Standard ion transfer potential at the water|butyronitrile interface

Butyronitrile is an organic solvent stable enough to be used in photochemical reactions at liquid/liquid interfaces. However, it provides a rather short polarisation window making the analysis of ion transfer across the water|butyronitrile interface challenging. Here, steady-state cyclic voltammetry, at microhole-supported micro-interfaces, was used to measure Gibbs energies of transfer. A linear relationship between the standard Gibbs energies of ion partition for the water|butyronitrile interface and the water|1,2-dichloroethane and water|nitrobencene interfaces was found, making easy to extrapolate the Gibbs energy of other ions from this empiric correlation.Fil: Riva, Julieta Soledad. Swiss Federal Institute Of Technology Epfl; Suiza. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Córdoba. Facultad de Matemática, Astronomía y Física; ArgentinaFil: Bassetto, V. C.. Swiss Federal Institute Of Technology Epfl; SuizaFil: Girault, Hubert. Swiss Federal Institute Of Technology Epfl; SuizaFil: Olaya, A. J.. Swiss Federal Institute Of Technology Epfl, Lausanne

On the numerical approximation of p-biharmonic and ∞-biharmonic functions

In [KP16] (arXiv:1605.07880) the authors introduced a second-order variational problem in L∞. The associated equation, coined the ∞-Bilaplacian, is a \emph{third order} fully nonlinear PDE given by Δ2∞u:=(Δu)3|D(Δu)|2=0. In this work we build a numerical method aimed at quantifying the nature of solutions to this problem which we call ∞-Biharmonic functions. For fixed p we design a mixed finite element scheme for the pre-limiting equation, the p-Bilaplacian Δ2pu:=Δ(|Δu|p−2Δu)=0. We prove convergence of the numerical solution to the weak solution of Δ2pu=0 and show that we are able to pass to the limit p→∞. We perform various tests aimed at understanding the nature of solutions of Δ2∞u and in 1-d we prove convergence of our discretisation to an appropriate weak solution concept of this problem, that of -solutions

Hot Adsorbate-Induced Retardation of the Internal Thermalization of Nonequilibrium Electrons in Adsorbate-Covered Metal Nanoparticles

Femtosecond transient absorption spectroscopy has been used to investigate the electron-electron scattering dynamics in sulfate-covered gold nanoparticles of 2.5 and 9.2 nm in diameter. We observe an unexpected retardation of the absolute internal thermalization time compared to bulk gold, which is attributed to a negative feedback by the vibrationally excited sulfate molecules. These hot adsorbates, acting as a transient energy reservoir, result from the back and forth inelastic scattering of metal nonequilibrium electrons into the ð* orbital of the sulfate. The vibrationally excited adsorbates temporarily govern the dynamical behavior of nonequilibrium electrons in the metal by re-emitting hot electrons. In other terms, metal electrons reabsorb the energy deposited in the hot sulfates by a mechanism involving the charge resonance between the sulfate molecules and the gold NPs. The higher surface-to-volume ratio of sulfate-covered gold nanoparticles of 2.5 nm leads to a stronger inhibition of the internal thermalization. Interestingly, we also note an analogy between the mechanism described here for the slow-down of electron-electron scattering in metal nanoparticles by the hot adsorbates and the hot phonon-induced retardation of hot charge carriers cooling in semiconductors

Study of peptide on-line complexation with transition-metal ions generated from sacrificial electrodes in thin-chip polymer microsprays

A miniaturized polymer electrospray-type interface is used to study metal-ion chelation with model peptides. Taking advantage of the intrinsic electrochemical behavior of electrospray, a sacrificial electrode is used to generate at the same time electrospray and transition-metal ions coming from the anodic dissolution of the electrode. The microspray interface provides enhanced mass transport due to its small dimensions, increasing the yield of possible reactions, in particular complex formation. Transition-metal electrodes, e.g. copper, zinc, nickel, iron and silver, are used to obtain on-line complexation with model peptides. It is demonstrated that the use of in-reservoir sacrificial electrodes is an efficient way to generate metal ions in order to form and study complexes with peptides, avoiding the addition of metallic salts

Probing Cysteine Reactivity in Proteins by Mass Spectrometric EC-Tagging

The on-line electrochemical tagging (EC-tagging) of cysteine residues in proteins during mass spectrometry is studied to probe the cysteine environment. Benzoquinone probes electrogenerated at a microspray electrode react with the thiol functions of the proteins within a microchannel and the products are analyzed by mass spectrometry. The fundamentals of the technique are discussed, with a focus on the kinetic aspects. The EC-tagging efficiency of the cysteine residues in proteins is used to probe their environment. Experiments with unmodified proteins and their chemically reduced forms highlight the strong effect of the cysteine site reactivity on the tagging efficiencies. This study highlights relevant parameters for such on-line electrochemical derivatization/MS detection strategies

Size Dependence of Investigations of Hot Electron Cooling Dynamincs in Metal/Adsorbates Nanoparticles

The size dependence of electron-phonon coupling rate has been investigated by femtosecond transient absorption spectroscopy for gold nanoparticles (NPs) wrapped in a shell of sulfate with diameter varying from 1.7 to 9.2 nm. Broad-band spectroscopy gives an overview of the complex dynamics of nonequilibrium electrons and permits the choice of an appropriate probe wavelength for studying the electron-phonon coupling dynamics. Ultrafast experiments were performed in the weak perturbation regime (less than one photon in average per nanoparticle), which allows the direct extraction of the hot electron cooling rates in order to compare different NPs sizes under the same conditions. Spectroscopic data reveals a decrease of hot electron energy loss rates with metal/adsorbates nanosystem sizes. Electron-phonon coupling time constants obtained for 9.2 nm NPs are similar to gold bulk materials (a. 1 ps) whereas an increase of hot electron cooling time up to 1.9 ps is observed for sizes of 1.7 nm. This is rationalized by the domination of surface effects over size (bulk) effects. The slow hot electron cooling is attributed to the adsorbates-induced long-lived nonthermal regime, which significantly reduces the electron-phonon coupling strength (average rate of phonon emission)