Chemoselective Polymerization Control: From Mixed‐Monomer Feedstock to Copolymers

A novel chemoselective polymerization control yields predictable (co)polymer compositions from a mixture of monomers. Using a dizinc catalyst and a mixture of caprolactone, cyclohexene oxide, and carbon dioxide enables the selective preparation of either polyesters or polycarbonates or copoly(ester‐carbonates). The selectivity depends on the nature of the zinc–oxygen functionality at the growing polymer chain end, and can be controlled by the addition of exogeneous switch reagents.     

Predicting New Ugi–Smiles Couplings: A Combined Experimental and Theoretical Study

Following our previous mechanistic studies of multicomponent Ugi‐type reactions, theoretical calculations have been performed to predict the efficiency of new substrates in Ugi–Smiles couplings. First, as predicted, 2,4,6‐trichlorophenol experimentally gave the corresponding aryl‐imidate. Theoretical predictions of nitrosophenols as good acidic partners were then successfully confirmed by experiments. In the latter case, the reaction offers a new access to benzimidazoles.     

Influence of chain structure on crystal polymorphism of poly(lactic acid). Part 1: effect of optical purity of the monomer

The influence of chain structure on crystal polymorphism of poly(lactic acid) (PLA) with high l-lactic acid content (97.8–100 %) is detailed in this contribution. Upon usual processing conditions of PLA, only α and α′ crystals grow, which makes these two polymorphs of major interest for research. The two crystal modifications have similar chain packing, which complicates their quantitative analysis by diffraction methods. The two crystal modifications are instead easily identified by analysis of the crystallization kinetics, which varies not only with temperature, but also with crystal polymorphism. The dependence of the rate of ordering on temperature shows two distinct maxima around 105–110 and 120–125 °C, which are related to growth of α′ and α crystals, respectively. Addition of d-lactic acid co-units leads to a decrease of the overall crystallization rate of PLA, as well as of the rate of spherulite growth (G) of both the crystal modifications. The relative crystallization rates of α and α′ forms are highly affected by stereoregularity, especially in the PLA grades that have a high crystallization rate. A high d-lactic acid content results not only in an overall slower crystal growth, but also in a varied temperature range where each of the two crystal modifications prevail, with a shift to lower temperatures of both the maxima of the G vs. temperature plots, indicating that inclusion of d-lactic acid units in the PLA chain affects crystallization rate of both α and α′ crystal modifications.     

The (010) Surface of the Al45Cr7 Complex Intermetallic Compound: Insights from Density Functional Theory

The Al₄₅Cr₇ compound is considered to exhibit an approximant structure of the icosahedral Al₄Cr phase. Its (010) surface has been investigated in detail using density functional calculations. Surface energy calculations show that the stable terminations result from a cleavage of the crystal between adjacent atomic planes, in agreement with the layered structure of the compound. The integrity of the icosahedral atomic arrangements (icosahedral clusters) found in the bulk structure, is predicted to be removed at the surface. This result is in contrast to what has been previously concluded for the (010) surface of the Al₁₃Fe₄ quasicrystal approximant. Our findings are discussed in relation to the bonding network in the compound, calculated using the Crystal Orbital Hamiltonian Population approach, as possible reasons for such contrasted behavior.     

Etude par Spectrométrie Infrarouge et Raman des Phases Cristallines Basses Temperatures de (NH4)3H(SO4)2

The Raman and infrared spectra of (NH₄)₃H(SO₄)₂ crystal were investigated in the range 20–300 K. An assignment of bands due to internal and external vibrations is given. The crystalline phases designated II, III, V and VII were identified and characterized spectroscopically. Hydrogen bonding, the nature and degree of structural (dis)order and the mechanisms of the phase transitions are discussed. The NH₄⁺ ions show an important orientational disorder and become fully ordered in phase VII only. They are involved in all transitions and seem the main cause of the ferroelectricity at low temperature.     

Left inverses of matrices with polynomial decay

It is known that the algebra of Schur operators on ?² (namely operators bounded on both ?¹ and ?^∞) is not inverse-closed. When ?²=?²(X) where X is a metric space, one can consider elements of the Schur algebra with certain decay at infinity. For instance if X has the doubling property, then Q. Sun has proved that the weighted Schur algebra Aω(X) for a strictly polynomial weight ω is inverse-closed. In this paper, we prove a sharp result on left-invertibility of the these operators. Namely, if an operator A∈Aω(X) satisfies ‖Afp_‖?‖fp_‖, for some 1?p?∞, then it admits a left-inverse in Aω(X). The main difficulty here is to obtain the above inequality in ?². The author was both motivated and inspired by a previous work of Aldroubi, Baskarov and Krishtal (2008) [1], where similar results were obtained through different methods for X=Zd, under additional conditions on the decay.     

Two-Photon Absorption and Cell Imaging of Fluorene-Functionalized Epicocconone Analogues

Epicocconone 1 is a natural chromophore isolated from the fungus Epicoccum nigrum that has shown applications in proteomics and fluorescent microscopy thanks to its unique pro-fluorescence properties. The modification of the skeleton of the natural product by replacing the triene side chain by a fluorenyl scaffold can noticeably increase the fluorophore's absorption coefficient. The synthesis of the analogues of the natural product has been made possible by the use of a palladium-catalyzed carbonylation reaction, allowing the construction of the β-keto-dioxinone key intermediate. Two-photon absorption cross-section measurements of the fluorenyl epicocconone analogues show a structure dependency with values ranging from 60 to 280 GM and live cell imaging show intense staining of intracellular vesicle-like structures around the nucleus.     

Ethynylation of Cysteine Residues: From Peptides to Proteins in Vitro and in Living Cells

Current approaches to introduce terminal alkynes for bioorthogonal reactions into biomolecules still present limitations in terms of either reactivity, selectivity, or adduct stability. We present a method for the ethynylation of cysteine residues based on the use of ethynylbenziodoxolone (EBX) reagents. The acetylene group is directly introduced onto the thiol group of cysteine and can be used for copper‐catalyzed alkyne‐azide cycloaddition (CuAAC) without further processing. Labeling proceeded with reaction rates comparable to or higher than the most often used iodoacetamide on peptides or maleimide on the antibody trastuzumab, and high cysteine selectivity was observed. The reagents were also used in living cells for cysteine proteomic profiling and displayed improved coverage of the cysteinome compared to previously reported iodoacetamide or hypervalent iodine reagents. Fine‐tuning of the EBX reagents allows optimization of their reactivity and physical properties.