A molecular-dynamics study of a model S(N)1 dissociation reaction at the water liquid/vapor interface

The thermodynamics and dynamics of a model S(N)1 reaction: t-BuCl --> t-Bu+ + Cl- is studied at the water liquid/vapor interface using molecular-dynamics computer simulations. The empirical valence bond approach is used to couple two diabatic states, covalent and ionic, in the electronically adiabatic limit. Umbrella sampling calculations are used to calculate the potential of mean force along the reaction coordinate (defined as the t-Bu to Cl distance) in bulk water and in several locations at the interface. We find a significant increase of the dissociation barrier height and of the reaction free energy at the interface relative to the bulk. This is shown to be due to the reduced polarity of the interface. Reactive flux correlation function calculations show significant deviation of the rate constant from the transition-state theory: The transmission coefficients range from 0.49 in the bulk to 0.05 above the Gibbs surface. The low transmission coefficient at the interface despite the lower friction is shown to be due to slow vibrational relaxation.     

Phosphazene-based ionic liquids: synthesis, temperature-dependent viscosity, and effect as additives in water lubrication of silicon nitride ceramics

Phosphazene rings with (dimethylamino)ethoxy (1, 2), pyridylmethoxy (3), or (dimethylamino)propoxy (4) chains were synthesized and quaternized at the substitutent nitrogen by treatment with methyl iodide at 35 degrees C over 3-6 h to give polyiodo salts, 5-8. Subsequent metathesis with LiN(SO(2)CF(3))(2) or NaBF(4) gave the respective ionic salts, 9-13. The amide salts, 9-12, were viscous liquids with pour points at 55-100 degrees C, and the tetrafluoroborate salt, 13, was a solid, mp 168 degrees C. The compositions of 2 and 5-13 were confirmed by elemental analysis and spectroscopic methods. Compounds 1, 2, and 4 were viscous liquids (d(25) = 1.67 g cm(-3); eta(25) = 0.76-1.56 mPa s(-1) ) with pour points at approximately 15 degrees C. The solid polyquaternary salts, 5-8, melted at 130-194 degrees C. The ionic liquids, 9-12, had an average density of approximately 1.73 g cm(-3) at 25 degrees C, and viscosities (25 degrees C) ranged between 68.3 and 139.2 mPa s(-1). A plot of the viscosities of 9-12 vs temperature revealed an almost linear correlation between 55 and 120 degrees C. Friction and wear properties of water with 0.25 wt % of 9-12 as boundary lubricant additives were evaluated on Si(3)N(4)/Si(3)N(4) ceramic interfaces. The most significant observation is that they caused a decrease in the running-in period.     

Screening an In-House Isoquinoline Alkaloids Library for New Blockers of Voltage-Gated Na+ Channels Using Voltage Sensor Fluorescent Probes: Hits and Biases

Voltage-gated Na⁺ (Na_V) channels are significant therapeutic targets for the treatment of cardiac and neurological disorders, thus promoting the search for novel Na_V channel ligands. With the objective of discovering new blockers of Na_V channel ligands, we screened an In-House vegetal alkaloid library using fluorescence cell-based assays. We screened 62 isoquinoline alkaloids (IA) for their ability to decrease the FRET signal of voltage sensor probes (VSP), which were induced by the activation of Na_V channels with batrachotoxin (BTX) in GH3b6 cells. This led to the selection of five IA: liriodenine, oxostephanine, thalmiculine, protopine, and bebeerine, inhibiting the BTX-induced VSP signal with micromolar IC₅₀. These five alkaloids were then assayed using the Na⁺ fluorescent probe ANG-2 and the patch-clamp technique. Only oxostephanine and liriodenine were able to inhibit the BTX-induced ANG-2 signal in HEK293-hNa_V1.3 cells. Indeed, liriodenine and oxostephanine decreased the effects of BTX on Na⁺ currents elicited by the hNa_V1.3 channel, suggesting that conformation change induced by BTX binding could induce a bias in fluorescent assays. However, among the five IA selected in the VSP assay, only bebeerine exhibited strong inhibitory effects against Na⁺ currents elicited by the hNav1.2 and hNav1.6 channels, with IC₅₀ values below 10 µM. So far, bebeerine is the first BBIQ to have been reported to block Na_V channels, with promising therapeutical applications.     

