Effect of the surface free energy on the behaviour of surface and guided waves

The aim of this paper is to evaluate the influence of the surface free energy upon the propagation of the eigenmodes of structures, by studying successively (a) the Rayleigh wave for an elastic half-space, (b) the Lamb waves for an elastic layer, and (c) the guided modes for a tri-layer structure (e.g., metal/adhesive/metal). The surface free energy is a parameter which appears in the jump conditions of stresses and displacements at each interface, and which consequently modifies the eigenmodes, solutions of the boundary conditions system. As expected, the Rayleigh wave is dispersive and its velocity increases when the surface free energy increases. In the same way, the velocity of Lamb waves also increases except at normal angle of propagation where the surface free energy does not arise. Moreover, near the Rayleigh angle, the behaviour of the A₀ and S₀ Lamb modes varies strongly according to the surface free energy. Similar results are observed for the tri-layer structure.     

SSPaQ: A Subtractive Segmentation Approach for the Exhaustive Parallel Quantification of the Extent of Protein Modification at Every Possible Site

Protein modifications, whether chemically induced or post-translational (PTMs), play an essential role for the biological activity of proteins. Understanding biological processes and alterations thereof will rely on the quantification of these modifications on individual residues. Here we present SSPaQ, a subtractive method for the parallel quantification of the extent of modification at each possible site of a protein. The method combines uniform isotopic labeling and proteolysis with MS, followed by a segmentation approach, a powerful tool to refine the quantification of the degree of modification of a peptide to a segment containing a single modifiable amino acid. The strength of this strategy resides in: (1) quantification of all modifiable sites in a protein without prior knowledge of the type(s) of modified residues; (2) insensitivity to changes in the solubility and ionization efficiency of peptides upon modification; and (3) detection of missed cleavages caused by the modification for mitigation. The SSPaQ method was applied to quantify modifications resulting from the interaction of human phosphatidyl ethanolamine binding protein 1 (hPEBP1), a metastasis suppressor gene product, with locostatin, a covalent ligand and antimigratory compound with demonstrated activity towards hPEBP1. Locostatin is shown to react with several residues of the protein. SSPaQ can more generally be applied to induced modification in the context of drugs that covalently bind their target protein. With an alternate front-end protocol, it could also be applied to the quantification of protein PTMs, provided a removal tool is available for that PTM.

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Access to L- and D-iminosugar C-glycosides from a D-gluco-derived 6-azidolactol exploiting a ring isomerization/alkylation strategy

A flexible synthetic access to six-membered L- and D-iminosugar C-glycosides is reported starting from the easily available 6-azido-6-deoxy-2,3,4-tri-O-benzyl-D-glucopyranose precursor. This methodology involves a highly diastereoselective tandem ring enlargement/alkylation and a stereocontrolled ring contraction. It allows an efficient synthesis of iminosugar C-glycosides displaying structural diversity at both C-1 and C-6.     

A polymer surfactant corona dynamically replaces water in solvent-free protein liquids and ensures macromolecular flexibility and activity

The observation of biological activity in solvent-free protein-polymer surfactant hybrids challenges the view of aqueous and nonaqueous solvents being unique promoters of protein dynamics linked to function. Here, we combine elastic incoherent neutron scattering and specific deuterium labeling to separately study protein and polymer motions in solvent-free hybrids. Myoglobin motions within the hybrid are found to closely resemble those of a hydrated protein, and motions of the polymer surfactant coating are similar to those of the hydration water, leading to the conclusion that the polymer surfactant coating plasticizes protein structures in a way similar to hydration water.     

Interplay between Cationic and Neutral Species in the Rhodium‐Catalyzed Hydroaminomethylation Reaction

The reactivity of [Rh(CO)₂{(R,R)‐Ph? BPE}]BF₄ ( 2 ) toward amine, CO and/or H₂ was examined by high‐pressure NMR and IR spectroscopy. The two cationic pentacoordinated species [Rh(CO)₃{(R,R)‐Ph? BPE}]BF₄ ( 4 ) and [Rh(CO)₂(NHC₅H₁₀){(R,R)‐Ph‐BPE}]BF₄ ( 8 ) were identified. The transformation of 2 into the neutral complex [RhH(CO)₂{(R,R)‐Ph? BPE}] ( 3 ) under hydroaminomethylation conditions (CO/H₂, amine) was investigated. The full mechanisms related to the formation of 3 , 4 and 8 starting from 2 are supported by DFT calculations. In particular, the pathway from 2 to 3 revealed the deprotonation by the amine of the dihydride species [Rh(H)₂(CO)₂{(R,R)‐Ph? BPE}]BF₄ ( 6 ), resulting from the oxidative addition of H₂ on 2 .     

Swelling instability of surface-attached gels as a model of soft tissue growth under geometric constraints

The purpose of this work is to provide a theoretical analysis of the mechanical behavior of the growth of soft materials under geometrical constraints. In particular, we focus on the swelling of a gel layer clamped to a substrate, which is still the subject of many experimental tests. Because the constrained swelling process induces compressive stresses, all these experiments exhibit surface instabilities, which ultimately lead to cusp formation. Our model is based on fixing a neo-Hookean constitutive energy together with the incompressibility requirement for a volumetric, homogeneous mass addition. Our approach is developed mostly, but not uniquely, in the plane strain configuration. We show how the standard equilibrium equations from continuum mechanics have a similarity with the two-dimensional Stokes flows, and we use a nonlinear stream function for the exact treatment of the incompressibility constraint. A free energy approach allows the extension both to arbitrary hyperelastic strain energies and to additional interactions, such as surface energies. We find that, at constant volumetric growth, the threshold for a wavy instability is completely governed by the amount of growth. Nevertheless, the determination of the wavelength at threshold, which scales with the initial thickness of the gel layer, requires the coupling with a surface effect. Our findings, which are valid in proximity of the threshold, are compared to experimental results. The proposed treatment can be extended to weakly nonlinearities within the aim of the theory of bifurcations.     

Bis(crown ether) and Azobenzocrown Derivatives of Calix[4]arene. A Review of Structural Information from Crystallographic and Modelling Studies

The association within one molecule ofcalix[4]arene and crown ether moieties leads toligands with new complexing properties. In particular,calix[4]arene bis(crown-6) and some of itsderivatives have been shown to be highly selectiveextractants for caesium ions. This review presents thebackground of the study and the results of crystalstructure determinations and molecular modellingcalculations performed during the investigation of twomolecular families, the bis(crown ether) and theazobenzocrown derivatives of calix[4]arene.