Abstract Selective chemical modifications of biomolecules are in high demand for the development and implementation of chemical biology strategies. Methods involving radicals have emerged as powerful options yet potentially generate side reactivities when involving harsh reaction conditions. We…
Abstract We report the design and synthesis of ratiometric 19F-ATCUN (Xxx-Zzz-His) peptide probes for the selective and reversible detection of Ni2⁺ and Cu2⁺ by 19F NMR spectroscopy. In contrast to fluorescence-based approaches, 19F NMR enables background-free detection in biological media, due to…
Abstract Cooperative multielectron transfer is central to electron storage strategies and small-molecule activation and involves a thermodynamically favored second electron transfer occurring after the first electron transfer. This is the trademark of molecular systems with inverted redox…
Abstract Selective and strategic modification of redox cofactors offers significant advantages for the design of molecular probes, including high compatibility and affinity. This is particularly relevant in the case of redox cofactors with innate fluorescence properties, such as flavins, and…
Abstract IspH is the last enzyme of the methylerythritol phosphate pathway. It catalyzes the reductive dehydroxylation of (E)-4-hydroxy-3-methyl-but-2-en-1-yl diphosphate into isopentenyl diphosphate (IPP) and dimethylallyl diphosphate (DMAPP), which are precursors for the biosynthesis of…
Summary Calcium salts consisting of Ca2+ weakly coordinated by carborate counterions have been prepared through anhydrous and aqueous methods. The Ca2+ center is sufficiently Lewis acidic to weakly coordinate olefins, alkynes and aromatics, and catalyze the hydrosilylation of 1-hexene and several…
Abstract Purpose of Review Although the biological mechanism of skin sensitization is a quite complex multi-stage process, the sensitization potency (or absence of potency) of a chemical is dependent on its chemical properties. Here we present an overview of the advances that have been made in our…
Abstract Quantum mechanical tunneling (QMT) is the mechanism by which a particle can pass through a high potential energy barrier. Although rooted in quantum physics, QMT influences key chemical reactions in a number of ways. Here, we show that a new iridium dihydride complex IrH2 bearing a N,B-bid…
Abstract Four cis-chelating diphosphanes derived from cyclodextrins (CDs), each featuring a distinct intracavity environment, compel NiII or PdII metal centers to reside within α- or β-CD cavities. Nickel(II) complexes of these metal-confining ligands act as active catalysts in ethylene…
Abstract Dielectric and magnetoelectric (ME) studies were conducted on polycrystalline samples of the molecular spin triangle [Fe3O(O2CPh)6(py)3]ClO4·py (Fe3) and on its diamagnetic isostructural GaIII analogue (Ga3). Dielectric studies revealed a thermally activated process between approximately…
Abstract Promising results in preclinical diagnosis based on 89Zr-immunoPET have fostered the development of efficient chelators for this tetravalent metal. Leads in this area are octadentate ligands obtained by extension of the desferrioxamine B trihydroxamic acid DFO with a fourth bidentate…
Abstract The first soluble and stable Mg2+ dication stabilized only by weakly coordinating and chemically robust carborate anions [HexCB11Cl11]− is described. Mg[HexCB11Cl11]2 (1), prepared by reaction of Mg(nBu)2 with 2 equiv of [Ph3C][HexCB11Cl11], consists, in the solid state, of a central Mg2+…
Abstract Ru complexes are widely studied in photodynamic therapy. The type I mechanism of action is based on a photoinduced electron transfer from the complex to O2 and needs an electron donor to be catalytic. Little is known about electron donors among physiologically relevant compounds. Hence, we…
Abstract Hypersaline environments, including brines and brine inclusions of evaporite crystals, are currently of great interest due to their unique preservation properties for the search for terrestrial and potentially extraterrestrial biosignatures of ancient life. However, much is still unclear…
Abstract Archaeal membranes exhibit remarkable stability under extreme environmental conditions, a feature attributed to their unique lipid composition. While it is widely accepted that tetraether lipids confer structural integrity by forming monolayers, the role of bilayer-forming diether lipids…
Abstract Cu(II) coordination complexes are emerging as promising anticancer agents due to their ability to induce oxidative stress through reactive oxygen species (ROS) generation. In this study, we synthesized and characterized two novel Cu(II) metallopeptide systems, 1/Cu(II) and 2/Cu(II),…
Abstract Oxidatively induced reductive elimination (OIRE) has become a crucial chemical process to enable the effective formation of otherwise much less accessible products. The chemically, electrochemically, or photochemically triggered oxidation of appropriate metal complexes leading to a…
Abstract Electric fields represent an ideal means for controlling spins at the nanoscale and, more specifically, for manipulating protected degrees of freedom in multispin systems. Here we perform low-temperature magnetic far-IR spectroscopy on a molecular spin triangle (Fe3) and provide initial…
Absract Iron-copper complexes have been extensively studied in the search for efficient cytochrome c oxidase models. Whereas most dinuclear materials usually focus on fine-tuning the coordination of heme-Fe, this work shows that the coordination of copper in cytochrome c oxidase models should be…
Abstract The present study details the synthesis and characterization of a robust, monomeric Al–H aluminate supported by a tridentate tris-phenolate ligand, isolated as [2][Li(THF)4] and [2][N(nBu)4] salts, which were then exploited as CO2 hydroboration catalysts. As initial reactivity studies, it…
