therapeutic efficacy, the incorporation of gold (Au) and Ag into bimetallic Ag–Au NPs is a promising strategy, as it has the potential to increase biocompatibility and maintain antibacterial activity. Toward this end, we prepared a series of bimetallic Ag–Au NPs and studied them with X-ray absorption spectroscopy (XAS) in order to elucidate the correlation of atomic structure to their bioactivities. The addition of Au was found to drastically change the atomic structure of the Ag NPs; namely, the Ag core of the NPs was gradually replaced with Au, while Ag was found mostly on the surface. Next, NP antibacterial activity toward S. aureus and cytotoxicity toward NIH-3T3 fibroblast cells were assessed. It was found that the antibacterial activity of the bimetallic NPs was lower than pure Ag N...

Surface plasmon resonance (SPR)-based biosensing is a powerful tool to study the recognition processes between biomolecules in real-time without need for labels. The use of thiol chemistry is a critical component in surface functionalization of various SPR biosensor surfaces on gold. However, its use is hampered by the high propensity for oxidation of the gold-thiol linkage even in ambient atmosphere, resulting in a short lifetime of SPR sensor chips unless strict precautions are taken. Herein, we describe an approach to overcome this limitation by employing highly robust self-assembled monolayers (SAMs) of alkylated N-heterocyclic carbenes (NHCs) on gold. An alkylated NHC sensor surface was developed and its biosensing capabilities were compared to a commercial thiol-based analogue-a hydrophobic association (HPA) chip-in terms of its ability to act as a reliable platform for biospecific interaction analysis under a wide range of conditions. The NHC-based SPR sensor outperforms related thiol-based sesnsors in several aspects, including lower nonspecific binding capacity, better chemical stability, higher reproducibility, shorter equilibration time, and longer life span. We also demonstrate that the NHC-based sensor can be used for rapid and efficient formation of a hybrid lipid bilayer for use in membrane interaction studies. Overall, this work identifies the great promise in designing NHC-based surfaces as a new technology platform for SPR-based biosensing.

The characterization of nanometer-scale interactions between carbon-containing substrates and alumina surfaces is of paramount importance to industrial and academic catalysis applications, but it is also very challenging. Here, we demonstrate that dynamic nuclear polarization surface-enhanced NMR spectroscopy (DNP SENS) allows the unambiguous description of the coordination geometries and conformations of the substrates at the alumina surface through high-resolution measurements of 13C–27Al distances. We apply this new technique to elucidate the molecular-level geometry of 13C-enriched methionine and natural abundance poly(vinyl alcohol) adsorbed on γ-Al2O3-supported Pd catalysts, and we support these results with element-specific X-ray absorption near-edge measurements. This work clearly demonstrates a surprising bimodal coordination of methionine at the Pd–Al2O3 interface.

With the recent determination of the unexpected surface structure for thiolate-protected gold nanoparticles (−SR–Au–SR– staple-like motif for Au102), it is of great interest to determine whether or not similar systems such as silver exhibit this special surface structure. A detailed study of the structure and composition of a series of organosulfur-stabilized silver nanoparticles (AgNPs) was carried out using X-ray absorption near-edge (XANES) and extended X-ray absorption fine structure (EXAFS) from a multielement (Ag, S) and multicore (Ag K- and L-edge) perspective. It was determined that AgNPs of varied sizes prepared with dodecanethiol did not exhibit either a staple-like surface structure or the traditional metal–thiolate structure (e.g., thiolate on 3-fold hollow site of metal surface), and instead adopted a layer of silver sulfide on the surface of metallic silver cores. The amount of the sulfide formed was found to be dependent on the AgNP size. Moreover, a comparison of the surface structure of t...

Understanding the surface structure of metal nanocrystals with specific facet indices is important due to its impact on controlling nanocrystal shape and functionality. However, this is particularly challenging for halide-adsorbed nanocrystals due to the difficulty in analysing interactions between metals and light halides (for example, chloride). Here we uncover the surface structures of chloride-adsorbed, silver-coated gold nanocrystals with {111}, {110}, {310} and {720} indexed facets by X-ray absorption spectroscopy and density functional theory modelling. The silver–chloride, silver–silver and silver–gold bonding structures are markedly different between the nanocrystal surfaces, and are sensitive to their formation mechanism and facet type. A unique approach of combining the density functional theory and experimental/simulated X-ray spectroscopy further verifies the surface structure models and identifies the previously indistinguishable valence state of silver atoms on the nanocrystal surfaces. Overall, this work elucidates the thus-far unknown chloride–metal nanocrystal surface structures and sheds light onto the halide-induced growth mechanism of anisotropic nanocrystals., Nanocrystal surface structure affects many properties but is tough to determine for halide-adsorbed materials. Here, the authors combine X-ray absorption measurements and computational modelling to elucidate the chloride metal surface structures for silver-coated gold nanocrystals with controlled shapes.

