Synthesis and Diversification of Macrocyclic Alkynediyl Sulfide Peptides

The synthesis of rare macrocyclic alkynediyl sulfides by a Cu-catalyzed C_sp−S cross-coupling is presented. The catalytic protocol (Cu(MeCN)₄PF₆/dtbbpy) promotes macrocyclization of peptides, dipeptides and tripeptides at ambient temperature (14 examples, 23→73 % yields) via thiols and bromoalkynes, and is chemoselective with regards to terminal alkynes. Importantly, the underexplored alkynediyl sulfide functionality incorporates a rigidifying structural element and opens new opportunities for diversification of macrocyclic frameworks through S oxidation, halide addition and azide–alkyne cycloaddition chemistries to integrate sulfones, halides or valuable fluorophores (7 examples, 37→92 % yields).     

Engineering of Silicon Core-Shell Structures for Li-ion Anodes

The amount of silicon in anode materials for Li-ion batteries is still limited by the huge volume changes during charge-discharge cycles. Such changes lead to the loss of electrical contacts, as well as mechanical and surface electrolyte interphase (SEI) instabilities, strongly reducing the cycle life. Core-shell structures have attracted a vast research interest due to the possibility of modifying some properties with a judicious choice of the shell. It is, for example, possible to improve the electronic conductivity and ionic diffusion, or buffer volume variations. This review gives a comprehensive overview of the recent developments and the different strategies used for the design, synthesis and electrochemical performance of silicon-based core-shells. It is based on a selection of the main types of silicon coatings reported in the literature, including carbon, inorganic, organic and double-layer coatings, Finally, a summary of the advantages and drawbacks of these different types of core-shells as anode materials for Li-ion batteries and some insightful suggestions in regards to their use are provided.     

Effect of a post‐annealing process on microstructure and mechanical properties of high‐density polyethylene/silica nanocomposites

High‐density polyethylene (HDPE) and nanosilica nanocomposites were prepared for SiO₂ content up to 15 wt%. Microstructural characterization evidenced a homogenous distribution of silica aggregates with a mean size increasing with the filler content finally resulting in a rheological percolation between 7.5 and 10 wt%. Nanoparticles did not induce any significant impact on the matrix crystallinity but led to a real improvement on elastic properties accompanied with a large embrittlement above the percolation threshold. The effect of annealing near HDPE melting temperature was studied. Differential scanning calorimetry, X‐ray diffraction, and small‐angle X‐ray scattering analyses showed a significant change in the HDPE microstructure after annealing at 125°C. A large increase in the crystallinity (from 68 to 76%) and a clear improvement of Young's modulus (by 55%) were observed prior to polymer degradation. A valuable impact of silica particles on thermal stability was also obvious regarding the evolution of elastic properties for extended exposure times (850–1,200 h). © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 535–546     

Study of the 1D lattice Boltzmann shallow water equation and its coupling to build a canal network

The D1Q3 lattice Boltzmann (LB) shallow water equation is analyzed in detail and compared with other numerical schemes. Analytical results are derived and used to discuss the accuracy and stability of the model. We show how such D1Q3 LB models for canal reaches may be easily coupled with various hydraulic interconnection structures to build models of complex irrigation networks.     

Pyrimidine (6-4) pyrimidone photoproduct mapping after sublethal UVC doses: nucleotide resolution using terminal transferase-dependent PCR

UVC irradiation of genomic DNA induces two main types of potentially mutagenic base modifications: cyclobutane pyrimidine dimers (CPDs) and the less frequent (15-30% of CPD levels) pyrimidine (6-4) pyrimidone photoproducts (6-4PP). Ligation-mediated PCR (LMPCR), a genomic sequencing technique, allows CPD mapping at nucleotide resolution following irradiation with sublethal doses of UVB or UVC for most cell types. In contrast, a dose of 80 J/m(2) of UVC that is lethal for the majority of cell types is necessary to map 6-4PP by the LMPCR technique. This compromises the use of LMPCR to study the repair of 6-4PP. To date, no other techniques have been developed to study 6-4PP repair at nucleotide resolution. We have therefore adapted a recently developed technique for the mapping of 6-4PP: terminal transferase-dependent PCR (TDPCR). TDPCR is in many ways similar to LMPCR. This technique is more sensitive and allows the mapping of 6-4PP at UVC doses as low as 10 J/m(2) in genomic DNA and in living cells.     

