Understanding the Reshaping of Fluorinated Polyester Vitrimers by Kinetic and DFT Studies of the Transesterification Reaction

Vitrimers are a third class of polymers gathering the mechanical properties and solvent resistance of 3D thermosets and the reprocessability of thermoplastics. This unique behaviour is due to the triggering of certain covalent exchange reactions that allow the network to rearrange upon application of a stimulus. The constitutive feature of vitrimers is the adoption of a glass-like viscosity during the rearrangement of the network, often due to an associative mechanism for the exchange reaction. Transesterification networks are one of the most studied type of vitrimers that usually require the incorporation of a catalyst, implying the associated drawbacks. Following up on a recent report on catalyst-free transesterification vitrimers in which the ester functions are particularly reactive thanks to the presence of fluorine atoms in α- or β-position, parallel DFT calculations and an experimental kinetic study on model molecules are presented in order to quantitatively assess the effect of neighbouring fluorinated groups on the transesterification reaction rate.     

CPMD Simulation of a Bimolecular Chemical Reaction: Nucleophilic Attack of a Disulfide Bond under Mechanical Stress

Previous single‐molecule atomic force microscopy (AFM) experiments showed a change in the reactivity of a bimolecular substitution reaction with a definite force acting on a protein containing disulfide bonds. Using Car–Parrinello molecular dynamics (CPMD) simulations, we analyse the relevant reaction pathways for the breaking of a disulfide bond in the presence of nucleophiles.     

Microextraction techniques for the determination of volatile and semivolatile organic compounds from plants: A review

Vegetables and fruits are necessary for human health, and traditional Chinese medicine that uses plant materials can cure diseases. Thus, understanding the composition of plant matrix has gained increased attention in recent years. Since plant matrix is very complex, the extraction, separation and quantitation of these chemicals are challenging.     

Tuneable Sagnac comb filter including two wave retarders

In this paper we study theoretically and experimentally a wavelength-tuneable Sagnac birefringence filter. The device is a Sagnac interferometer including a symmetric fibre coupler and a length of high-birefringence fibre in the loop. A wave retarder is inserted at each end of the birefringent fibre for absolute wavelength tuning. We show theoretically that wavelength tuning through wave plate orientation ensuring constant amplitude of the filtering function is possible only if a minimum of two wave retarders are included in the setup. The position of the transmission peaks then varies linearly with the angle of one of the retarders and can be adjusted over one entire channel spacing. This happens only when a quarter-wave retarder and a half-wave retarder are used, if the former is oriented at 45° with respect to the fibre birefringence axes, while the orientation of the latter serves as the adjustment parameter. The theoretical predictions are confirmed by the experimental results.     

Structural Basis for Copper–Oxygen Mediated C−H Bond Activation by the Formylglycine-Generating Enzyme

The formylglycine-generating enzyme (FGE) is a unique copper protein that catalyzes oxygen-dependent C−H activation. We describe 1.66 Å- and 1.28 Å-resolution crystal structures of FGE from Thermomonospora curvata in complex with either Ag^I or Cd^II providing definitive evidence for a high-affinity metal-binding site in this enzyme. The structures reveal a bis-cysteine linear coordination of the monovalent metal, and tetrahedral coordination of the bivalent metal. Similar coordination changes may occur in the active enzyme as a result of Cu^I/II redox cycling. Complexation of copper atoms by two cysteine residues is common among copper-trafficking proteins, but is unprecedented for redox-active copper enzymes or synthetic copper catalysts.