Three‐Dimensional Branched and Faceted Gold–Ruthenium Nanoparticles: Using Nanostructure to Improve Stability in Oxygen Evolution Electrocatalysis

Achieving stability with highly active Ru nanoparticles for electrocatalysis is a major challenge for the oxygen evolution reaction. As improved stability of Ru catalysts has been shown for bulk surfaces with low‐index facets, there is an opportunity to incorporate these stable facets into Ru nanoparticles. Now, a new solution synthesis is presented in which hexagonal close‐packed structured Ru is grown on Au to form nanoparticles with 3D branches. Exposing low‐index facets on these 3D branches creates stable reaction kinetics to achieve high activity and the highest stability observed for Ru nanoparticle oxygen evolution reaction catalysts. These design principles provide a synthetic strategy to achieve stable and active electrocatalysts.     

Magnetically Induced Continuous CO2 Hydrogenation Using Composite Iron Carbide Nanoparticles of Exceptionally High Heating Power

The use of magnetic nanoparticles to convert electromagnetic energy into heat is known to be a key strategy for numerous biomedical applications but is also an approach of growing interest in the field of catalysis. The heating efficiency of magnetic nanoparticles is limited by the poor magnetic properties of most of them. Here we show that the new generation of iron carbide nanoparticles of controlled size and with over 80 % crystalline Fe_2.2C leads to exceptional heating properties, which are much better than the heating properties of currently available nanoparticles. Associated to catalytic metals (Ni, Ru), iron carbide nanoparticles submitted to magnetic excitation very efficiently catalyze CO₂ hydrogenation in a dedicated continuous‐flow reactor. Hence, we demonstrate that the concept of magnetically induced heterogeneous catalysis can be successfully applied to methanation of CO₂ and represents an approach of strategic interest in the context of intermittent energy storage and CO₂ recovery.     

Mechanistic analysis of the photocycloaddition of silyl-tethered alkenes

The photochemistry of substituted cinnamyloxy silanes has been examined in both cyclohexane and acetonitrile solvents. Alkene isomerization occurs in addition to cycloaddition. Fluorescence quantum yields and excited singlet state lifetimes have been determined for each compound. We have used the information in order to better understand the regio- and stereoselectivity of photocycloaddition between silyl-tethered cinnamyl groups. This study allows us to conclude that the 2 + 2 photocycloaddition between alkenes is not a Woodward-Hoffmann orbital symmetry controlled event. The most consistent explanation for the excellent regio- and stereoselectivity is that the photocycloaddition is conformationally controlled.     

Electrostastic control of spontaneous curvature in catanionic reverse micelles

By means of small-angle neutron scattering and conductivity measurements, we study the microstructure of octylammoniumoctanoate/octane/water catanionic reverse microemulsions with an excess of anionic or cationic surfactant. Increasing the surface charge makes the microemulsion able to incorporate much more water than in the neutral case, up to 10 water molecules per surfactant. Even with charges in the surfactant film, wormlike micelles are present in the microemulsion domain. Along water dilution lines, the classical rod-to-sphere transition due to the minimization of the curvature energy of the rigid surfactant film is observed. When temperature is decreased, a re-entrant phase transition associated with the liquid-gas equilibrium of attractive cylinders is observed. Using the framework of the Tlusty-Safran theory, attraction could originate from junctions between wormlike reverse micelles. In any case, the spontaneous curvature of the catanionic surfactant film depends on both the temperature and the net charge, whatever the sign of the latter.     

Electron transfer and ligand addition to atomic mercury cations in the gas phase: kinetic and equilibrium studies at 295 k

Results are reported for experimental measurements of the room-temperature chemical reactions between ground-state Hg*+ ions and 16 important environmental and biological gases: SF6, CO, CO2, N2O, D2O, CH4, CH3F, O2, CH3Cl, OCS, CS2, NH3, C6F6, NO2, NO*, and C6H6. The inductively coupled plasma/selected-ion flow tube tandem mass spectrometer used for these measurements has provided both rate and equilibrium constants. Efficient electron transfer (>19%) is observed with CS2, NH3, C6F6, NO2, NO*, and C6H6, molecular addition occurs with D2O, CH4, CH3F, CH3Cl, and OCS, and SF6, CO, CO2, N2O, and O2 showed no measurable reactivity with Hg*+. Theory is used to explore the stabilities and structures of both the observed and unobserved molecular adducts of Hg*+, and reasonable agreement is obtained with experimental observations, given the uncertainties of the theory and experiments. A correlation is reported between the Hg*+ and proton affinities of the ligands investigated. Solvation of Hg*+ with formic acid was observed to increase the rate of electron transfer from NO* by more than 20%.     

Multivariate analysis approach to the plasma protein profile of patients with advanced colorectal cancer

The aim of the present study was to identify the pattern of plasma protein species of interest as markers of colorectal cancer (CRC). Using matrix-assisted laser desorption/ionization-mass spectrometry (MALDI-MS), the plasma protein profile was determined in nine stage IV CRC patients (study group) and nine clean-colon healthy subjects (control group). Multivariate analysis methods were employed to identify distinctive disease patterns at protein spectrum. In the study and control groups, cluster analysis (CA) on the complete MALDI-MS spectra plasma protein profile showed a distinction between CRC patients and healthy subjects, thus allowing the identification of the most discriminating ionic species. Principal component analysis (PCA) and linear discriminant analysis (LDA) yielded similar grouping results. LDA with leave-one-out cross validation achieved a correct classification rate of 89% in both the patients and the healthy subjects.     

Development of a novel label-free amperometric immunosensor for the detection of okadaic acid

Okadaic acid (OA), a lipophilic phycotoxin is mainly produced by toxigenic dinoflagellates. The need to develop high performing methods for OA analysis able to improve the traditional ones is evident. In this work, a novel experimental methodology for label-free detection of OA was developed. Protein G magnetic beads (protein-G-MBs) modified gold electrode was used to immobilize anti-OA monoclonal antibody (anti-OA-MAb). Preliminary, colorimetric tests were performed in order to validate protein-G-MBs and anti-OA-MAb reaction. Electrochemical detection was carried out by differential pulse voltammetry in ferri/ferrocyanide solution. The limit of detection value obtained (0.5 μg L⁻¹) validated the developed electrochemical immunosensor as a promising tool for routine use. The matrix effect and the recovery rate were also assessed with real samples, showing a good percentage of recovery.