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.

Ultrathin Atomic Layer Deposited Al2O3 Overcoat Stabilizes Al2O3-Pt/Ni-Foam Hydrogenation Catalysts.

Galvanic exchange seeds the growth of Pt nanostructures on the Ni foam monolith. Subsequent atomic layer deposition of ultrathin Al2O3 followed by annealing under air affords supported Pt catalysts with ultralow loading (0.020 ppm). In addition to the expected enhancement of the stability of the Pt particles on the surface, the ∼2 nm Al2O3 overcoat appears to also play a crucial role in the overall structural integrity of the NiOx nanoplates that grow on the Ni foam surface as a result of the preparative route. The resulting material is physically robust toward repeated handling and showcases retention of catalytic activity over 10 standard catalyst recycling trials, standing in marked contrast to the uncoated samples. Catalyst activity was tested via the hydrogenation of various functionalized styrenes at low temperatures and low hydrogen pressure in ethanol as a solvent, with a TOF as high as 9.5 × 106 h-1 for unfunctionalized styrene. Notably, the catalysts show excellent tolerance toward F, Cl, and Br substituents and no hydrogenation of the aromatic ring.

Semiconductive and Biocompatible Nanofibrils from the Self-Assembly of Amyloid π-Conjugated Peptides.

Owing to their capacity to self-assemble into organized nanostructures, amyloid polypeptides can serve as scaffolds for the design of biocompatible semiconductive materials. Herein, symmetric and asymmetric amyloid π-conjugated peptides were prepared through condensation of perylene diimide (PDI) with a natural amyloidogenic sequence derived from the islet amyloid polypeptide. These PDI-bioconjugates assembled into long and linear nanofilaments in aqueous solution, which were characterized by a cross-ß-sheet quaternary organization. Current-voltage curves exhibited a clear signature of semiconductors, whereas the cellular assays revealed cytocompatibility and potential application in fluorescence microscopy. Although the incorporation of a single amyloid peptide appeared sufficient to drive the self-assembly into organized fibrils, the incorporation of two peptide sequences at the PDI's imide positions significantly enhanced the conductivity of nanofibril-based films. Overall, this study exposes a novel strategy based on amyloidogenic peptide to guide the self-assembly of π-conjugated systems into robust, biocompatible, and optoelectronic nanofilaments.

Monomeric and Polymeric Mesoionic N-Heterocyclic Carbene-Tethered Silver Nanoparticles: Synthesis, Stability, and Catalytic Activity.

In recent years, N-heterocyclic carbenes (NHCs) have garnered significant attention as promising alternatives to thiols to stabilize metallic nanoparticles and planar surfaces. While most studies thus far have focused on NHC-functionalized gold nanoparticles (AuNPs), as an ideal platform to investigate the role of NHCs in stabilizing such nanoparticles, their ability to protect more unstable coinage metal nanoparticles, such as silver nanoparticles (AgNPs), has been largely overlooked. This is despite the fact that AgNPs possess a much more sensitive optical response that, upon their enhanced stability, can broaden their scope of application in various fields, including nanomedicine and catalysis. In this study, the synthesis and use of monomeric and polymeric mesoionic NHC-Ag(I) complexes as precursors to mono- and multidentate NHC-tethered AgNPs are reported. The polymeric analog was obtained by first synthesizing a polymer, containing 1,2,3-triazole repeat units, employing the copper-catalyzed alkyne-azide cycloaddition click polymerization of monomers containing diazide- and dialkyne functional groups. Subsequent quaternization of the triazole moieties and Ag insertion yielded the target NHC-Ag-containing polymer. Using this polymer as well as its monomeric analog as substrates, AgNPs with either catenated networks of NHCs or monomeric NHCs were fabricated by their reduction using borane-tert-butylamine complex. Our stability studies demonstrate that while monomeric NHCs impart some degree of stability to AgNPs, particularly at elevated temperatures in aqueous as well as organic medium, their polymeric analogs further enhance their stability in acidic environment (pH = 2) and against glutathione (3 mM), as an example of a biologically relevant thiol, in aqueous media. To highlight the application of these NHC-functionalized AgNPs in catalysis, we explore the aqueous phase reduction of methyl orange and 4-nitrophenol.