STM observations of the first polymerization steps between hexahydroxy-tri-phenylene and benzene-di-boronic acid molecules

To understand the first polymerization steps between benzene-diboronic acid (BDBA) and hexahydroxy-triphenylene (HHTP) molecules, the peculiar self assemblies of HHTP molecules on an Ag(111) surface have been investigated in terms of substrate temperature during evaporation. Interaction of these different molecular structures with BDBA moieties has been researched. The results show that polymer tecton is based on an oligomer composed of one BDBA surrounded by two HHTPs, its shape being independent of the surrounding HHTP network. The geometry and functionality of this tecton determines the shape of the final structures obtained after covalent bonding.     

On the Design of Zinc‐Finger Models with Cyclic Peptides Bearing a Linear Tail

Cyclic peptides with a linear tail (CPLT) have been successfully used to model two zinc fingers (ZFs) adopting the treble‐clef‐ and loosened zinc‐ribbon folds. In this article, we examine the factors that may influence the design of such ZF models: mutations in the sequence, size of the cycle, and size of the tail. For this purpose, several peptides derived from the CPLT‐based models of the treble‐clef‐ and loosened zinc‐ribbon ZF were synthesized and studied. CPLT‐based models appear to be robust toward mutations, accommodate various cycle sizes, and are sensible to the size of the linking region of the tail located between the cycle and the coordinating amino acids. Based on these criteria, we describe the design of a new CPLT‐based model for the zinc‐ribbon ZFs, L_ZR, and compare it to a linear analogue, L_ZR^lin. The model complex Zn ? L_ZR is able to fold correctly around the metal ion contrary to Zn ? L_ZR^lin, suggesting that CPLT‐based models are more likely to yield structurally meaningful models of ZF sites than linear peptide models. Finally, we draw some rules that could allow the design of new CPLT‐based metallopeptides with a controlled fold.     

Enantioenriched Methylene-Bridged Benzazocanes Synthesis by Organocatalytic and Superacid Activations

Achieving in a straightforward way the synthesis of enantioenriched elaborated three-dimensional molecules related to bioactive natural products remains a long-standing quest in organic synthesis. Enantioselective organocatalysis potentially offers a unique opportunity to solve this problem, especially when combined with complementary modes of activation. Here, we report the sequential association of organocatalytic and superacid activations of simple linear achiral readily available precursors to promote the formation of unique highly elaborated chiral methylene-bridged benzazocanes exhibiting three to five fully-controlled stereocenters. This peculiar backbone, difficult to assemble by standard synthetic approaches, is closely related to bioactive natural and synthetic morphinans and benzomorphans. The formation of a highly reactive chiral 7-membered ring N-acyl iminium superelectrophilic ion, evidenced by low-temperature in situ NMR experiments, triggers a challenging stereoselective Friedel–Crafts-type cyclization.     

Numerical solution of Cauchy problems in linear elasticity in axisymmetric situations

An iterative method for solving axisymmetric Cauchy problems in linear elasticity is presented. This kind of problem consists in recovering missing displacements and forces data on one part of a domain boundary from the knowledge of overspecified displacements and forces data on another part of this boundary. Numerical simulations using the finite element method highlight the algorithm’s efficiency, accuracy and robustness to noisy data as well as its ability to deblur noisy data. An application of the inverse technique to the identification of a friction coefficient is also presented.     

Study of a collocated Lagrange‐remap scheme for multi‐material flows adapted to HPC

This paper describes a collocated numerical scheme for multi‐material compressible Euler equations, which attempts to suit to parallel computing constraints. Its main features are conservativity of mass, momentum, total energy and entropy production, and second order in time and space. In the context of a Eulerian Lagrange‐remap scheme on planar geometry and for rectangular meshes, we propose and compare remapping schemes using a finite volume framework. We consider directional splitting or fully multi‐dimensional remaps, and we focus on a definition of the so‐called corner fluxes. We also address the issue of the internal energy behavior when using a conservative total energy remap. It can be perturbed by the duality between kinetic energy obtained through the conservative momentum remap or implicitly through the total energy remap. Therefore, we propose a kinetic energy flux that improves the internal energy remap results in this context. Copyright © 2016 John Wiley & Sons, Ltd.