CaII‐Catalyzed Alkenylation of Alcohols with Vinylboronic Acids

Direct alkenylation of a variety of alcohols with vinylboronic acids has been accomplished using the air‐stable calcium(II) complex Ca(NTf₂)₂ under mild conditions with short reaction times. For reluctant transformations, an ammonium salt was used as an additive to circumvent the reactivity issue.     

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     

Bi(OTf)3-catalyzed cycloisomerization of aryl-allenes

Intramolecular hydroarylation of allenes was achieved under very mild conditions using bismuth(III) triflate as the catalyst. Efficient functionalization of activated and nonactivated aromatic nuclei led to C-C bond formation through a formal Ar-H activation. A tandem bis-hydroarylation of the allene moiety was also developed giving access to various interesting polycyclic structures.     

N-donor ligands based on bipyridine and ionic liquids: an efficient partnership to stabilize rhodium colloids. Focus on oxygen-containing compounds hydrogenation

Polynitrogen ligands and/in ionic liquids (ILs) are described as a pertinent tandem to efficiently stabilize rhodium nanoparticles (NPs) in the size range of 2.0 nm for catalytic applications. Several N-donor ligands based on bipyridine skeleton were used as extra protective agents in [BMI][PF(6)] and compared in the hydrogenation of functionalized aromatic compounds at 80 °C and under 40 bar H(2). The nature of the bipyridine derivative and its influence on the coordination mode on the particle surface were proposed to explain the observed different kinetic properties. The hydrogenation of various oxygen-containing arenes was investigated and original results were described in the reduction of anisole and cresols as model lignin compounds, providing a significant ratio of ketone derivatives. A first explanation based on possible reaction routes is proposed to justify the formed products.     

Targeted energy transfer with parallel nonlinear energy sinks. Part I: Design theory and numerical results

In this paper, we study a Targeted Energy Transfer (TET) problem between a p degrees-of-freedom (dof) linear master structure and several coupled parallel slave Nonlinear Energy Sink (NES) systems. In detail, each lth dof l=1,2,…,p contains n _l parallel NES; so the linear structure has (n ₁+n ₂+⋅⋅⋅+n _l +⋅⋅⋅+n _p ) NES. We are interested to study analytically the TET phenomenon during the first mode of the compound system. To this end, complexification, averaging, and multiple scales methods are used.     

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.