Cold region data accessibility portal for Québec (CRDAP-QC): An integrated, multi-variable and multi-scale data repository for studying cold-region hydrological processes in Québec.

We present an integrated data portal and retrieval system for various variable related to hydrology and cryosphere of Québec, named Cold Region Data Accessibility Portal for Québec (CRDAP-QC). The raw data with which this integrated platform is built are pulled from various publicly available data sources. The platform integrates data variables related to climate (maximum, minimum and mean temperature along with total precipitation), snow accumulation (snow cover and depth) as well as Freeze-Thaw characteristics. The platform enables downloading, visualizing, and comparing these data across various temporal (monthly, seasonal and annual) and spatial scales (from 25 × 25 km2 grids, to sub-basin and basin, to the whole province). The platform also provides a Printable Document File with summary of the data, an additional set of information on elevation, land-use, and land-cover as well as the location of climate and hydrometric stations within the chosen area. The portal is available in both English and French.

A locally relevant framework for assessing the risk of sea level rise under changing temperature conditions: Application in New Caledonia, Pacific Ocean.

Sea level rise is a key feature in a warmer world and its impact can be seen globally. Assessing climate change-induced sea level rise, therefore, is urgently needed particularly in small island nations, where the threats of sea level rise are immediate, but the level of preparedness is low. Here, we propose a stochastic simulator to link changes in Mean Annual Temperature (MAT) to Mean Annual Sea Level (MASEL) at the local scale. This is through what-if scenarios that are developed based on the association between local temperature and sea level. The model can provide a basis for a bottom-up impact assessment by addressing limitations of applying large-scale projections in small islands and facilitating the accessibility of the impact assessment to stakeholders. For this purpose, we decompose the MAT and MASEL signals into their linear trend and autocorrelation components as well as independent and identically distributed residual terms. We further explore the association between trend and residual terms of MAT and MASEL. If such dependencies exist, scenarios of sea level can be synthesized based on the trend and residual terms of temperature. We use linear regression to link trends of MAT and MASEL, and copulas to formulate dependencies between residuals. This allows stochastic sampling of MASEL conditioned to trend and random variability in MAT. This framework is used for retrospective and prospective simulations of MASEL in Nouméa, the capital city of New Caledonia, the Pacific. We set up six different model configurations for developing the stochastic sampler, each including various parametric options. By selecting the best setup from each configuration, we provide a multi-model stochastic projection of MASEL, assuming the persistence in current long-term trend in MAT and MASEL. We demonstrate how such simulations can be used for a risk-based impact assessments and discuss sources of uncertainty in future projections.

Supramolecular Nanostructures Based on Perylene Diimide Bioconjugates: From Self-Assembly to Applications.

Self-assembling π-conjugated systems constitute efficient building blocks for the construction of supramolecular structures with tailored functional properties. In this context, perylene diimide (PDI) has attracted attention owing to its chemical robustness, thermal and photo-stability, and outstanding optical and electronic properties. Recently, the conjugation of PDI derivatives to biological molecules, including oligonucleotides and peptides, has opened new avenues for the design of nanoassemblies with unique structures and functionalities. In the present review, we offer a comprehensive summary of supramolecular bio-assemblies based on PDI. After briefly presenting the physicochemical, structural, and optical properties of PDI derivatives, we discuss the synthesis, self-assembly, and applications of PDI bioconjugates.

Compound changes in temperature and snow depth lead to asymmetric and nonlinear responses in landscape freeze-thaw.

Cycles of freeze-thaw (FT) are among the key landscape processes in cold regions. Under current global warming, understanding the alterations in FT characteristics is of a great importance for advising land management strategies in northern latitudes. Using a generic statistical approach, we address the impacts of compound changes in air temperature and snow depth on FT responses across Québec, a Canadian province ~ 2.5 times larger than France. Our findings show significant and complex responses of landscape FT to compound changes in temperature and snow depth. We note a vivid spatial divide between northern and southern regions and point to the asymmetric and nonlinear nature of the FT response. In general, the response of FT characteristics is amplified under compound warming compared to cooling conditions. In addition, FT responses include nonlinearity, meaning that compounding changes in temperature and snow depth have more severe impacts compared to the cumulative response of each individually. These asymmetric and nonlinear responses have important implications for the future environment and socio-economic management in a thawing Québec and highlight the complexity of landscape responses to climatic changes in cold regions.

