Metalloenzyme-Mediated Thiol-Yne Addition Towards Photoisomerizable Fluorescent Dyes

Proteins are able to irreversibly assemble biologically active ligands from building blocks bearing complementary reactive functions due their spatial proximity, through a kinetic target-guided synthetic process (also named in situ click chemistry). Although linkages thus formed are mostly passive, some of them have shown to significantly contribute to the protein binding through for instance hydrogen bonding and stacking interactions. Biocompatible reactions and click chemistry are a formidable source of inspiration for developing such new protein-directed ligations. This study reports a proximity-induced thiol-yne synthesis of carbonic anhydrase inhibitors. Not only this example widens the arsenal of kinetic target-guided synthesis (KTGS) eligible reactions, but the obtained product displayed unsuspected photophysical properties. The corresponding vinyl sulfide linkage conjugated to a coumarin core proved to be engaged in a monodirectional Z to E photoisomerization process. Further investigations guided by theoretical calculations showed that fine-tuning of the nature of the substituents on the coumarin moiety allows to obtain a bidirectional photochemical process, thus discovering a new photoswitching moiety, displaying moreover fluorescence properties. Due to the spectral tunability of coumarin derivatives, this work should open new opportunities for the design of vinyl sulfide-based photoswitch systems with modular photophysical properties.     

Efficient and Magnetically Recoverable “Click” PEGylated γ‐Fe2O3–Pd Nanoparticle Catalysts for Suzuki–Miyaura,Sonogashira, and Heck Reactions with Positive Dendritic Effects

The engineering of novel catalytic nanomaterials that are highly active for crucial carbon–carbon bond formations, easily recoverable many times, and biocompatible is highly desirable in terms of sustainable and green chemistry. To this end, catalysts comprising dendritic “click” ligands that are immobilized on a magnetic nanoparticle (MNP) core, terminated by triethylene glycol (TEG) groups, and incorporate Pd nanoparticles (PdNPs) have been prepared. These nanomaterials are characterized by transmission electron microscopy (TEM), high‐resolution TEM, inductively coupled plasma analysis, Fourier transform infrared spectroscopy, X‐ray photoelectron spectra and energy‐dispersive X‐ray spectroscopy. They are shown to be highly active, dispersible, and magnetically recoverable many times in Suzuki, Sonogashira, and Heck reactions. In addition, a series of pharmacologically relevant or natural products were successfully synthesized using these magnetic PdNPs as catalyst. For comparison, related PdNP catalysts deposited on MNPs bearing linear “click” PEGylated ligands are also prepared. Strong positive dendritic effects concerning ligand loading, catalyst loading, catalytic activity, and recyclability are observed, that is, the dendritic catalysts are much more efficient than non‐dendritic analogues.     

High order variational numerical schemes with application to Nash–MFG vaccination games

This paper introduces high-order explicit Runge–Kutta numerical schemes in metric spaces. We show that our approach reduces to the corresponding Runge–Kutta schemes if the ambient space is Hilbert. We apply these schemes to compute the Nash equilibrium in a mean field vaccination game. Numerical simulations show improvement in the speed of convergence towards the Nash equilibrium; the numerical scheme has high order (2–4) in time.     

An exact algorithm for the bi-objective timing problem

The timing problem in the bi-objective just-in-time single-machine job-shop scheduling problem (JiT-JSP) is the task to schedule N jobs whose order is fixed, with each job incurring a linear earliness penalty for finishing ahead of its due date and a linear tardiness penalty for finishing after its due date. The goal is to minimize the earliness and tardiness simultaneously. We propose an exact greedy algorithm that finds the entire Pareto front in \(O(N^2)\) time. This algorithm is asymptotically optimal.     

Global existence result for rate-independent processes in viscous solids with heat transfer

This note deals with three-dimensional models for rate-independent processes describing materials undergoing phase transformations with heat transfer. The problem is formulated within the framework of generalized standard solids by the coupling of the momentum equilibrium equation and the flow rule with the heat transfer equation. The existence of a global solution for this thermodynamically consistent problem is obtained by using a fixed-point argument combined with global energy estimates. (© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

No adaptation in the amplitude modulation domain in trained listeners

The present study shows that on average, exposure to a 15 min, 5 kHz tone modulated sinusoidally in amplitude at 16 Hz with a 100% depth does not affect significantly amplitude modulation (AM) detection thresholds measured between 4 and 64 Hz when listeners are extensively trained to the AM detection task, with and without adaptor before data collection. These results are compatible with previous work given that a clear 6-dB adaptation effect was observed during the first pilot trials. However, the results reveal that adaptation effects are not robust, and suggest that the mechanisms underlying adaptation to AM must be reevaluated.     

Univocal demonstration of the electrochemically mediated binding of Pb2+ by a modified surface incorporating a TTF-based redox-switchable ligand

A tetrathiafulvalene-based redox-switchable ligand with unprecedented electrochemical recognition properties for a metallic cation is described and is chemically immobilized onto a solid surface. The recognition properties for Pb2+ are maintained at the solid-liquid interface. Evidence of the modulation of the binding affinity of the modified surface, as a function of the potential applied, is given by EQCM analyses and by direct measurements of residual Pb2+ concentration in solution by atomic absorption.     

Étude d'un modèle thermo-chimique de formation d'un matériau composite

We consider a composite material constituted of carbon or glass fibres included in a resin which becomes solid when it is heated up (reaction of reticulation). The mathematical modelling of the cure process is given by a kinetic equation describing the evolution of the reaction of reticulation coupled with the heat equation. The geometry of the composite material is periodic, with a small period $?>0$. First we prove the existence and uniqueness of a solution by using Schauder's fixed point theorem. Then, by using an asymptotic expansion, we derive the homogenized problem which describes the macroscopic behaviour of the material. We prove the convergence of the solution of the problem to the solution of the homogenized problem when ? tends to zero and we obtain an error estimate in a case of weak non-linearity. Finally we solve numerically the homogenized problem. To cite this article: S. Meliani et al., C. R. Acad. Sci. Paris, Ser. I 339 (2004).