Efficient electron transfer through a triazole link in ruthenium(II) polypyridine type complexes

Spectroscopic, electrochemical and theoretical characterisations of photoactive systems readily assembled via click-chemistry show an efficient bi-directional charge shift through the triazole link.     

Back Cover: Bio-Inspired Bimetallic Cooperativity Through a Hydrogen Bonding Spacer in CO2 Reduction (Angew. Chem. Int. Ed. 8/2023)

At the core of carbon monoxide dehydrogenase (CODH) active site two metal ions together with hydrogen bonding scheme from amino acids orchestrate the interconversion between CO₂ and CO. We have designed a molecular catalyst implementing a bimetallic iron complex with an embarked second coordination sphere with multi-point hydrogen-bonding interactions. We found that, when immobilized on carbon paper electrode, the dinuclear catalyst enhances up to four fold the heterogeneous CO₂ reduction to CO in water with an improved selectivity and stability compared to the mononuclear analogue. Interestingly, quasi-identical catalytic performances are obtained when one of the two iron centers was replaced by a redox inactive Zn metal, questioning the cooperative action of the two metals. Snapshots of X-ray structures indicate that the two metalloporphyrin units tethered by a urea group is a good compromise between rigidity and flexibility to accommodate CO₂ capture, activation, and reduction.     

Influence of second sphere hydrogen bonding interaction on a manganese(II)-aquo complex

We have developed a pentadentate N(4)O ligand scaffold with a benzimidazole group placed in a rigid fashion to develop hydrogen bonding interaction with the ligand in the sixth position. The mononuclear Mn(II) complex with a water molecule was isolated and characterized. We discuss the role of the outer sphere ligand in stabilising a Mn(II)-aquo complex.     

Liquidus Curves of NaNO3(aq) Calculatedfrom the Modified Adsorption Isotherm Modelfor Aqueous Electrolytes

Summary.  The Stokes-Robinson modification of the Brunauer-Emmett-Teller (BET) adsorption isotherm is used to calculate the liquidus curve of NaNO₃(aq) including the eutectic point and metastable phases. The method described here represents a simplified approach to predict the liquidus curves with sparse information. Received August 9, 1999. Accepted November 4, 1999     

Ligand designed with pending phenol group

The synthesis of a salicylaldehyde derivative facing an encumbered phenol group on a naphthalene block as a molecular shaft is reported. This molecular unit has been designed to elaborate coordinating ligands holding non-coordinating phenol group for the generation of phenoxyl radical in the close proximity of a metal complex.     

Use of mucolytics to enhance magnetic particle retention at a model airway surface

A previous study has shown that retention of magnetic particles at a model airway surface requires prohibitively strong magnetic fields. As mucus viscoelasticity is the most significant factor contributing to clearance of magnetic particles from the airway surface, mucolytics are considered in this study to reduce mucus viscoelasticity and enable particle retention with moderate strength magnetic fields. The excised frog palate model was used to simulate the airway surface. Two mucolytics, N-acetylcysteine (NAC) and dextran sulfate (DS) were tested. NAC was found to enable retention at moderate field values (148 mT with a gradient of 10.2 T/m), whereas DS was found to be effective only for sufficiently large particle concentrations at the airway surface. The possible mechanisms for the observed behavior with different mucolytics are also discussed based on aggregate formation and the loading of cilia.