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.

Anthropogenic drought dominates groundwater depletion in Iran.

Using publicly-available average monthly groundwater level data in 478 sub-basins and 30 basins in Iran, we quantify country-wide groundwater depletion in Iran. Natural and anthropogenic elements affecting the dynamics of groundwater storage are taken into account and quantified during the period of 2002-2015. We estimate that the total groundwater depletion in Iran to be ~ 74 km3 during this period with highly localized and variable rates of change at basin and sub-basin scales. The impact of depletion in Iran's groundwater reserves is already manifested by extreme overdrafts in ~ 77% of Iran's land area, a growing soil salinity across the entire country, and increasing frequency and extent of land subsidence in Iran's planes. While meteorological/hydrological droughts act as triggers and intensify the rate of depletion in country-wide groundwater storage, basin-scale groundwater depletions in Iran are mainly caused by extensive human water withdrawals. We warn that continuation of unsustainable groundwater management in Iran can lead to potentially irreversible impacts on land and environment, threatening country's water, food, socio-economic security.

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.

Bottom-up device fabrication via the seeded growth of polymer-based nanowires.

The bottom-up assembly of nanoelectronic devices from molecular building blocks is a target of widespread interest. Herein we demonstrate an in situ seeded growth approach to produce a nanowire-based electrical device. This exploits the chemisorption of block terpolymer-based seed fibres with a thiophene-functionalised corona onto metal electrodes as the initial step. We then use these surface-bound seeds to initiate the growth of well-defined one-dimensional fibre-like micelles via the seeded growth method known as "Living crystallisation-driven self-assembly'' and demonstrate that they are capable of spanning an interelectrode gap. Finally, a chemical oxidation step was used to transform the nanofibres into nanowires to generate a two-terminal device. This seeded growth approach of growing well-defined circuit elements provides a useful new design tool for bottom-up device fabrication.

Nitrone-Modified Gold Nanoparticles: Synthesis, Characterization, and Their Potential as 18F-Labeled Positron Emission Tomography Probes via I-SPANC.

A novel bioorthogonal gold nanoparticle (AuNP) template displaying interfacial nitrone functional groups for bioorthogonal interfacial strain-promoted alkyne-nitrone cycloaddition reactions has been synthesized. These nitrone-AuNPs were characterized in detail using 1H nuclear magnetic resonance spectroscopy, transmission electron microscopy, thermogravimetric analysis, and X-ray photoelectron spectroscopy, and a nanoparticle raw formula was calculated. The ability to control the conjugation of molecules of interest at the molecular level onto the nitrone-AuNP template allowed us to create a novel methodology for the synthesis of AuNP-based radiolabeled probes.

Robust, Highly Luminescent Au13 Superatoms Protected by N-Heterocyclic Carbenes.

Gold superatom nanoclusters stabilized entirely by N-heterocyclic carbenes (NHCs) and halides are reported. The reduction of well-defined NHC-Au-Cl complexes produces clusters comprised of an icosahedral Au13 core surrounded by a symmetrical arrangement of nine NHCs and three chlorides. X-ray crystallography shows that the clusters are characterized by multiple CH-π and π-π interactions, which rigidify the ligand and likely contribute to the exceptionally high photoluminescent quantum yields observed, up to 16.0%, which is significantly greater than that of the most luminescent ligand-protected Au13 superatom cluster. Density functional theory analysis suggests that clusters are 8-electron superatoms with a wide HOMO-LUMO energy gap of 2 eV. Consistent with this, the clusters have high stability relative to phosphine stabilized clusters.

N-Heterocyclic Carbenes in Materials Chemistry.

N-Heterocyclic carbenes (NHCs) have become one of the most widely studied class of ligands in molecular chemistry and have found applications in fields as varied as catalysis, the stabilization of reactive molecular fragments, and biochemistry. More recently, NHCs have found applications in materials chemistry and have allowed for the functionalization of surfaces, polymers, nanoparticles, and discrete, well-defined clusters. In this review, we provide an in-depth look at recent advances in the use of NHCs for the development of functional materials.