Silver nanoparticles (Ag NPs) have attracted much attention in the past decade because of their unique physicochemical properties and notable antibacterial activities. In particular, thiol-protected Ag NPs have come to the forefront of metal nanoparticle studies, as they have been shown to possess high stability and interesting structure-property relationships. However, a clear correlation between thiol-protecting ligands, the resulting Ag NP surface structure, and their antibacterial properties has yet to be determined. Here, a multielement (Ag and S), multi-edge (Ag K-edge, Ag L3-edge, S K-edge) X-ray absorption spectroscopy (XAS) methodology was used to identify the structure and composition of Ag NPs protected with cysteine. XAS characterization was carried out on similar-sized Ag NPs protected with poly(vinylpyrrolidone) (PVP), in order to provide a valid comparison of the ligand effect on surface structure. The PVP-Ag NPs showed a metallic Ag surface and composition, consistent with metal NPs protected by weak protecting ligands. On the other hand, the Cys-Ag NPs exhibited a distinct surface shell of silver sulfide, which is remarkably different than previously studied Cys-Ag NPs. The minimum inhibitory concentration (MIC) of both types of Ag NPs against Gram-positive (+) and Gram-negative (-) bacteria were tested, including Staphylococcus aureus (+), Escherichia coli (-), and Pseudomonas aeruginosa (-). It was found that the MICs of the Cys-Ag NPs were significantly lower than the PVP-Ag NPs for each bacteria, implicating the influence of the sulfidized surface structure. Overall, this work shows the effect of ligand on the surface structure of Ag NPs, as well as the importance of surface structure in controlling antibacterial activity.

Modifying titanium (Ti) implant surfaces with functional proteins can strengthen the interface between prosthesis and bone. A prototype system was developed using gold nanoparticles (AuNPs) to immobilize proteins onto Ti. An electroless (galvanic displacement) deposition method was first used to form AuNPs of controlled size and coverage on commercial Ti foil (giving Ti-AuNPs). Parameters were then modified to create two groups of discs (n = 26) with different average AuNP diameters. Scanning electron microscopy and X-ray photoelectron spectroscopy were used to characterize the morphology and surface structure of Ti-AuNPs. To study the interaction of Ti-AuNPs with proteins, Ti discs (n = 8) modified with plain AuNPs and discs (n = 8) modified with thiol (HS--R--COOH)-functionalized AuNPs were treated with lysozyme solution. The amount and activity of the lysozyme on the discs were examined with Micro-BCA and enzymatic assays. Lysozyme was immobilized onto the discs, and the assays showed that the discs with thiol-functionalized AuNPs, discs with bare AuNPs, and Ti controls had average lysozyme adsorptions of 23 x 10(4), 2.3 x 10(4), and 5.7 x 10(4) microg/m2, respectively. The activity assays showed that 21.5, 18.4, and 12.5% of the adsorbed lysozyme was active on the discs with thiol-functionalized AuNPs, discs with bare AuNPs, and Ti controls, respectively. This technique holds promise for binding functional biomolecules to surgical implants, hence possibly creating implant surfaces that react to their local environment.

Following the recent breakthrough of total structural determination of a Au-thiolate nanocluster [P. Jadzinsky et al., Science 318, 430 (2007)], extensive interests have been stimulated to unveil (or revisit) the structure-property relationship of various thiolate-Au nanostructures in light of the new finding of -SR-(Au-SR)(x)- "staple" motif. Here, we present experimental x-ray absorption spectroscopy (XAS) and x-ray photoelectron spectroscopy (XPS) results on the local structure and electronic properties of thiolate-protected Au nanocluster encapsulated in bovine serum albumin (Au-BSA) together with theoretical calculation of projected local density of states (l-DOS) of Au(25)(SR)(18) model cluster. Analysis of the Au L(3)-edge extended x-ray absorption fine structure (EXAFS) of Au-BSA suggested that the nanocluster is Au(25) with Au-thiolate "staple" motif. X-ray absorption near-edge structure (XANES) and Au 4f XPS were used to probe the electronic behavior of Au-BSA. The Au d-electron density of Au-BSA was found to decrease by 0.047 e(-) relative to that of the bulk. A self-consistent real space Green's function approach implemented in ab initio FEFF8 program was used to calculate the l-DOS of Au(25)(SR)(18) and other model clusters from a site-specific perspective. The theoretical results are in good agreement with the experimental d-DOS data of Au-BSA and, importantly, systematically illustrate the effect of Au-thiolate "staple" motif on the electronic behavior of Au(25)(SR)(18). The present work sheds light on the structure-property relationship of thiolate-protected Au(25) from both experimental and theoretical perspectives and illustrates the usefulness of XAS/l-DOS method in such studies.