An Ambiphilic Phosphide with Three Different Coordination Modes to Group 7-10 Metals.

Phosphide anions PX with electron-withdrawing substituents display ambiphilic properties. The use of P(V) thiophosphorane substituents enables the coordination of the resulting bis(thiophosphoranyl)phosphide anion ( = ) to a variety of transition metals from groups 7 to 10. A series of homoleptic and heteroleptic complexes was synthesized and X-ray diffraction analysis revealed that, depending on the metal, may adopt three coordination modes (κ-(S, P, S); κ-(S, S); κ-(S, P)) supporting three distinct geometries (octahedral; tetrahedral; square planar).

Fluorogenic detection of cyanide ions in pure aqueous media through an intramolecular crossed-benzoin reaction: limitations unveiled and possible solutions.

Reaction-based fluorogenic sensing of lethal cyanide anions in aqueous matrices remains a big challenge. We have revisited the reported approach about an intramolecular crossed-benzoin reaction leading to the release of a phenol-based fluorophore. Fluorescence assays and RP-HPLC-MS analyses have helped us to highlight its limitations related to poor aqueous stability of probes and impossibility to achieve molecular amplification despite the assumed catalytic activation mechanism.

Molecular and Cellular Characterization of the Glutathione Transferases Involved in the Olfactory Metabolism of the Mammary Pheromone.

Odorant metabolizing enzymes, considered as critical olfactory perireceptor actors, control the odor molecules reaching the olfactory epithelium by biotransforming them. As an odorant, the mammary pheromone, i.e.

Combining Desferriferrioxamine B and 1-Hydroxy-2-Piperidone ((PIPO)H) to Chelate Zirconium. Solution Structure of a Model Complex of the [Zr]Zr-DFOcyclo*-mAb Radioimmunoconjugate.

Zr-immunoPET is a hot topic as Zr cumulates the advantages of Cu and I without their drawbacks. We report the synthesis of a model ligand of a chiral bioconjugable tetrahydroxamic chelator combining the desferriferrioxamine B siderophore and 1-hydroxy-2-piperidone ((PIPO)H), a chiral cyclic hydroxamic acid derivative, and the study by NMR spectroscopy of its zirconium complex. Nuclear Overhauser effect measurements (ROESY) indicated that the complex exists in the form of two diastereomers, in 77 : 23 ratio, resulting from the combination of the central chiralities at the 3-C of the (PIPO)H component and at the Zr cation.

Coordinatively Unsaturated Amidotitanocene Cations with Inverted σ and π Bond Strengths: Controlled Release of Aminyl Radicals and Hydrogenation/Dehydrogenation Catalysis.

Cationic amidotitanocene complexes [Cp Ti(NPhAr)][B(C F ) ] (Cp=η -C H ; Ar=phenyl (1 a), p-tolyl (1 b), p-anisyl (1 c)) were isolated. The bonding situation was studied by DFT (Density Functional Theory) using EDA-NOCV (Energy Decomposition Analysis with Natural Orbitals for Chemical Valence). The polar Ti-N bond in 1 a-c features an unusual inversion of σ and π bond strengths responsible for the balance between stability and reactivity in these coordinatively unsaturated species.

Fluorogenic Enzyme-Triggered Domino Reactions Producing Quinoxalin-2(1)-one-based Heterocycles.

A simple and effective biocompatible domino reaction triggered by a model protease and leading to the formation of strongly fluorescent quinoxalin-2(1)-one -heterocycles is described. Some positive attributes including versatility and the ability to provide outstanding fluorescence "OFF-ON" responses were revealed by this work. They open the way for practical applications of this novel type of "covalent-assembly"-based fluorescent probe in the fields of sensing and bioimaging.

The Taming of Redox-Labile Phosphidotitanocene Cations.

Tame d phosphidotitanocene cations stabilized with a pendant tertiary phosphane arm are reported. These compounds were obtained by one-electron oxidation of d precursors with [Cp Fe][BPh ]. The electronic structure of these compounds was studied experimentally (EPR, UV/Vis, and NMR spectroscopy, X-ray diffraction analysis) and through DFT calculations.