Amphiphilic N-Heterocyclic Carbene-Stabilized Gold Nanoparticles and Their Self-Assembly in Polar Solvents.

Soft matter-directed self-assembly of amphiphilic inorganic nanoparticles (NPs) has recently emerged as a promising approach to access NP ensembles with superior collective properties. While thiol-terminated molecules are primarily employed to tether the amphiphilic ligand to the metal, concerns remain regarding the stabilities of the resulting NPs and their corresponding aggregates. As an alternative, we report amphiphilic N-heterocyclic carbene (NHC)-functionalized gold nanoparticles (AuNPs). To accomplish this, an amphiphilic NHC-AuI complex based on an asymmetric triethylene glycol-/dodecyl-functionalized benzimidazole was first synthesized and used to prepare the corresponding stable amphiphilic NHC-decorated AuNPs. The resulting NPs were comprehensively characterized using both solution- and solid-state-based techniques such as proton nuclear magnetic resonance spectroscopy, dynamic light scattering, transmission electron microscopy, thermogravimetric analysis, and X-ray photoelectron spectroscopy. By optimizing the self-assembly behavior of these amphiphilic AuNPs in deionized water, ethanol, and their mixtures, we were able to fine-tune the plasmonic properties of the AuNPs in the wide range of 525-640 nm. Furthermore, when treated with thiols, the ensembles showed greater stability compared to their parent discrete AuNP counterparts at room temperature.

Dimensional Control and Morphological Transformations of Supramolecular Polymeric Nanofibers Based on Cofacially-Stacked Planar Amphiphilic Platinum(II) Complexes.

Square-planar platinum(II) complexes often stack cofacially to yield supramolecular fiber-like structures with interesting photophysical properties. However, control over fiber dimensions and the resulting colloidal stability is limited. We report the self-assembly of amphiphilic Pt(II) complexes with solubilizing ancillary ligands based on polyethylene glycol [PEGn, where n = 16, 12, 7]. The complex with the longest solubilizing PEG ligand, Pt-PEG16, self-assembled to form polydisperse one-dimensional (1D) nanofibers (diameters <5 nm). Sonication led to short seeds which, on addition of further molecularly dissolved Pt-PEG16 complex, underwent elongation in a "living supramolecular polymerization" process to yield relatively uniform fibers of length up to ca. 400 nm. The fiber lengths were dependent on the Pt-PEG16 complex to seed mass ratio in a manner analogous to a living covalent polymerization of molecular monomers. Moreover, the fiber lengths were unchanged in solution after 1 week and were therefore "static" with respect to interfiber exchange processes on this time scale. In contrast, similarly formed near-uniform fibers of Pt-PEG12 exhibited dynamic behavior that led to broadening of the length distribution within 48 h. After aging for 4 weeks in solution, Pt-PEG12 fibers partially evolved into 2D platelets. Furthermore, self-assembly of Pt-PEG7 yielded only transient fibers which rapidly evolved into 2D platelets. On addition of further fiber-forming Pt complex (Pt-PEG16), the platelets formed assemblies via the growth of fibers selectively from their short edges. Our studies demonstrate that when interfiber dynamic exchange is suppressed, dimensional control and hierarchical structure formation are possible for supramolecular polymers through the use of kinetically controlled seeded growth methods.

Uniform "Patchy" Platelets by Seeded Heteroepitaxial Growth of Crystallizable Polymer Blends in Two Dimensions.

Rectangular platelets formed by the self-assembly of block copolymers in selective solvents are of interest for a range of applications. Recently, we showed that the seeded growth of crystallizable blends of a block copolymer and homopolymer yields well-defined, low area dispersity examples of these two-dimensional (2D) structures. The key feature was the use of the same crystallizable polymer segment in the seed and blend components to enable an efficient homoepitaxial growth process. Herein we demonstrate that this 2D crystallization-driven self-assembly approach can be extended to heteroepitaxial growth by the use of different crystallizable polymers with compatible crystal structures. This allows the formation of well-defined "patchy" rectangular platelets and platelet block comicelles with different core chemistries. The use of scanning transmission electron microscopy-energy-dispersive X-ray spectroscopy provided key information on the spatial location of the components in the resulting assemblies and thereby valuable insight into the 2D heteroepitaxial growth process.