Strengthening the Connection between Science,Society and Environment to Develop Future French and European Bioeconomies: Cutting-Edge Research of VAALBIO Team at UCCS

The development of the future French and European bioeconomies will involve developing new green chemical processes in which catalytic transformations are key. The VAALBIO team (valorization of alkanes and biomass) of the UCCS laboratory (Unité de Catalyse et Chimie du Solide) are working on various catalytic processes, either developing new catalysts and/or designing the whole catalytic processes. Our research is focused on both the fundamental and applied aspects of the processes. Through this review paper, we demonstrate the main topics developed by our team focusing mostly on oxygen- and hydrogen-related processes as well as on green hydrogen production and hybrid catalysis. The social impacts of the bioeconomy are also discussed applying the concept of the institutional compass.     

Inner multipliers of de Branges's spaces

For a given functionb in the unit ball ofH and an arbitraryH functionm, the question of whenm is a multiplier of the de Branges space (that is, when is invariant under multiplication bym) is examined. Some necessary and sufficient conditions thatm be a multiplier of are found and it is shown that there are no nonconstant inner multipliers of whenb is a nonconstant extreme point of the unit ball ofH . A new proof is given of the known fact that is invariant under multiplication byz whenb is not an extreme point of the unit ball ofH . Finally, we give a new proof of the known fact that an inner functionm is a multiplier of forb(z)=(1+z)/2 if and only ifm belongs to the range of .Some of the work in this paper originally appeared in the author's doctoral disseratation written at the University of California at Berkeley under the supervision of Donald Sarason.     

Bayesian inference for the power law process

The power law process has been used to model reliability growth, software reliability and the failure times of repairable systems. This article reviews and further develops Bayesian inference for such a process. The Bayesian approach provides a unified methodology for dealing with both time and failure truncated data. As well as looking at the posterior densities of the parameters of the power law process, inference for the expected number of failures and the probability of no failures in some given time interval is discussed. Aspects of the prediction problem are examined. The results are illustrated with two data examples.     

Homologies cyclique et de Hochschild de certains espaces homogènes quantiques

Nous quantifions certaines inclusions d'algèbres de Lie semi-simpleshg. Nous calculons les homologies associées aux quantifications, surC((h)), d'une part des algèbres de fonctions formelles surG/H, pourHG une inclusion de groupes de Lie semi-simples associée, et d'autre part des fonctions algébriques sur SL(2,C)/T.We quantize certain inclusions of semisimple Lie algebrashg. We compute the cyclic and Hochschild homologies for theC((h))-quantizations of

Smart Geodesic Tracing in GRworkbench

We have developed a new tool for numerical work in General Relativity: GRworkbench. We discuss how GRworkbench's implementation of a numerically-amenable analogue to Differential Geometry facilitates the development of robust and chart-independent numerical algorithms. We consider, as an example, geodesic tracing on two charts covering the exterior Schwarzschild space-time.     

The 19F and 31P magnetic resonance spectra of phosphorus trifluoride in nematic solution

The phosphorus and fluorine N.M.R. spectra of PF₃ in a nematic solvent (EBBA) are discussed. The molecular geometry is found to agree with structures obtained from microwave and electron diffraction studies. The sign of the ordering parameter is assumed negative, the signs of the phosphorus fluorine coupling constant and of the chemical shift anisotropies follow from this assumption, and are found to be in agreement with theoretical predictions. The effect of temperature on the isotropic chemical shift of fluorine is discussed.     

High pressure stability of protein complexes studied by static and dynamic light scattering

The high pressure dissociation of hemocyanin prepared from the lobster Homarus americanus and casein micelles from cow milk were observed by in situ light scattering. The hemocyanin dodecamer dissociated via a hexamer into monomers in a two-step three-species reaction. The influence of ligands and the effector l-lactate on the dissociation behavior was investigated. While no effect by carbon monoxide after exchanging the ligand oxygen was observed, the addition of the effector l-lactate led to a decrease in the pressure stability. Due to a trimer intermediate which was found to be stabilized by l-lactate, the dissociation reaction in the presence of the effector was analyzed by a three-step four-species reaction. In the case of casein micelles, a two-step dissociation mechanism was found. The stabilizing interactions of casein micelles were identified and separated.