N-Heterocyclic Carbene Boranes: Dual Reagents for the Synthesis of Gold Nanoparticles.

N-Heterocyclic carbenes (NHCs) have drawn considerable interest in the field of nanomaterials chemistry as highly stabilizing ligands enabling the formation of strong and covalent carbon-metal bonds. Applied to gold nanoparticles synthesis, the most common strategy consists of the reduction of a preformed NHC-AuI complex with a large excess of a reducing agent that makes the particle size difficult to control. In this paper, we report the straightforward synthesis of NHC-coated gold nanoparticles (NHC-AuNPs) by treating a commercially available gold(I) precursor with an easy-to-synthesize NHC-BH3 reagent. The latter acts as both the reducing agent and the source of surface ligands operating under mild conditions. Mechanistic studies including NMR spectroscopy and mass spectrometry demonstrate that the reduction of gold(I) generates NHC-BH2 Cl as a by-product. This strategy gives efficient control over the nucleation and growth of gold particles by varying the NHC-borane/gold(I) ratio, allowing unparalleled particle size variation over the range of 4.9±0.9 to 10.0±2.7 nm. Our strategy also allows an unprecedented precise and controlled seeded growth of gold nanoparticles. In addition, the as-prepared NHC-AuNPs exhibit narrow size distributions without the need for extensive purification or size-selectivity techniques, and are stable over months.

Bio-inspired hydrophobicity promotes CO2 reduction on a Cu surface.

The aqueous electrocatalytic reduction of CO2 into alcohol and hydrocarbon fuels presents a sustainable route towards energy-rich chemical feedstocks. Cu is the only material able to catalyse the substantial formation of multicarbon products (C2/C3), but competing proton reduction to hydrogen is an ever-present drain on selectivity. Here, a superhydrophobic surface was generated by 1-octadecanethiol treatment of hierarchically structured Cu dendrites, inspired by the structure of gas-trapping cuticles on subaquatic spiders. The hydrophobic electrode attained a 56% Faradaic efficiency for ethylene and 17% for ethanol production at neutral pH, compared to 9% and 4% on a hydrophilic, wettable equivalent. These observations are assigned to trapped gases at the hydrophobic Cu surface, which increase the concentration of CO2 at the electrode-solution interface and consequently increase CO2 reduction selectivity. Hydrophobicity is thus proposed as a governing factor in CO2 reduction selectivity and can help explain trends seen on previously reported electrocatalysts.

Direct Synthesis of N-Heterocyclic Carbene-Stabilized Copper Nanoparticles from an N-Heterocyclic Carbene-Borane.

N-Heterocyclic carbene (NHC)-stabilized copper nanoparticles (NPs) were synthesized from an NHC-borane adduct and mesitylcopper(I) under thermal conditions (refluxing toluene for 2.5 h). NPs with a size distribution of 11.6±1.8 nm were obtained. The interaction between Cu NPs and NHC ligands was probed by X-ray photoelectron spectroscopy, which showed covalent binding of the NHC to the surface of the NPs. Mechanistic studies suggested that NHC-borane plays two roles: contributing to the reduction of [CuMes]2 to release Cu0 species and providing NHC ligands to stabilize the copper NPs.

Elaboration, activity and stability of silica-based nitroaromatic sensors.

Functionalized silica-based thin films, modified with hydrophobic groups, were synthesized and used as sensors for nitroaromatic compound (NAC) specific detection. Their performance and behavior, in terms of stability, ageing and regeneration, have been fully characterized by combining chemical characterization techniques and electron microscopy. NAC was efficiently and specifically detected using these silica-based sensors, but showed a great degradation in the presence of humidity. Moreover, the sensor sensitivity seriously decreases with storage time. Methyl- and phenyl-functionalization helped to overcome this humidity sensitivity. Surface characterization enabled us to establish a direct correlation between the appearance, and increasing amount, of adsorbed carbonyl-containing species, and sensor efficiency. This contamination, appearing after only one month, was particularly important when sensors were stored in plastic containers. Rinsing with cyclohexane enables us to recover part of the sensor performance but does not yield a complete regeneration of the sensors. This work led us to the definition of optimized elaboration and storage conditions for nitroaromatic sensors.

EPS for bacterial anti-adhesive properties investigated on a model metal surface.

Understanding Extracellular Polymeric Substances (EPS) interaction on a well-defined chromium surface is of importance especially for biocorrosion processes. Adsorption of EPS extracted from Pseudoalteromonas NCIMB 2021 on Cr surfaces was investigated using in situ quartz crystal microbalance (QCM) and X-ray photoelectron spectroscopy (XPS). We show that EPS adsorption is an irreversible process. The amount of adsorbed EPS increases with increasing EPS concentration in solution. For low EPS concentration, the surface is only partially covered by EPS, whereas a continuous organic film of around 15 nm is formed at the surface for high EPS concentrations. An in-depth structuration of this organic layer is evidenced with a strong enrichment of proteins in the inner part and of polysaccharides in the outer part. Adhesion of Pseudoalteromonas NCIMB 2021 has been tested on Cr surfaces covered or not by EPS extracted from Pseudoalteromonas NCIMB 2021. EPS conditioning with a 15 nm film inhibits bacterial adhesion on Cr, showing that this organic film has efficient anti-adhesive properties.

