A HF Loaded Lewis-Acidic Aluminium Chlorofluoride for Hydrofluorination Reactions

The very strong Lewis acid aluminium chlorofluoride (ACF) was loaded with anhydrous HF. The interaction between the surface of the catalyst and HF was investigated using a variety of characterization methods, which revealed the formation of polyfluorides. Moreover, the reactivity of the HF-loaded ACF towards the hydrofluorination of alkynes was studied.     

DMT1 Inhibitors Kill Cancer Stem Cells by Blocking Lysosomal Iron Translocation

Cancer stem cells (CSC) constitute a cell subpopulation in solid tumors that is responsible for resistance to conventional chemotherapy, metastasis and cancer relapse. The natural product Salinomycin can selectively target this cell niche by directly interacting with lysosomal iron, taking advantage of upregulated iron homeostasis in CSC. Here, inhibitors of the divalent metal transporter 1 (DMT1) have been identified that selectively target CSC by blocking lysosomal iron translocation. This leads to lysosomal iron accumulation, production of reactive oxygen species and cell death with features of ferroptosis. DMT1 inhibitors selectively target CSC in primary cancer cells and circulating tumor cells, demonstrating the physiological relevance of this strategy. Taken together, this opens up opportunities to tackle unmet needs in anti-cancer therapy.     

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.     

Star-Shaped Ruthenium Complexes as Prototypes of Molecular Gears

The design and synthesis of two families of molecular-gear prototypes is reported, with the aim of assembling them into trains of gears on a surface and ultimately achieving controlled intermolecular gearing motion. These piano-stool ruthenium complexes incorporate a hydrotris(indazolyl)borate moiety as tripodal rotation axle and a pentaarylcyclopentadienyl ligand as star-shaped cogwheel, equipped with five teeth ranging from pseudo-1D aryl groups to large planar 2D paddles. A divergent synthetic approach was followed, starting from a pentakis(p-bromophenyl)cyclopentadienyl ruthenium(II) complex as key precursor or from its iodinated counterpart, obtained by copper-catalyzed aromatic Br/I exchange. Subsequent fivefold cross-coupling reactions with various partners allowed high structural diversity to be reached and yielded molecular-gear prototypes with aryl-, carbazole-, BODIPY- and porphyrin-derived teeth of increasing size and length.     

Probing the Local Magnetic Structure of the [FeIII(Tp)(CN)3]− Building Block Via Solid-State NMR Spectroscopy,Polarized Neutron Diffraction,and First-Principle Calculations

The local magnetic structure in the [Fe^III(Tp)(CN)₃]⁻ building block was investigated by combining paramagnetic Nuclear Magnetic Resonance (pNMR) spectroscopy and polarized neutron diffraction (PND) with first-principle calculations. The use of the pNMR and PND experimental techniques revealed the extension of spin-density from the metal to the ligands, as well as the different spin mechanisms that take place in the cyanido ligands: Spin-polarization on the carbon atoms and spin-delocalization on the nitrogen atoms. The results of our combined density functional theory (DFT) and multireference calculations were found in good agreement with the PND results and the experimental NMR chemical shifts. Moreover, the ab-initio calculations allowed us to connect the experimental spin-density map characterized by PND and the suggested distribution of the spin-density on the ligands observed by NMR spectroscopy. Interestingly, significant differences were observed between the pseudo-contact contributions of the chemical shifts obtained by theoretical calculations and the values derived from NMR spectroscopy using a simple point-dipole model. These discrepancies underline the limitation of the point-dipole model and the need for more elaborate approaches to break down the experimental pNMR chemical shifts into contact and pseudo-contact contributions.     

Silica-Supported MnII Sites as Efficient Catalysts for Carbonyl Hydroboration,Hydrosilylation, and Transesterification

Manganese, the third most abundant transition-metal element after iron and titanium, has recently been demonstrated to be an effective homogeneous catalyst in numerous reactions. Herein, the preparation of silica-supported Mn^II sites is reported using Surface Organometallic Chemistry (SOMC), combined with tailored thermolytic molecular precursors approach based on Mn₂[OSi(OtBu)₃]₄ and Mn{N(SiMe₃)₂}₂⋅THF. These supported Mn^II sites, free of organic ligands, efficiently catalyze numerous reactions: hydroboration and hydrosilylation of ketones and aldehydes as well as the transesterification of industrially relevant substrates.     

A Facile Method for the Separation of Methionine Sulfoxide Diastereomers,Structural Assignment,and DFT Analysis

Methionine (Met) oxidation is an important biological redox node, with hundreds if not thousands of protein targets. The process yields methionine oxide (MetO). It renders the sulfur chiral, producing two distinct, diastereomerically related products. Despite the biological significance of Met oxidation, a reliable protocol to separate the resultant MetO diastereomers is currently lacking. This hampers our ability to make peptides and proteins that contain stereochemically defined MetO to then study their structural and functional properties. We have developed a facile method that uses supercritical CO₂ chromatography and allows obtaining both diastereomers in purities exceeding 99 %. ¹H NMR spectra were correlated with X-ray structural information. The stereochemical interconversion barrier at sulfur was calculated as 45.2 kcal mol⁻¹, highlighting the remarkable stereochemical stability of MetO sulfur chirality. Our protocol should open the road to synthesis and study of a wide variety of stereochemically defined MetO-containing proteins and peptides.     

Travelling wave mathematical analysis and efficient numerical resolution for a one-dimensional model of solid propellant combustion

We investigate a model of solid propellant combustion involving surface pyrolysis coupled to finite activation energy gas-phase combustion. Existence and uniqueness of a travelling wave solution are established by extending dynamical system tools classically used for premixed flames, dealing with the additional difficulty arising from the surface regression and pyrolysis. An efficient shooting method allows to solve the problem in phase space without resorting to space discretisation nor fixed-point Newton iterations. The results are compared to solutions from a CFD code developed at ONERA, assessing the efficiency and potential of the method, and the impact of the modelling assumptions is evaluated through parametric studies.     

Thermo‐ and pH‐sensitive triblock copolymers with tunable hydrophilic/hydrophobic properties

Polymers consisting of poly(acrylic acid) (PAA) and statistical poly[(acrylic acid)‐co‐(tert‐butylacrylate)] (P(AA‐co‐tBA)), attached to both extremities of Jeffamine® (D series based on a poly(propylene oxide) (PPO) with one amine function at each end) using atom transfer radical polymerization (ATRP) are presented in this article. An original bifunctional amide‐based macroinitiator was first elaborated from Jeffamine®. tBA polymerization was subsequently initiated from this macroinitiator. This polymerization occurs in a well‐controlled manner leading to narrow molecular weights distribution. Amphiphilic copolymers were finally obtained after complete or partial hydrolysis of the PtBA blocks into PAA. The control of the partial hydrolysis of tBA units, conducted in a concentrated HCl/tetrahydrofuran mixture, is demonstrated. The properties of the triblock copolymers were preliminary investigated in aqueous solution by absorbance, DLS measurements and SEC/MALS/DV/DRI analysis as a function of temperature and pH modifications, providing evidences of thermo‐ and pH‐sensitive self‐assembly of the copolymers. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2606–2616