Optical microscopy to study single nanoparticles electrochemistry: From reaction to motion

Nanoparticles (NPs)-based electrochemical devices are generating a growing interest and optical microscopy has recently proven to be a powerful tool to apprehend their electrochemical behavior. Through several striking examples, this review demonstrates how label-free optical imaging coupled to an electrochemical actuation can be used to probe operando the physical and electrochemical properties of single NPs, with high resolution and sensitivity and without additional emitters. Such an approach can be particularly relevant to establish clear structure-motion/reactivity relationships required to optimize NPs exploited as electrode materials.     

Snake Venom Components: Tools and Cures to Target Cardiovascular Diseases

Cardiovascular diseases (CVDs) are considered as a major cause of death worldwide. Therefore, identifying and developing therapeutic strategies to treat and reduce the prevalence of CVDs is a major medical challenge. Several drugs used for the treatment of CVDs, such as captopril, emerged from natural products, namely snake venoms. These venoms are complex mixtures of bioactive molecules, which, among other physiological networks, target the cardiovascular system, leading to them being considered in the development and design of new drugs. In this review, we describe some snake venom molecules targeting the cardiovascular system such as phospholipase A2 (PLA2), natriuretic peptides (NPs), bradykinin-potentiating peptides (BPPs), cysteine-rich secretory proteins (CRISPs), disintegrins, fibrinolytic enzymes, and three-finger toxins (3FTXs). In addition, their molecular targets, and mechanisms of action—vasorelaxation, inhibition of platelet aggregation, cardioprotective activities—are discussed. The dissection of their biological effects at the molecular scale give insights for the development of future snake venom-derived drugs.     

gem-Heteroatom-Substituted Fluoroalkenes as Mimics of Amide Derivatives or Phosphates: A Comprehensive Review

gem-Heteroatom-substituted fluoroalkenes have received little attention despite their great potential in medicinal chemistry or in fine chemistry. Indeed, due to the electronic and steric similarity between the fluoroalkene moiety and the amide bond as well as the high strength of the carbon-fluorine bond, these gem-heteroatom-substituted fluoroalkenes could be envisioned as stable mimics of various important organic functions, such as phosphates, carbamates, S-thiocarbamates and ureas. We present herein an overview describing the syntheses over the last decade of heteroatom-substituted fluoroalkenes in geminal position. This review will be divided into several sections covering each the common following heteroatom: oxygen-, nitrogen-, sulfur-, phosphorus-, boron- and silicon-substituted fluoroalkenes.     

Spin State Tunes Oxygen Atom Transfer towards FeIVO Formation in FeII Complexes

Oxoiron(IV) complexes bearing tetradentate ligands have been extensively studied as models for the active oxidants in non-heme iron-dependent enzymes. These species are commonly generated by oxidation of their ferrous precursors. The mechanisms of these reactions have seldom been investigated. In this work, the reaction kinetics of complexes [Fe^II(CH₃CN)₂L](SbF₆)₂ ( [1](SbF₆)₂ and [2](SbF₆)₂ ) and [Fe^II(CF₃SO₃)₂L] ( [1](OTf)₂ and [2](OTf)₂ ( 1 , L=^Me,HPytacn; 2 , L=^nP,HPytacn; ^R,R′Pytacn=1-[(6-R′-2-pyridyl)methyl]-4,7- di-R-1,4,7-triazacyclononane) with Bu₄NIO₄ to form the corresponding [Fe^IV(O)(CH₃CN)L]²⁺ ( 3 , L=^Me,HPytacn; 4 , L=^nP,HPytacn) species was studied in acetonitrile/acetone at low temperatures. The reactions occur in a single kinetic step with activation parameters independent of the nature of the anion and similar to those obtained for the substitution reaction with Cl⁻ as entering ligand, which indicates that formation of [Fe^IV(O)(CH₃CN)L]²⁺ is kinetically controlled by substitution in the starting complex to form [Fe^II(IO₄)(CH₃CN)L]⁺ intermediates that are converted rapidly to oxo complexes 3 and 4 . The kinetics of the reaction is strongly dependent on the spin state of the starting complex. A detailed analysis of the magnetic susceptibility and kinetic data for the triflate complexes reveals that the experimental values of the activation parameters for both complexes are the result of partial compensation of the contributions from the thermodynamic parameters for the spin-crossover equilibrium and the activation parameters for substitution. The observation of these opposite and compensating effects by modifying the steric hindrance at the ligand illustrates so far unconsidered factors governing the mechanism of oxygen atom transfer leading to high-valent iron oxo species.     

Linearly repetitive Delone sets are rectifiable

We show that every linearly repetitive Delone set in the Euclidean d  -space R^d${\mathbb{R}}^d$, with d?2$d?2$, is equivalent, up to a bi-Lipschitz homeomorphism, to the integer lattice Z^d${\mathbb{Z}}^d$. In the particular case when the Delone set X   in R^d${\mathbb{R}}^d$ comes from a primitive substitution tiling of R^d${\mathbb{R}}^d$, we give a condition on the eigenvalues of the substitution matrix which ensures the existence of a homeomorphism with bounded displacement from X   to the lattice βZ^d$\beta {\mathbb{Z}}^d$ for some positive β. This condition includes primitive Pisot substitution tilings but also concerns a much broader set of substitution tilings.     

Finite element approximation of the Neumann eigenvalue problem in domains with multiple cracks

^** Email: belhach{at}poncelet.univ-metz.fr^*** Email: bucur{at}math.univ-metz.fr^**** Email: jmse{at}math.univ-metz.fr We study the Neumann–Laplacian eigenvalue problem in domainswith multiple cracks. We derive a mixed variational formulationwhich holds on the whole geometric domain (including the cracks)and implements efficient finite-element discretizations forthe computation of eigenvalues. Optimal error estimates aregiven and several numerical examples are presented, confirmingthe efficiency of the method. As applications, we numericallyinvestigate the behaviour of the low eigenvalues in domainswith a large number of cracks.     

Variance limite d'une marche aléatoire réversible en milieu aléatoire sur Z

The Central Limit Theorem for the random walk on a stationary random network of conductances has been studied by several authors. In one dimension, when conductances and resistances are integrable, and following a method of martingale introduced by S. Kozlov (1985), we can prove the Quenched Central Limit Theorem. In that case the variance of the limit law is not null. When resistances are not integrable, the Annealed Central Limit Theorem with null variance was established by Y. Derriennic and M. Lin (personal communication). The quenched version of this last theorem is proved here, by using a very simple method. The similar problem for the continuous diffusion is then considered. Finally our method allows us to prove an inequality for the quadratic mean of a diffusion. To cite this article: J. Depauw, J.-M. Derrien, C. R. Acad. Sci. Paris, Ser. I 347 (2009).     

A hyperbolic three-phase flow model

We introduce a hyperbolic entropy-consistent model to describe three-phase flows, which ensures that void fractions, mass fractions and pressures remain positive through single waves occurring in the one dimensional solution of the Riemann problem. To cite this article: J.-M. Hérard, C. R. Acad. Sci. Paris, Ser. I 342 (2006).     

Non-rigidity of Spherical Inversive Distance Circle Packings

We give a counterexample of Bowers–Stephenson’s conjecture in the spherical case: spherical inversive distance circle packings are not determined by their inversive distances.