Synthesis and grafting of a BTP derivative onto a quartz crystal microbalance for lanthanide detection.

The ability of bis-triazinylpyridine (BTP) molecules to complex lanthanides is well-known in solution and can be judiciously utilized to elaborate solid sensing surfaces. This was done by synthesizing a new BTP derivative and covalently anchoring it onto gold surfaces. The BTP grafting, its chemical modification and the resultant lanthanide complexation were evaluated by combining X-ray Photoelectron Spectroscopy (XPS) and Polarization Modulation-Infrared Reflection Absorption Spectroscopy (PM-IRRAS). The detection of neodynium and europium cations was measured by a Quartz Crystal Microbalance (QCM). Interestingly, when immobilized on gold, BTP appeared to show very distinct sensitivities towards Eu(3+) and Nd(3+). Moreover, these sensitivities could be controlled by varying the pH and/or the nitrate concentration in solution. This novel strategy, consisting of the immobilization of BTP sensing molecules, is thus very promising for sensitive and specific lanthanide detection.

Early stage of marine biofilm formation on duplex stainless steel.

The aim of this work was to investigate the bacteria-surface interactions occurring during the first hour of adhesion of marine Pseudoalteromonas NCIMB 2021 at the surface of 2304 lean duplex stainless steel in artificial seawater. A complete characterization of the biofilm and the passive film was performed coupling epifluorescence microscopy, scanning electron microscopy (SEM), x-ray photoelectron spectroscopy (XPS), and time of flight secondary ion mass spectrometry (ToF-SIMS). The coupling of XPS and ToF-SIMS analyses revealed that (1) protein and polysaccharide contents in the biofilm are similar in the presence or absence of nutrients, (2) the biofilm is mainly composed of proteins and the protein content is similar to the one of Tightly Bound EPS, (3) increased bacterial activity due to nutrients leads to chromium enrichment in the passive film in close vicinity to the bacteria.

Zn-Cu Alloy Nanofoams as Efficient Catalysts for the Reduction of CO2 to Syngas Mixtures with a Potential-Independent H2 /CO Ratio.

Alloying strategies are commonly used to design electrocatalysts that take on properties of their constituent elements. Herein, such a strategy is used to develop Zn-Cu alloyed electrodes with unique hierarchical porosity and tunable selectivity for CO2 versus H+ reduction. By varying the Zn/Cu ratio, tailored syngas mixtures are obtained without the production of other gaseous products, which is attributed to preferential CO- and H2 -forming pathways on the alloys. The syngas ratios are also significantly less sensitive to the applied potential in the alloys relative to pure metal equivalents; an essential quality when coupling electrocatalysis with renewable power sources that have fluctuating intensity. As such, industrially relevant syngas ratios are achieved at large currents (-60 mA) for extensive operating times (>9 h), demonstrating the potential of this strategy for fossil-free fuel production.

Grafting of architecture controlled poly(styrene sodium sulfonate) onto titanium surfaces using bio-adhesive molecules: Surface characterization and biological properties.

This contribution reports on grafting of bioactive polymers such as poly(sodium styrene sulfonate) (polyNaSS) onto titanium (Ti) surfaces. This grafting process uses a modified dopamine as an anchor molecule to link polyNaSS to the Ti surface. The grafting process combines reversible addition-fragmentation chain transfer polymerization, postpolymerization modification, and thiol-ene chemistry. The first step in the process is to synthetize architecture controlled polyNaSS with a thiol end group. The second step is the adhesion of the dopamine acrylamide (DA) anchor onto the Ti surfaces. The last step is grafting polyNaSS to the DA-modified Ti surfaces. The modified dopamine anchor group with its bioadhesive properties is essential to link bioactive polymers to the Ti surface. The polymers are characterized by conventional methods (nuclear magnetic resonance, size exclusion chromatography, and attenuated total reflection-Fourier-transformed infrared), and the grafting is characterized by x-ray photoelectron spectroscopy, time-of-flight secondary ion mass spectrometry, and quartz crystal microbalance with dissipation monitoring. To illustrate the biocompatibility of the grafted Ti-DA-polyNaSS surfaces, their interactions with proteins (albumin and fibronectin) and cells are investigated. Both albumin and fibronectin are readily adsorbed onto Ti-DA-polyNaSS surfaces. The biocompatibility of modified Ti-DA-polyNaSS and control ungrafted Ti surfaces is tested using human bone cells (Saos-2) in cell culture for cell adhesion, proliferation, differentiation, and mineralization. This study presents a new, simple way to graft bioactive polymers onto Ti surfaces using a catechol intermediary with the aim of demonstrating the biocompatibility of these size controlled polyNaSS grafted surfaces.