Unprecedented Kinetic Inertness for a Mn2+‐Bispidine Chelate: A Novel Structural Entry for Mn2+‐Based Imaging Agents

The search for more biocompatible alternatives to Gd³⁺‐based MRI agents, and the interest in ⁵²Mn for PET imaging call for ligands that form inert Mn²⁺ chelates. Given the labile nature of Mn²⁺, high inertness is challenging to achieve. The strongly preorganized structure of the 2,4‐pyridyl‐disubstituted bispidol ligand L₁ endows its Mn²⁺ complex with exceptional kinetic inertness. Indeed, MnL₁ did not show any dissociation for 140 days in the presence of 50 equiv. of Zn²⁺ (37 °C, pH 6), while recently reported potential MRI agents MnPyC3A and MnPC2A‐EA have dissociation half‐lives of 0.285 h and 54.4 h under similar conditions. In addition, the relaxivity of MnL₁ (4.28 mm ^?1 s^?1 at 25 °C, 20 MHz) is remarkable for a monohydrated, small Mn²⁺ chelate. In vivo MRI experiments in mice and determination of the tissue Mn content evidence rapid renal clearance of MnL₁. Additionally, L₁ could be radiolabeled with ⁵²Mn and the complex revealed good stability in biological media.     

Application of ultrasound‐assisted liquid–liquid microextraction coupled with gas chromatography and mass spectrometry for the rapid determination of synthetic cannabinoids and metabolites in biological samples

The constant emergence of new psychoactive substances is a challenge to clinical and forensic toxicologists who need to constantly update analytical techniques to detect them. A large portion of these substances are synthetic cannabinoids. The aim of this study was to develop a rapid and simple method for the determination of synthetic cannabinoids and their metabolites in urine and blood using gas chromatography–mass spectrometry. The method involves an ultrasound‐assisted dispersive liquid–liquid microextraction that implies a rapid procedure, giving excellent extraction efficiencies with minimal use of toxic solvents. This is followed by silylation and analysis with gas chromatography–mass spectrometry. The chromatographic method allows for the separation and identification of 29 selected synthetic cannabinoids and some metabolites. The method was validated on urine and blood samples with the ability to detect and quantify all analytes with satisfactory limits of detection (from 1 to 5 ng/mL), limits of quantification (5 ng/mL), and selectivity and linearity (in the range of 5–200 ng/mL). The developed assay is highly applicable to laboratories with limited instrumental availability, due to the use of efficient and low‐cost sample preparation and instrumental equipment. The latter may contribute to enhance the detection of new psychoactive substances in clinical and forensic toxicology laboratories.     

Modulating the Enantiodiscrimination Features of Inherently Chiral Selectors by Molecular Design: A HPLC and Voltammetry Study Case with Atropisomeric 2,2’-Biindole-Based Monomers and Oligomer Films

A family of inherently chiral electroactive selectors based on the 2,2’-biindole atropisomeric scaffold, of easy synthesis and modulable functional properties, is studied in cascade in two enantioselection contexts. They are at first investigated as probes in enantioselective HPLC, studying molecular structure and temperature effects, and achieving very efficient semipreparative enantioseparation. The enantiomers thus obtained, of remarkable chiroptical features (optical rotation as well as circular dichroism), are successfully applied as selectors in chiral voltammetry in different media for discrimination of the enantiomers of chiral electroactive probes, either by conversion into enantiopure electroactive electrode surfaces by electrooligomerization on glassy carbon substrate (the two monomers with shorter alkyl chains), or as chiral additive in achiral ionic liquid (the monomer with longest alkyl chains). Discrimination is conveniently and reproducibly achieved in terms of significant potential differences for the two enantiomers, specularly inverting either probe or selector configuration. In one case successful discrimination is also observed with the two probe enantiomers concurrently present, either as racemate or with enantiomeric excesses, neatly accounted for by the peak current ratios.     

Optical imaging and magnetophoresis of nanorods

Peclet number analysis is performed to probe the convective motion of nanospheres and nanorods under the influence of magnetophoresis and diffusion. Under most circumstances, magnetophoretic behaviour dominates diffusion for nanorods, as the magnetic field lines tend to align the magnetic moment along the rod axis. The synthesis and dispersion of fluorophore-tagged nanorods are described. Fluorescence microscopy is employed to image the nanorod motion in a magnetic field gradient. The preliminary experimental data are consistent with the Peclet number analysis.     

A geometric characterisation of Desarguesian spreads

We construct and describe the basic properties of a family of semifields in characteristic 2. The construction relies on the properties of projective polynomials over finite fields. We start by associating non-associative products to each such polynomial. The resulting presemifields form the degenerate case of our family. They are isotopic to the Knuth semifields which are quadratic over left and right nuclei. The non-degenerate members of our family display a very different behavior. Their left and right nuclei agree with the center, the middle nucleus is quadratic over the center. None of those semifields is isotopic or Knuth equivalent to a commutative semifield. As a by-product we obtain the complete taxonomy of the characteristic 2 semifields which are quadratic over the middle nucleus, bi-quadratic over the left and right nuclei and not isotopic to twisted fields. This includes determining when two such semifields are isotopic and the order of the autotopism group.     

High diffusion barrier and piezoelectric nanocomposites based on polyvinylidene fluoride‐trifluoroethylene copolymer and hydrophobized clay

Nanocomposites based on polyvinylidene fluoride–trifluoroethylene copolymer and up to 4 vol % of hydrophobized clay nanoparticles are investigated. The structure, piezoelectric properties, and oxygen permeability of solvent cast films are analyzed before and after annealing above the Curie temperature of the polymer. Exfoliation of the clay takes place at concentrations up to 1 vol %, beyond which it rapidly drops and is absent at a concentration of 4 vol %. The presence of clay does not change the crystallinity of the polymer, but leads to a threefold decrease of the oxygen permeability at a concentration of 0.5 vol %. Annealing at 130 °C increases the crystallinity, the proportion of β phase up to 94%, and the piezoelectric coefficient by 20–40% at clay fractions below 1 vol %. Annealing also leads to a remarkable 3‐ to 10‐fold decrease of O₂ permeability and to intriguing changes of the activation energy for O₂ transport, which decreases from 56 kJ/mol for the as‐cast polymer to below 10 kJ/mol for the polymer and exfoliated composite. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1828–1836     

Novel synthetic approach to alfaprostol key intermediates via Stille coupling with an alkyne

Novel intermediates based on the Corey skeleton for preparation of the ω-chain of non-halogenated unnatural prostaglandin analogues containing a triple bond at position 13–14 (PG numbering) were synthesized. The utilization of a novel synthetic approach towards a new tin intermediate, and subsequent Stille coupling opens up new possibilities for preparing these important pharmaceutical intermediates.